EP2366011A1 - Improvements relating to fabric treatment compositions - Google Patents
Improvements relating to fabric treatment compositionsInfo
- Publication number
- EP2366011A1 EP2366011A1 EP09756758A EP09756758A EP2366011A1 EP 2366011 A1 EP2366011 A1 EP 2366011A1 EP 09756758 A EP09756758 A EP 09756758A EP 09756758 A EP09756758 A EP 09756758A EP 2366011 A1 EP2366011 A1 EP 2366011A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- powder
- composition according
- cationic
- composition
- fabric
- 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
- 239000000203 mixture Substances 0.000 title claims abstract description 78
- 239000004744 fabric Substances 0.000 title claims abstract description 44
- 239000000843 powder Substances 0.000 claims abstract description 108
- 239000002245 particle Substances 0.000 claims abstract description 34
- 230000008021 deposition Effects 0.000 claims abstract description 32
- 125000002091 cationic group Chemical group 0.000 claims abstract description 29
- 239000004902 Softening Agent Substances 0.000 claims abstract description 12
- 230000003750 conditioning effect Effects 0.000 claims abstract description 10
- 229920000642 polymer Polymers 0.000 claims description 17
- 241000283690 Bos taurus Species 0.000 claims description 13
- 238000000034 method Methods 0.000 claims description 13
- 239000003795 chemical substances by application Substances 0.000 claims description 12
- 235000013312 flour Nutrition 0.000 claims description 10
- 150000003856 quaternary ammonium compounds Chemical group 0.000 claims description 10
- 239000010903 husk Substances 0.000 claims description 9
- 229920003171 Poly (ethylene oxide) Polymers 0.000 claims description 8
- 230000008901 benefit Effects 0.000 claims description 8
- 239000001913 cellulose Substances 0.000 claims description 8
- 229920002678 cellulose Polymers 0.000 claims description 8
- 150000002148 esters Chemical class 0.000 claims description 8
- 229920002472 Starch Polymers 0.000 claims description 7
- 150000005690 diesters Chemical class 0.000 claims description 7
- -1 polyethylene terephthalate-polyoxyethylene terephthalate Polymers 0.000 claims description 7
- 230000008569 process Effects 0.000 claims description 7
- 235000019698 starch Nutrition 0.000 claims description 7
- 240000002943 Elettaria cardamomum Species 0.000 claims description 6
- 240000007594 Oryza sativa Species 0.000 claims description 6
- 235000007164 Oryza sativa Nutrition 0.000 claims description 6
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 claims description 6
- 244000273928 Zingiber officinale Species 0.000 claims description 6
- 235000006886 Zingiber officinale Nutrition 0.000 claims description 6
- 235000005300 cardamomo Nutrition 0.000 claims description 6
- 235000008397 ginger Nutrition 0.000 claims description 6
- 239000002304 perfume Substances 0.000 claims description 6
- 235000009566 rice Nutrition 0.000 claims description 6
- 235000005979 Citrus limon Nutrition 0.000 claims description 5
- 244000131522 Citrus pyriformis Species 0.000 claims description 5
- 244000007835 Cyamopsis tetragonoloba Species 0.000 claims description 5
- 235000006679 Mentha X verticillata Nutrition 0.000 claims description 5
- 235000002899 Mentha suaveolens Nutrition 0.000 claims description 5
- 235000001636 Mentha x rotundifolia Nutrition 0.000 claims description 5
- 229920002873 Polyethylenimine Polymers 0.000 claims description 5
- 229920002401 polyacrylamide Polymers 0.000 claims description 5
- 229920001592 potato starch Polymers 0.000 claims description 5
- 241001672694 Citrus reticulata Species 0.000 claims description 4
- 244000165082 Lavanda vera Species 0.000 claims description 4
- 235000010663 Lavandula angustifolia Nutrition 0.000 claims description 4
- 235000010654 Melissa officinalis Nutrition 0.000 claims description 4
- 244000062730 Melissa officinalis Species 0.000 claims description 4
- 235000010627 Phaseolus vulgaris Nutrition 0.000 claims description 4
- 244000046052 Phaseolus vulgaris Species 0.000 claims description 4
- 239000001102 lavandula vera Substances 0.000 claims description 4
- 235000018219 lavender Nutrition 0.000 claims description 4
- 229920005615 natural polymer Polymers 0.000 claims description 4
- 239000008107 starch Substances 0.000 claims description 4
- 229920001059 synthetic polymer Polymers 0.000 claims description 4
- 150000005691 triesters Chemical class 0.000 claims description 4
- 235000009024 Ceanothus sanguineus Nutrition 0.000 claims description 3
- 244000223760 Cinnamomum zeylanicum Species 0.000 claims description 3
- 235000008733 Citrus aurantifolia Nutrition 0.000 claims description 3
- 235000002787 Coriandrum sativum Nutrition 0.000 claims description 3
- 244000018436 Coriandrum sativum Species 0.000 claims description 3
- 235000003392 Curcuma domestica Nutrition 0.000 claims description 3
- 244000008991 Curcuma longa Species 0.000 claims description 3
- 235000006200 Glycyrrhiza glabra Nutrition 0.000 claims description 3
- 244000303040 Glycyrrhiza glabra Species 0.000 claims description 3
- 235000013628 Lantana involucrata Nutrition 0.000 claims description 3
- 240000005183 Lantana involucrata Species 0.000 claims description 3
- 240000003553 Leptospermum scoparium Species 0.000 claims description 3
- 235000015459 Lycium barbarum Nutrition 0.000 claims description 3
- 235000006677 Monarda citriodora ssp. austromontana Nutrition 0.000 claims description 3
- 244000223014 Syzygium aromaticum Species 0.000 claims description 3
- 235000016639 Syzygium aromaticum Nutrition 0.000 claims description 3
- 244000269722 Thea sinensis Species 0.000 claims description 3
- 235000011941 Tilia x europaea Nutrition 0.000 claims description 3
- 235000021307 Triticum Nutrition 0.000 claims description 3
- 244000098338 Triticum aestivum Species 0.000 claims description 3
- 235000017803 cinnamon Nutrition 0.000 claims description 3
- 235000003373 curcuma longa Nutrition 0.000 claims description 3
- LPLVUJXQOOQHMX-QWBHMCJMSA-N glycyrrhizinic acid Chemical compound O([C@@H]1[C@@H](O)[C@H](O)[C@H](O[C@@H]1O[C@@H]1C([C@H]2[C@]([C@@H]3[C@@]([C@@]4(CC[C@@]5(C)CC[C@@](C)(C[C@H]5C4=CC3=O)C(O)=O)C)(C)CC2)(C)CC1)(C)C)C(O)=O)[C@@H]1O[C@H](C(O)=O)[C@@H](O)[C@H](O)[C@H]1O LPLVUJXQOOQHMX-QWBHMCJMSA-N 0.000 claims description 3
- 239000004571 lime Substances 0.000 claims description 3
- 235000011477 liquorice Nutrition 0.000 claims description 3
- 229920000058 polyacrylate Polymers 0.000 claims description 3
- 238000010298 pulverizing process Methods 0.000 claims description 3
- 235000013976 turmeric Nutrition 0.000 claims description 3
- 235000013668 Aloysia triphylla Nutrition 0.000 claims description 2
- 240000008554 Aloysia triphylla Species 0.000 claims description 2
- 240000000662 Anethum graveolens Species 0.000 claims description 2
- 235000003092 Artemisia dracunculus Nutrition 0.000 claims description 2
- 240000001851 Artemisia dracunculus Species 0.000 claims description 2
- 241001164374 Calyx Species 0.000 claims description 2
- 235000002568 Capsicum frutescens Nutrition 0.000 claims description 2
- 235000005747 Carum carvi Nutrition 0.000 claims description 2
- 240000000467 Carum carvi Species 0.000 claims description 2
- 235000013912 Ceratonia siliqua Nutrition 0.000 claims description 2
- 240000008886 Ceratonia siliqua Species 0.000 claims description 2
- 240000000560 Citrus x paradisi Species 0.000 claims description 2
- 235000007129 Cuminum cyminum Nutrition 0.000 claims description 2
- 244000304337 Cuminum cyminum Species 0.000 claims description 2
- 240000004784 Cymbopogon citratus Species 0.000 claims description 2
- 235000017897 Cymbopogon citratus Nutrition 0.000 claims description 2
- 235000009419 Fagopyrum esculentum Nutrition 0.000 claims description 2
- 240000008620 Fagopyrum esculentum Species 0.000 claims description 2
- 240000006927 Foeniculum vulgare Species 0.000 claims description 2
- 235000004204 Foeniculum vulgare Nutrition 0.000 claims description 2
- 240000003293 Magnolia grandiflora Species 0.000 claims description 2
- 235000008512 Magnolia grandiflora Nutrition 0.000 claims description 2
- 244000179970 Monarda didyma Species 0.000 claims description 2
- 235000010672 Monarda didyma Nutrition 0.000 claims description 2
- 240000005125 Myrtus communis Species 0.000 claims description 2
- 235000013418 Myrtus communis Nutrition 0.000 claims description 2
- 235000010676 Ocimum basilicum Nutrition 0.000 claims description 2
- 240000007926 Ocimum gratissimum Species 0.000 claims description 2
- 235000011203 Origanum Nutrition 0.000 claims description 2
- 240000000783 Origanum majorana Species 0.000 claims description 2
- 240000004371 Panax ginseng Species 0.000 claims description 2
- 235000005035 Panax pseudoginseng ssp. pseudoginseng Nutrition 0.000 claims description 2
- 235000003140 Panax quinquefolius Nutrition 0.000 claims description 2
- 244000178231 Rosmarinus officinalis Species 0.000 claims description 2
- 241000533293 Sesbania emerus Species 0.000 claims description 2
- 244000299461 Theobroma cacao Species 0.000 claims description 2
- 235000009470 Theobroma cacao Nutrition 0.000 claims description 2
- 235000007303 Thymus vulgaris Nutrition 0.000 claims description 2
- 240000002657 Thymus vulgaris Species 0.000 claims description 2
- 235000015724 Trifolium pratense Nutrition 0.000 claims description 2
- 235000009499 Vanilla fragrans Nutrition 0.000 claims description 2
- 244000263375 Vanilla tahitensis Species 0.000 claims description 2
- 235000012036 Vanilla tahitensis Nutrition 0.000 claims description 2
- KZNIFHPLKGYRTM-UHFFFAOYSA-N apigenin Chemical compound C1=CC(O)=CC=C1C1=CC(=O)C2=C(O)C=C(O)C=C2O1 KZNIFHPLKGYRTM-UHFFFAOYSA-N 0.000 claims description 2
- WHGYBXFWUBPSRW-FOUAGVGXSA-N beta-cyclodextrin Chemical compound OC[C@H]([C@H]([C@@H]([C@H]1O)O)O[C@H]2O[C@@H]([C@@H](O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O3)[C@H](O)[C@H]2O)CO)O[C@@H]1O[C@H]1[C@H](O)[C@@H](O)[C@@H]3O[C@@H]1CO WHGYBXFWUBPSRW-FOUAGVGXSA-N 0.000 claims description 2
- 235000013399 edible fruits Nutrition 0.000 claims description 2
- 235000008434 ginseng Nutrition 0.000 claims description 2
- 235000008216 herbs Nutrition 0.000 claims description 2
- 239000000865 liniment Substances 0.000 claims description 2
- 239000001417 melissa officinalis l. Substances 0.000 claims description 2
- 235000013526 red clover Nutrition 0.000 claims description 2
- 235000002020 sage Nutrition 0.000 claims description 2
- ANRHNWWPFJCPAZ-UHFFFAOYSA-M thionine Chemical compound [Cl-].C1=CC(N)=CC2=[S+]C3=CC(N)=CC=C3N=C21 ANRHNWWPFJCPAZ-UHFFFAOYSA-M 0.000 claims description 2
- 239000001585 thymus vulgaris Substances 0.000 claims description 2
- 239000000463 material Substances 0.000 description 18
- 229920000728 polyester Polymers 0.000 description 18
- 125000000217 alkyl group Chemical group 0.000 description 14
- 150000001875 compounds Chemical class 0.000 description 11
- 239000000758 substrate Substances 0.000 description 10
- 241000196324 Embryophyta Species 0.000 description 9
- 229930006000 Sucrose Natural products 0.000 description 8
- 230000005540 biological transmission Effects 0.000 description 8
- 239000005720 sucrose Substances 0.000 description 8
- 235000014113 dietary fatty acids Nutrition 0.000 description 7
- 239000000194 fatty acid Substances 0.000 description 7
- 229930195729 fatty acid Natural products 0.000 description 7
- 150000004665 fatty acids Chemical class 0.000 description 7
- 239000003381 stabilizer Substances 0.000 description 7
- CZMRCDWAGMRECN-UGDNZRGBSA-N Sucrose Chemical compound O[C@H]1[C@H](O)[C@@H](CO)O[C@@]1(CO)O[C@@H]1[C@H](O)[C@@H](O)[C@H](O)[C@@H](CO)O1 CZMRCDWAGMRECN-UGDNZRGBSA-N 0.000 description 6
- HNISBEDGGYMSJH-UHFFFAOYSA-N 2-[bis(2-hydroxyethyl)amino]ethanol;methyl hydrogen sulfate Chemical compound COS(O)(=O)=O.OCCN(CCO)CCO HNISBEDGGYMSJH-UHFFFAOYSA-N 0.000 description 5
- 125000003342 alkenyl group Chemical group 0.000 description 5
- 125000003118 aryl group Chemical group 0.000 description 5
- 239000003093 cationic surfactant Substances 0.000 description 5
- 238000001914 filtration Methods 0.000 description 5
- 238000003801 milling Methods 0.000 description 5
- 239000003760 tallow Substances 0.000 description 5
- 125000006656 (C2-C4) alkenyl group Chemical group 0.000 description 4
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 4
- 239000003205 fragrance Substances 0.000 description 4
- 125000002768 hydroxyalkyl group Chemical group 0.000 description 4
- 229910052740 iodine Inorganic materials 0.000 description 4
- 239000011630 iodine Substances 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 235000010420 locust bean gum Nutrition 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 125000001453 quaternary ammonium group Chemical group 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- 238000005406 washing Methods 0.000 description 4
- 239000002671 adjuvant Substances 0.000 description 3
- 239000002752 cationic softener Substances 0.000 description 3
- 239000004927 clay Substances 0.000 description 3
- 239000003995 emulsifying agent Substances 0.000 description 3
- 238000005194 fractionation Methods 0.000 description 3
- 125000001183 hydrocarbyl group Chemical group 0.000 description 3
- 239000012535 impurity Substances 0.000 description 3
- 229920005610 lignin Polymers 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- UMSVPCYSAUKCAZ-UHFFFAOYSA-N propane;hydrochloride Chemical compound Cl.CCC UMSVPCYSAUKCAZ-UHFFFAOYSA-N 0.000 description 3
- 238000000926 separation method Methods 0.000 description 3
- 239000000344 soap Substances 0.000 description 3
- 239000007921 spray Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 2
- 229920000742 Cotton Polymers 0.000 description 2
- 229920000161 Locust bean gum Polymers 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 239000004480 active ingredient Substances 0.000 description 2
- 125000002947 alkylene group Chemical group 0.000 description 2
- 230000000844 anti-bacterial effect Effects 0.000 description 2
- DMSMPAJRVJJAGA-UHFFFAOYSA-N benzo[d]isothiazol-3-one Chemical compound C1=CC=C2C(=O)NSC2=C1 DMSMPAJRVJJAGA-UHFFFAOYSA-N 0.000 description 2
- 125000004432 carbon atom Chemical group C* 0.000 description 2
- 150000001768 cations Chemical class 0.000 description 2
- 239000000084 colloidal system Substances 0.000 description 2
- 239000003599 detergent Substances 0.000 description 2
- POULHZVOKOAJMA-UHFFFAOYSA-N dodecanoic acid Chemical compound CCCCCCCCCCCC(O)=O POULHZVOKOAJMA-UHFFFAOYSA-N 0.000 description 2
- 239000000839 emulsion Substances 0.000 description 2
- 125000004185 ester group Chemical group 0.000 description 2
- 235000019387 fatty acid methyl ester Nutrition 0.000 description 2
- 238000009472 formulation Methods 0.000 description 2
- 235000021588 free fatty acids Nutrition 0.000 description 2
- 235000015143 herbs and spices Nutrition 0.000 description 2
- 239000004615 ingredient Substances 0.000 description 2
- 238000004900 laundering Methods 0.000 description 2
- 239000000711 locust bean gum Substances 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- 239000004669 nonionic softener Substances 0.000 description 2
- 239000003921 oil Substances 0.000 description 2
- 235000019198 oils Nutrition 0.000 description 2
- 239000000049 pigment Substances 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 238000006467 substitution reaction Methods 0.000 description 2
- 125000000185 sucrose group Chemical group 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 239000000341 volatile oil Substances 0.000 description 2
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 description 1
- OVSKIKFHRZPJSS-UHFFFAOYSA-N 2,4-D Chemical compound OC(=O)COC1=CC=C(Cl)C=C1Cl OVSKIKFHRZPJSS-UHFFFAOYSA-N 0.000 description 1
- PUAQLLVFLMYYJJ-UHFFFAOYSA-N 2-aminopropiophenone Chemical compound CC(N)C(=O)C1=CC=CC=C1 PUAQLLVFLMYYJJ-UHFFFAOYSA-N 0.000 description 1
- 229940100555 2-methyl-4-isothiazolin-3-one Drugs 0.000 description 1
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 description 1
- QYYMDNHUJFIDDQ-UHFFFAOYSA-N 5-chloro-2-methyl-1,2-thiazol-3-one;2-methyl-1,2-thiazol-3-one Chemical compound CN1SC=CC1=O.CN1SC(Cl)=CC1=O QYYMDNHUJFIDDQ-UHFFFAOYSA-N 0.000 description 1
- 229940100484 5-chloro-2-methyl-4-isothiazolin-3-one Drugs 0.000 description 1
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 description 1
- 241000195940 Bryophyta Species 0.000 description 1
- GAWIXWVDTYZWAW-UHFFFAOYSA-N C[CH]O Chemical group C[CH]O GAWIXWVDTYZWAW-UHFFFAOYSA-N 0.000 description 1
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 1
- 240000003538 Chamaemelum nobile Species 0.000 description 1
- 235000007866 Chamaemelum nobile Nutrition 0.000 description 1
- 235000013162 Cocos nucifera Nutrition 0.000 description 1
- 244000060011 Cocos nucifera Species 0.000 description 1
- GUBGYTABKSRVRQ-CUHNMECISA-N D-Cellobiose Chemical compound O[C@@H]1[C@@H](O)[C@H](O)[C@@H](CO)O[C@H]1O[C@@H]1[C@@H](CO)OC(O)[C@H](O)[C@H]1O GUBGYTABKSRVRQ-CUHNMECISA-N 0.000 description 1
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 1
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 description 1
- 235000010469 Glycine max Nutrition 0.000 description 1
- 244000068988 Glycine max Species 0.000 description 1
- 239000004705 High-molecular-weight polyethylene Substances 0.000 description 1
- 229920000663 Hydroxyethyl cellulose Polymers 0.000 description 1
- 239000004354 Hydroxyethyl cellulose Substances 0.000 description 1
- 239000004166 Lanolin Substances 0.000 description 1
- 239000005639 Lauric acid Substances 0.000 description 1
- 235000007232 Matricaria chamomilla Nutrition 0.000 description 1
- 101100412856 Mus musculus Rhod gene Proteins 0.000 description 1
- 238000005481 NMR spectroscopy Methods 0.000 description 1
- 239000005642 Oleic acid Substances 0.000 description 1
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 description 1
- 241000282372 Panthera onca Species 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- 239000006096 absorbing agent Substances 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 125000000129 anionic group Chemical group 0.000 description 1
- 239000003945 anionic surfactant Substances 0.000 description 1
- 230000003712 anti-aging effect Effects 0.000 description 1
- 230000003110 anti-inflammatory effect Effects 0.000 description 1
- 230000000845 anti-microbial effect Effects 0.000 description 1
- 239000004599 antimicrobial Substances 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 235000006708 antioxidants Nutrition 0.000 description 1
- 239000012736 aqueous medium Substances 0.000 description 1
- 239000008346 aqueous phase Substances 0.000 description 1
- 239000003899 bactericide agent Substances 0.000 description 1
- 239000003139 biocide Substances 0.000 description 1
- 230000001680 brushing effect Effects 0.000 description 1
- 238000011088 calibration curve Methods 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 229960004424 carbon dioxide Drugs 0.000 description 1
- 235000011089 carbon dioxide Nutrition 0.000 description 1
- 239000004359 castor oil Substances 0.000 description 1
- 235000019438 castor oil Nutrition 0.000 description 1
- 229920006317 cationic polymer Polymers 0.000 description 1
- 229920003086 cellulose ether Polymers 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- DHNRXBZYEKSXIM-UHFFFAOYSA-N chloromethylisothiazolinone Chemical compound CN1SC(Cl)=CC1=O DHNRXBZYEKSXIM-UHFFFAOYSA-N 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 239000002537 cosmetic Substances 0.000 description 1
- 230000001877 deodorizing effect Effects 0.000 description 1
- IQDGSYLLQPDQDV-UHFFFAOYSA-N dimethylazanium;chloride Chemical compound Cl.CNC IQDGSYLLQPDQDV-UHFFFAOYSA-N 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- NOPFSRXAKWQILS-UHFFFAOYSA-N docosan-1-ol Chemical compound CCCCCCCCCCCCCCCCCCCCCCO NOPFSRXAKWQILS-UHFFFAOYSA-N 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000032050 esterification Effects 0.000 description 1
- 238000005886 esterification reaction Methods 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000002979 fabric softener Substances 0.000 description 1
- 150000002190 fatty acyls Chemical group 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 239000006260 foam Substances 0.000 description 1
- 238000005187 foaming Methods 0.000 description 1
- 239000004088 foaming agent Substances 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- 238000013467 fragmentation Methods 0.000 description 1
- 238000006062 fragmentation reaction Methods 0.000 description 1
- 239000000499 gel Substances 0.000 description 1
- 239000003349 gelling agent Substances 0.000 description 1
- 239000008103 glucose Substances 0.000 description 1
- 150000004676 glycans Chemical class 0.000 description 1
- ZEMPKEQAKRGZGQ-XOQCFJPHSA-N glycerol triricinoleate Natural products CCCCCC[C@@H](O)CC=CCCCCCCCC(=O)OC[C@@H](COC(=O)CCCCCCCC=CC[C@@H](O)CCCCCC)OC(=O)CCCCCCCC=CC[C@H](O)CCCCCC ZEMPKEQAKRGZGQ-XOQCFJPHSA-N 0.000 description 1
- 235000009569 green tea Nutrition 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 235000019447 hydroxyethyl cellulose Nutrition 0.000 description 1
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 description 1
- 235000019388 lanolin Nutrition 0.000 description 1
- 229940039717 lanolin Drugs 0.000 description 1
- 239000000787 lecithin Substances 0.000 description 1
- 235000010445 lecithin Nutrition 0.000 description 1
- 239000012263 liquid product Substances 0.000 description 1
- 230000005923 long-lasting effect Effects 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- JZMJDSHXVKJFKW-UHFFFAOYSA-M methyl sulfate(1-) Chemical compound COS([O-])(=O)=O JZMJDSHXVKJFKW-UHFFFAOYSA-M 0.000 description 1
- BEGLCMHJXHIJLR-UHFFFAOYSA-N methylisothiazolinone Chemical compound CN1SC=CC1=O BEGLCMHJXHIJLR-UHFFFAOYSA-N 0.000 description 1
- 235000011929 mousse Nutrition 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 239000002736 nonionic surfactant Substances 0.000 description 1
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- 239000003346 palm kernel oil Substances 0.000 description 1
- 235000019865 palm kernel oil Nutrition 0.000 description 1
- 229940055076 parasympathomimetics choline ester Drugs 0.000 description 1
- 239000006072 paste Substances 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 150000003904 phospholipids Chemical class 0.000 description 1
- 230000019612 pigmentation Effects 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 229920001184 polypeptide Polymers 0.000 description 1
- 229920001282 polysaccharide Polymers 0.000 description 1
- 239000005017 polysaccharide Substances 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 229940068984 polyvinyl alcohol Drugs 0.000 description 1
- 235000019422 polyvinyl alcohol Nutrition 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 239000012254 powdered material Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 239000003755 preservative agent Substances 0.000 description 1
- 239000011164 primary particle Substances 0.000 description 1
- 102000004196 processed proteins & peptides Human genes 0.000 description 1
- 108090000765 processed proteins & peptides Proteins 0.000 description 1
- 108090000623 proteins and genes Proteins 0.000 description 1
- 102000004169 proteins and genes Human genes 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000012216 screening Methods 0.000 description 1
- 238000007873 sieving Methods 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 239000003549 soybean oil Substances 0.000 description 1
- 235000012424 soybean oil Nutrition 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 229910021653 sulphate ion Inorganic materials 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 235000013616 tea Nutrition 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- 239000011882 ultra-fine particle Substances 0.000 description 1
- 150000004670 unsaturated fatty acids Chemical class 0.000 description 1
- 235000021122 unsaturated fatty acids Nutrition 0.000 description 1
- 239000000052 vinegar Substances 0.000 description 1
- 235000021419 vinegar Nutrition 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
- 239000004562 water dispersible granule Substances 0.000 description 1
- 230000036642 wellbeing Effects 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
- C11D3/38—Products with no well-defined composition, e.g. natural products
- C11D3/382—Vegetable products, e.g. soya meal, wood flour, sawdust
Definitions
- the present invention relates to fabric conditioning compositions comprising micro powders of botanical origin.
- US2003/0087788 discloses water dispersible granules comprising a hydrophobic fragrance in the form of droplets, which is finely divided in and encapsulated by a water-soluble/dispersible solid organic matrix, which may be polypeptides of plant or synthetic origin, such as soya or wheat.
- EP0908171 (Gem Energy Industry Ltd) discloses a dry powder herbal cleaning composition containing (a) a herb which acts as a soap or detergent; (b) a herb which acts as a foaming accelerating agent; (c) a herb which acts as a foaming agent; (d) a herb which acts as a pigmentation or colour restoring or maintenance agent; and (e) a herb which acts as a conditioner.
- WO00/77153 discloses a detergent tablet containing (a) particles which contain organic surfactant and detergency builder; and (b) water insoluble but water swellable particles of plant material which contain both cellulose and lignin, such as coconut husk, obtainable by fragmentation of plant material without separation of its fibres into a liquid dispersion.
- a detergent tablet containing (a) particles which contain organic surfactant and detergency builder; and (b) water insoluble but water swellable particles of plant material which contain both cellulose and lignin, such as coconut husk, obtainable by fragmentation of plant material without separation of its fibres into a liquid dispersion.
- Such powders include ginger for fragrance; lime, lemon or orange rind for freshness; flower petals for perfume; exfoliating agents such as oat kernel flour, rice or rice bran flour; various pigments of natural origin, such as turmeric powder for anti-inflammatory benefit; seed derivatives such as cardamom and coriander for perfuming; various dried herbs such as mint, oregano, green tea, bay leaf and tea-tree for perfuming and anti-microbial benefits.
- the present invention provides a fabric conditioning composition, which comprises:
- the powder of botanical origin has a particle size of from 0.1 to
- a method of preparing a composition comprising the step of pulverizing the powder of botanical origin to a particle size of from 0.1 to 100 microns preferably from 0.2 to 90 microns, more preferably from 0.5 to 60, even more preferably from 1 to 45 microns and most preferably from 2 to 30 microns.
- the present invention requires the use of ultra-fine powders.
- the powders suitable for use in the compositions of the invention are sparingly soluble, preferably insoluble particulate structures of botanical origin. They are preferably aromatic and as such preferably comprise one or more aromatic essential oils.
- the powders of the present invention can be of any shape and are not necessarily spherical and can have aspect ratio (ratio of length to diameter) greater than 1.
- aspect ratio ratio of length to diameter
- micronised, ultra-fine, or finely divided particle sizes having a maximum axis of from 0.1 to 100 microns preferably from 0.2 to 90 microns, more preferably from 0.5 to 60, even more preferably from 1 to 45 microns and most preferably from 2 to 30 microns.
- Particles of suitable size may be obtained by any suitable process, for example pulverizing, milling, etc. Fractionation, for example by sieving, may be used to separate the required particle size range.
- the powder is a material of botanical origin, and may be derived from any part of the plant, such as tubers, fruits, flowers, flower parts (calyx, stamen, etc), seeds, beans, pods, pith, woods, barks, stalks, stems, leaves, roots, rhizomes, husks, skins, rinds and mixtures thereof.
- aromatic powders examples include vanilla bean powder, ginger powder, cinnamon powder, cocoa powder, clove powder, cardamom powder, coriander - A -
- herb powders for example, rosemary, thyme, sweet bay, sage, tarragon, mint, basil, balm, lemon verbena, red bergamot, marjoram, lavender and oregano
- chamomile powder for example, rosemary, thyme, sweet bay, sage, tarragon, mint, basil, balm, lemon verbena, red bergamot, marjoram, lavender and oregano
- chamomile powder for example, rosemary, thyme, sweet bay, sage, mint, basil, balm, lemon verbena, red bergamot, marjoram, lavender and oregano
- chamomile powder for example, rosemary, thyme, sweet bay, sage, mint, basil, balm, lemon verbena, red bergamot, marjoram, lavender and oregano
- chamomile powder for example, rosemary, thyme, sweet bay, sage, mint, basil, balm, lemon verbena, red berga
- Preferred non-aromatic powders include ginseng powder, rice husk flour, wheat husk flour, buckwheat husk flour and mixtures thereof.
- the powdered material can be in native form or may result from processes such as ageing, fermenting and roasting that would increase or alter the constituent aroma chemicals.
- the plant powders of the invention can be incorporated into laundry compositions in a similar fashion as other powdered ingredients.
- the powder of botanical origin is present in an amount of from 0.1 to 10 wt %, preferably from 0.3 to 6 wt %, more preferably from 0.4 to 4 wt % and most preferably from 0.5 to 3 wt % by weight of the total composition.
- the powders of botanical origin suitable for use in the invention are not extracted or isolated materials, such as polymers, for example lignin, starches or proteins, but are plant parts that are powdered in their bulk state.
- the powders are not intended to include cellulose or cellulose derivatives such as polymeric derivatives such as cellulose ethers.
- the plant parts (i.e. pre-powdered) and the powders are not subject to chemical purification, for example, to remove components such as lignin or pigments (but may, of course, be washed or cleaned).
- Deposition of micro-powder from the laundry formulations of the invention onto a substrate may be achieved by any suitable route.
- the particle size of the powder is such that the particles are trapped between the fibres of the fabric.
- the filtration mechanism requires particles or clusters of primary particles of a size comparable with the interyarn pore size.
- the particle size suitable for filtration is typically in the range of from 1 to 30 microns. Larger particles begin to be visible to the unaided eye, whereas smaller particles tend to be removed in the wash. Particles of around from 5 to 15 microns are preferred as they tend to be invisible to the eye and exhibit good deposition by filtration onto fabrics.
- Deposition of micro-powders from laundry formulations of the invention may also be achieved and enhanced over and above the delivery by filtration method, by polymer aided deposition.
- the polymeric deposition aid is suitably present at a level of from 0.01 to 5% by total weight of the composition preferably from 0.02 to 3%, more preferably from 0.2 to 2 % and most preferably from 0.5 to 1 .6 %.
- Polymeric deposition agent suitable for use in the present invention include modified natural polymers and synthetic polymers.
- Polymers suitable for the deposition of micro-powders are disclosed in WO9709406, particularly high MW polyethylene oxides (PEO) which are used to deposit clay particles in the main wash;
- EP0299575B1 and WO9527037 disclose high MW PEO, polyacrylates, polyacryl amides, poly vinyl alcohol and poly ethylene imines, which are used to deposit clay particles in the main wash;
- EP0387426B1 which utilizes a similar list of polymers as well as guar gums.
- WO 01/07546 A1 discloses suitable rinse stage polymeric deposition aids for emulsion droplets including cationic guar polymers, cationic polyacrylamides, cationic potato starch, and cationic cellulose derivates.
- Preferred modified natural polymers suitable for use in the present invention may be selected from the group consisting of cationic starches, cationic guars, cationic cellulose, and nonionic locust bean gums (LBGs).
- a preferred cationic starch is a cation ical Iy modified potato starch.
- cationic polymers include cationic guar polymers such as Jaguar (ex Rhone Poulenc), cationic cellulose derivatives such as Celquats (ex National Starch), Flocaid (ex National Starch), cationic potato starch such as Softgel (ex Aralose) and cationic polyacrylamides such as PCG (ex Allied Colloids).
- cationic guar polymers such as Jaguar (ex Rhone Poulenc), cationic cellulose derivatives such as Celquats (ex National Starch), Flocaid (ex National Starch), cationic potato starch such as Softgel (ex Aralose) and cationic polyacrylamides such as PCG (ex Allied Colloids).
- Suitable non-ionic deposition aids include high molecular weight polyethylene glycols, for example PEO WSRN 750 (ex Union Carbide).
- Preferred synthetic polymers for use as a deposition aid, may be selected from the group consisting of polyethylene oxide (PEO), polyethylene imine (PEI), poly (acrylate), poly (acrylamide), polyethylene terephthalate-polyoxyethylene terephthalate (PET/POET) polymers and mixtures thereof.
- PEO polyethylene oxide
- PEI polyethylene imine
- PET polyoxyethylene terephthalate
- the fabric conditioning composition of the invention is suitable for use in a laundry process.
- a rinse treatment e.g. conditioner or finisher
- a post-treatment 'wet tissue' type product e.g. conditioner or finisher
- the compositions of the present invention are preferably rinse-added softening compositions.
- compositions of the invention may be in any physical form e.g. a tablet, a bar, a paste, gel or liquid, spray, stick, impregnated substrate, foam or mousse.
- compositions may be liquid or unit dose such as a pouch.
- the liquid products of the invention may have pH ranging from 2.5 to 7. This pH range preferably remains stable over the shelf life of the product.
- the active ingredient in the compositions is a fabric conditioning agent. More than one active ingredient may be included.
- the conditioning agents may be cationic or non-ionic. They may for example be used in amounts from 0.5% to 35%, preferably from 1 % to 30% more preferably from 3% to 25% by weight of the composition.
- the preferred softening active for use in rinse conditioner compositions of the invention is a quaternary ammonium compound.
- the quaternary ammonium fabric softening material for use in compositions of the present invention can be an ester-linked triethanolamine (TEA) quaternary ammonium compound comprising a mixture of mono-, di- and tri-ester linked components.
- TAA ester-linked triethanolamine
- TEA-based fabric softening compounds comprise a mixture of mono, di- and tri-ester forms of the compound where the di-ester linked component comprises no more than 70% by weight of the fabric softening compound, preferably no more than 60%, e.g. no more than 55%, or even no more than 45% of the fabric softening compound and at least 10% of the monoester linked component by weight of the fabric softening compound.
- a first group of quaternary ammonium compounds (QACs) suitable for use in the present invention is represented by formula (I):
- each R is independently selected from a C 5-35 alkyl or alkenyl group;
- R 1 represents a Ci -4 alkyl, C 2-4 alkenyl or a Ci -4 hydroxyalkyl group;
- T is generally O- CO. (i.e. an ester group bound to R via its carbon atom), but may alternatively be CO-O (i.e. an ester group bound to R via its oxygen atom);
- n is a number selected from 1 to 4;
- m is a number selected from 1 , 2, or 3;
- X ⁇ is an anionic counter- ion, such as a halide or alkyl sulphate, e.g. chloride or methylsulphate.
- Di-esters variants of formula I i.e.
- each R 1 group is independently selected from Ci -4 alkyl, hydroxyalkyl or C 2-4 alkenyl groups; and wherein each R 2 group is independently selected from Cs- 2 s alkyl or alkenyl groups; and wherein n, T, and X " are as defined above.
- Preferred materials of this second group include 1 ,2 ⁇ b/s[tallowoyloxy]-3- trimethylamine propane chloride, 1 ,2 ⁇ b/s[hardened tallowoyloxy]-3-thmethylamine propane chloride, 1 ,2- ⁇ b/s[oleoyloxy]-3-thmethylanr ⁇ ine propane chloride, and 1 ,2 ib/s[stearoyloxy]-3-thmethylamine propane chloride.
- Such materials are described in US 4,137,180 (Lever Brothers).
- these materials also comprise an amount of the corresponding mono-ester.
- a third group of QACs suitable for use in the invention is represented by formula
- each R 1 group is independently selected from Ci -4 alkyl, or C 2-4 alkenyl groups; and wherein each R 2 group is independently selected from C 8- 28 alkyl or alkenyl groups; and n, T, and X " are as defined above.
- Preferred materials of this third group include bis(2-tallowoyloxyethyl)dimethyl ammonium chloride and hardened versions thereof.
- the iodine value of the quaternary ammonium fabric softening material is from 0 to 60, preferably from 0 to 45, more preferably from 0 to 30, and most preferably from 0 to 20.
- Iodine value is defined as the number of grams of iodine absorbed per 100 g of test material. NMR spectroscopy is a suitable technique for determining the iodine value of the softening agents of the present invention, using the method described in Anal. Chem., 34, 1136 (1962) by Johnson and Shoolery and in EP 593,542 (Unilever, 1993).
- the non-ester softening compound preferably has the alkyl or alkenyl chain lengths referred to above for the non-ester softening compound.
- non-ester softening compound is a quaternary ammonium material represented by formula (IV):-
- each R 1 group is independently selected from Ci -4 alkyl, hydroxyalkyl or C 2-4 alkenyl groups; R 2 group is independently selected from C 8- 28 alkyl or alkenyl groups, and X " is as defined above.
- compositions may comprise a total amount of from 0.5 wt % to 40 wt % by weight of the fabric softening compounds, preferably from 1.5 wt % to 30 wt %, more preferably from 4 to 25 wt %, most preferably from 10 to 30 wt %, based on the total weight of the composition.
- compositions may alternatively or additionally contain nonionic fabric softening agents such as lanolin and derivatives thereof.
- nonionic fabric softening agent suitable for use in the compositions of the invention is Castor oil, for example, from Now Chemicals.
- Lecithins and other phospholipids are also suitable softening compounds.
- a further preferred type of softening agent is a sugar polyester.
- the sugar polyester is preferably selected from the group consisting of sucrose polyesters, glucose polyesters and cellobiose polyesters, and is most preferably a sucrose polyester.
- the sugar polyester may be liquid, soft solid or solid.
- the preferred sucrose polyesters for use in the present invention have 2 to 4 hydrocarbon chains per sugar ring, where the hydrocarbon chain has a length of from 12 to 22 carbon atoms.
- a particularly preferred sucrose polyester is sucrose tetraerucate.
- sucrose polyester is Ryoto Sugar Ester ER290 supplied by Mitsubishi Kagaku Foods Corporation, which is a sucrose tetraerucate and according to the manufacturer's specification is mainly Tetraerucate, Pentaerucate and Hexaerucate and has a HLB value of 2.
- the sugar polyester may be pure, or may contain impurities.
- the impurities are preferably selected from the group consisting of free fatty acid, fatty acid methyl ester, soap, inorganic salts and mixtures thereof.
- the most preferred SPEs are commercially available, such as Emanon SCR-PK (ex KAO), which is a palm kernel derived SPE containing mainly C12-C14 with about 20% C18 mono unsaturatation and SPE-THSBO (ex Clahant), which is derived from touch hardened soy bean oil, having mainly C16-C18 chains with about 80% mono and di unsaturation.
- Emanon SCR-PK ex KAO
- SPE-THSBO (ex Clahant)
- the average degree of esterification of the above preferred SPEs is from 4.2 to 4.7.
- SCR-PK contains up to 20% impurities but SPE-THSBO is pure.
- SCR-PK contains from 4 to 6 wt% of K soap, 2.5 wt% of free fatty acid, from 10 to 15 wt% of fatty acid methyl ester and less than 1 % of KCI.
- the sugar polyester being non-ionic oil, requires an emulsifier, that is to say, the sugar polyester must be in an emulsified form.
- the emulsifier is preferably selected from cationic surfactant, anionic surfactant, non-ionic surfactant, and mixtures thereof.
- the ultra-fine particles of the invention themselves can act as stabilizer and emulsifier for the nonionic softeners such as sugar polyesters (SPEs).
- SPEs sugar polyesters
- a nonionic stabilising agent may be present in fabric softening compositions.
- Suitable nonionic stabilising agents may be present such as linear Cs to C22 alcohols alkoxylated with 10 to 20 moles of alkylene oxide, C10 to C20 alcohols, or mixtures thereof.
- Other stabilising agents include the deflocculating polymers as described in EP 0415698A2 and EP 0458599B1.
- the nonionic stabilising agent is a linear Cs to C22 alcohol alkoxylated with 10 to 20 moles of alkylene oxide.
- the level of nonionic stabiliser is within the range from 0.1 to 10% by weight, more preferably from 0.5 to 5% by weight, most preferably from 1 to 4% by weight.
- the mole ratio of the quaternary ammonium compound and/or other cationic softening agent to the nonionic stabilising agent is suitably within the range from 40:1 to about 1 :1 , preferably within the range from 18:1 to about 3:1.
- the composition can also contain fatty acids, for example Cs to C2 4 alkyl or alkenyl monocarboxylic acids or polymers thereof.
- the fatty acid is non-saponified, more preferably the fatty acid is free, for example oleic acid, lauric acid or tallow fatty acid.
- the level of fatty acid material is preferably more than 0.1 % by weight, more preferably more than 0.2% by weight.
- Concentrated compositions may comprise from 0.5 to 20% by weight of fatty acid, more preferably 1 % to 10% by weight.
- the weight ratio of quaternary ammonium material or other cation ic softening agent to fatty acid material is preferably from 10:1 to 1 :10.
- Cationic surfactants which can be used in main-wash compositions for fabrics.
- Cationic surfactants that may be used include quaternary ammonium salts of the general formula R1 R2R3R4NT X " wherein the R groups are long or short hydrocarbon chains, typically alkyl, hydroxyalkyl or ethoxylated alkyl groups, and X is a counter-ion (for example, compounds in which R1 is a C8-C22 alkyl group, preferably a Cs-Cio or C12-C14 alkyl group, R2 is a methyl group, and R3 and R4, which may be the same or different, are methyl or hydroxyethyl groups); and cationic esters (for example, choline esters).
- aqueous rinse added conditioners the level of cationic or nonionic softener varies from 3 to 30% more preferably from 5 to 25%.
- botanical powders can be incorporated in predominately non-aqueous systems containing up to 60% fabric softening actives.
- the fabric conditioning compositions of the invention can also contain adjuvants that are normal in the cosmetic, pharmaceutical and/or dermatological field, such as hydrophilic or lipophilic gelling agents, hydrophilic or lipophilic active agents, preserving agents, antioxidants, solvents, fragrances, fillers, screening agents, bactericides, odour absorbers, photobleaches (singlet oxygen or radical type) and dyestuffs.
- adjuvants that are normal in the cosmetic, pharmaceutical and/or dermatological field, such as hydrophilic or lipophilic gelling agents, hydrophilic or lipophilic active agents, preserving agents, antioxidants, solvents, fragrances, fillers, screening agents, bactericides, odour absorbers, photobleaches (singlet oxygen or radical type) and dyestuffs.
- the amounts of these various adjuvants are those conventionally used in the field under consideration and are, for example, from 0.01 to 20% of the total weight of the composition. Depending on their nature, these adjuvants can be introduced into the
- the substrate When used in laundering, the substrate may be any substrate onto which it is desirable to deposit the botanical particles and which is subjected to treatment such as a washing or rinsing process.
- the substrate may be a textile fabric.
- the treatment of the substrate with the composition of the invention can be made by any suitable method such as washing, soaking or rinsing of the substrate but also by direct application such as spraying, rubbing, spotting, smearing, etc.
- the treatment may involve contacting the substrate with an aqueous medium comprising the material of the invention.
- the treatment may be provided as a spray composition e.g., for domestic (or industrial) application to fabric in a treatment separate from a conventional domestic laundering process.
- Suitable spray dispensing devices are disclosed in WO 96/15310 (Procter & Gamble) and are incorporated herein by reference.
- the compositions of the invention may be used to provide a perfume and/or odour benefit, for example a reduction in malodour, to fabric.
- Example 1 Preparation of powders for use in the invention
- Plant powders having a particle size within the claimed range were prepared using a Retsch ZM1000 Ultra Centrifugal Mill operating at a speed of 10,000 rpm. The mill was fitted with a 24 tooth rotor and a 0.12 mm screen.
- Table 1 gives two examples of the size fractions that remained on each sieve from 10g of the starting powder.
- Table 1 Weight fractions remaining on the sieve from 10g of starting powder after 30 minutes of shaking (for ginger) and by brushing (for cardamom).
- Example 2 Softener compositions 1 to 4 comprising herbs and spices, according to the invention Fabric conditioner compositions 1 to 4 in Table 2 containing herbs and spices according to the invention.
- ** TEA quat is a cationic softener based on thethanolamine with tallow or hard tallow chains and 15% IPA as solvent.
- Emanon SCR-PK is Sucrose Poly Ester softening oil derived from palm kernel oil.
- Example 3 Evaluation of deposition of powders onto fabrics
- the level of deposition of the particles from a rinse solution can be quantified by measuring the turbidity, or light transmission, of the rinse solution before and after the solution is contacted with the fabrics.
- Light transmission or turbidity measurements for this purpose cannot be conducted in the presence of cationic softeners because of their inherent milkiness.
- CAC cationic surfactant
- CAC Cetylthmethylammonium chloride
- the Linitester temperature was set to 40 0 C.
- Table 3 summarizes the deposition from the rinse solution for mint particles ⁇ 45 ⁇ m in the presence of 3 different deposition polymers. Deposition is expressed as a percentage of the total amount of added particles in the solution.
- Table 3 Deposition of mint particles onto cotton, polycotton and polyester in the presence of Softgel BDA, Locust Bean Gum and Polymer JR from rinse solutions containing 0.002 % polymeric deposition aids.
- Softgel BDA (Avebe) is a cationic potato starch with low, 0.05%, degree of substitution (charge).
- Ucare polymer JR-30M (Amerchol) is a cationic hydroxyethyl cellulose with a 1.5-
- LBG (Sigma) is a non-ionic locust bean gum polysaccharide.
- the level of delivery from the rinse solution simulating the washing machine condition is surprisingly good from the cationic solution alone compared to water.
- the polymers have improved the deposition except for polyester where the high charged density JR polymer has improved deposition over and above that of control CTAC.
- LBG has improved the deposition on cotton and polycotton (positively charged substrates in CTAC) most likely through its affinity and recognition of cellulose units.
- the wet monitors had a strong smell of the deposited particles which on drying had a faint remnant. On synthetics like polyester this was sufficient to mask the dusty vinegar smell of polyester fabric to a pleasant smell.
Landscapes
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Wood Science & Technology (AREA)
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Organic Chemistry (AREA)
- Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
- Detergent Compositions (AREA)
Abstract
A fabric conditioning composition, which comprises: a) at least one cationic or nonionic softening agent, b) a powder of botanical origin, and c) an optional polymeric deposition aid, wherein the powder of botanical origin has a particle size of from 0.1 to 100 μm, preferably from 0.5 to 50 and most preferably from 1 to 45 μm.
Description
IMPROVEMENTS RELATING TO FABRIC TREATMENT COMPOSITIONS
Technical Field
The present invention relates to fabric conditioning compositions comprising micro powders of botanical origin.
Background
Using clay particles to impart softness to fabrics from the wash or from the rinse is well known in the art. Similarly the use of nano-particles of silica or titanium dioxide and micro-encapsulated perfume particles are now quite well documented for enhanced perfume impact.
US2003/0087788 (Rhodia Inc) discloses water dispersible granules comprising a hydrophobic fragrance in the form of droplets, which is finely divided in and encapsulated by a water-soluble/dispersible solid organic matrix, which may be polypeptides of plant or synthetic origin, such as soya or wheat.
EP0908171 (Gem Energy Industry Ltd) discloses a dry powder herbal cleaning composition containing (a) a herb which acts as a soap or detergent; (b) a herb which acts as a foaming accelerating agent; (c) a herb which acts as a foaming agent; (d) a herb which acts as a pigmentation or colour restoring or maintenance agent; and (e) a herb which acts as a conditioner.
WO00/77153 (Unilever pic) discloses a detergent tablet containing (a) particles which contain organic surfactant and detergency builder; and (b) water insoluble but water swellable particles of plant material which contain both cellulose and lignin, such as coconut husk, obtainable by fragmentation of plant material without separation of its fibres into a liquid dispersion.
We have now discovered that micron ised powders of botanical origin can be deposited onto fabrics from a laundry rinse product to impart fabrics with benefit agents or for novel fragrance enhancement. Examples of such powders include ginger for fragrance; lime, lemon or orange rind for freshness; flower petals for perfume; exfoliating agents such as oat kernel flour, rice or rice bran flour; various pigments of natural origin, such as turmeric powder for anti-inflammatory benefit; seed derivatives such as cardamom and coriander for perfuming; various dried herbs such as mint, oregano, green tea, bay leaf and tea-tree for perfuming and anti-microbial benefits.
Definition of the Invention
In a first aspect, the present invention provides a fabric conditioning composition, which comprises:
a) at least one cationic or nonionic softening agent, c) a powder of botanical origin, and d) an optional polymeric deposition aid,
wherein the powder of botanical origin has a particle size of from 0.1 to
100 μm, preferably from 0.5 to 50 and most preferably from 1 to 45 μm.
In a second aspect of the present invention there is provided a process for treating fabric comprising the step of treating a fabric article with a composition as defined in any preceding claim.
In a further aspect of the invention, there is provided a method of preparing a composition, comprising the step of pulverizing the powder of botanical origin to a particle size of from 0.1 to 100 microns preferably from 0.2 to 90 microns, more
preferably from 0.5 to 60, even more preferably from 1 to 45 microns and most preferably from 2 to 30 microns.
Detailed Description of the Invention
The Powders of Botanical Origin
The present invention requires the use of ultra-fine powders. The powders suitable for use in the compositions of the invention are sparingly soluble, preferably insoluble particulate structures of botanical origin. They are preferably aromatic and as such preferably comprise one or more aromatic essential oils.
The powders of the present invention can be of any shape and are not necessarily spherical and can have aspect ratio (ratio of length to diameter) greater than 1. Within the context of this invention, by micronised, ultra-fine, or finely divided, is meant particle sizes having a maximum axis of from 0.1 to 100 microns preferably from 0.2 to 90 microns, more preferably from 0.5 to 60, even more preferably from 1 to 45 microns and most preferably from 2 to 30 microns.
Particles of suitable size may be obtained by any suitable process, for example pulverizing, milling, etc. Fractionation, for example by sieving, may be used to separate the required particle size range.
The powder is a material of botanical origin, and may be derived from any part of the plant, such as tubers, fruits, flowers, flower parts (calyx, stamen, etc), seeds, beans, pods, pith, woods, barks, stalks, stems, leaves, roots, rhizomes, husks, skins, rinds and mixtures thereof.
Examples of aromatic powders include vanilla bean powder, ginger powder, cinnamon powder, cocoa powder, clove powder, cardamom powder, coriander
- A -
powder, cumin powder, caraway powder, dill powder, chili powder, cyanine powder, turmeric powder, coffee bean powder, tea leaf powder, tea-tree powder, blackberry leaf powder, Lemon balm leaf powder, herb powders (for example, rosemary, thyme, sweet bay, sage, tarragon, mint, basil, balm, lemon verbena, red bergamot, marjoram, lavender and oregano), chamomile powder, fennel powder, lime rind powder, lemon rind powder, grapefruit rind powder, tangerine rind powder, mandarin rind powder, lemon grass powder, apple pomace powder, Lemon myrtle powder, red clover powder, liquorice powder and mixtures thereof.
Preferred non-aromatic powders include ginseng powder, rice husk flour, wheat husk flour, buckwheat husk flour and mixtures thereof.
The powdered material can be in native form or may result from processes such as ageing, fermenting and roasting that would increase or alter the constituent aroma chemicals.
Delivery of such powders onto fabrics and clothing by a laundry product can impart a host of benefits from ingredients in their natural state that otherwise would be difficult to deliver from laundry applications. These include long lasting perfume and freshness, anti-bacterial activity, deodorizing activity, skin anti- ageing and well-being activity, change of fabric feel (handle), cooling benefit and warming benefit.
The plant powders of the invention can be incorporated into laundry compositions in a similar fashion as other powdered ingredients.
The powder of botanical origin is present in an amount of from 0.1 to 10 wt %, preferably from 0.3 to 6 wt %, more preferably from 0.4 to 4 wt % and most preferably from 0.5 to 3 wt % by weight of the total composition.
The powders of botanical origin suitable for use in the invention are not extracted or isolated materials, such as polymers, for example lignin, starches or proteins, but are plant parts that are powdered in their bulk state. The powders are not intended to include cellulose or cellulose derivatives such as polymeric derivatives such as cellulose ethers. The plant parts (i.e. pre-powdered) and the powders are not subject to chemical purification, for example, to remove components such as lignin or pigments (but may, of course, be washed or cleaned).
The Polymeric Deposition Aid
Deposition of micro-powder from the laundry formulations of the invention onto a substrate may be achieved by any suitable route.
For example, by filtration, in which the particle size of the powder is such that the particles are trapped between the fibres of the fabric. The filtration mechanism requires particles or clusters of primary particles of a size comparable with the interyarn pore size.
The particle size suitable for filtration is typically in the range of from 1 to 30 microns. Larger particles begin to be visible to the unaided eye, whereas smaller particles tend to be removed in the wash. Particles of around from 5 to 15 microns are preferred as they tend to be invisible to the eye and exhibit good deposition by filtration onto fabrics.
Deposition of micro-powders from laundry formulations of the invention may also be achieved and enhanced over and above the delivery by filtration method, by polymer aided deposition. Where present, the polymeric deposition aid is suitably present at a level of from 0.01 to 5% by total weight of the composition preferably from 0.02 to 3%, more preferably from 0.2 to 2 % and most preferably from 0.5 to 1 .6 %.
Polymeric deposition agent suitable for use in the present invention include modified natural polymers and synthetic polymers.
Polymers suitable for the deposition of micro-powders are disclosed in WO9709406, particularly high MW polyethylene oxides (PEO) which are used to deposit clay particles in the main wash; EP0299575B1 and WO9527037 disclose high MW PEO, polyacrylates, polyacryl amides, poly vinyl alcohol and poly ethylene imines, which are used to deposit clay particles in the main wash; and EP0387426B1 which utilizes a similar list of polymers as well as guar gums.
WO 01/07546 A1 discloses suitable rinse stage polymeric deposition aids for emulsion droplets including cationic guar polymers, cationic polyacrylamides, cationic potato starch, and cationic cellulose derivates.
Preferred modified natural polymers suitable for use in the present invention may be selected from the group consisting of cationic starches, cationic guars, cationic cellulose, and nonionic locust bean gums (LBGs). A preferred cationic starch is a cation ical Iy modified potato starch.
Suitable examples of cationic polymers include cationic guar polymers such as Jaguar (ex Rhone Poulenc), cationic cellulose derivatives such as Celquats (ex National Starch), Flocaid (ex National Starch), cationic potato starch such as Softgel (ex Aralose) and cationic polyacrylamides such as PCG (ex Allied Colloids).
Suitable non-ionic deposition aids include high molecular weight polyethylene glycols, for example PEO WSRN 750 (ex Union Carbide).
Preferred synthetic polymers, for use as a deposition aid, may be selected from the group consisting of polyethylene oxide (PEO), polyethylene imine (PEI), poly
(acrylate), poly (acrylamide), polyethylene terephthalate-polyoxyethylene terephthalate (PET/POET) polymers and mixtures thereof.
The Fabric Softening Agent
The Fabric Conditioning Composition
The fabric conditioning composition of the invention is suitable for use in a laundry process. Examples include a rinse treatment (e.g. conditioner or finisher), or a post-treatment 'wet tissue' type product. The compositions of the present invention are preferably rinse-added softening compositions.
The compositions of the invention may be in any physical form e.g. a tablet, a bar, a paste, gel or liquid, spray, stick, impregnated substrate, foam or mousse. In particular the compositions may be liquid or unit dose such as a pouch.
The liquid products of the invention may have pH ranging from 2.5 to 7. This pH range preferably remains stable over the shelf life of the product.
The active ingredient in the compositions is a fabric conditioning agent. More than one active ingredient may be included.
The Softening Agent
Any conventional fabric conditioning agent may be used in the compositions of the present invention. The conditioning agents may be cationic or non-ionic. They may for example be used in amounts from 0.5% to 35%, preferably from 1 % to 30% more preferably from 3% to 25% by weight of the composition.
The preferred softening active for use in rinse conditioner compositions of the invention is a quaternary ammonium compound. The quaternary ammonium fabric softening material for use in compositions of the present invention can be an ester-linked triethanolamine (TEA) quaternary ammonium compound comprising a mixture of mono-, di- and tri-ester linked components.
Typically, TEA-based fabric softening compounds comprise a mixture of mono, di- and tri-ester forms of the compound where the di-ester linked component comprises no more than 70% by weight of the fabric softening compound, preferably no more than 60%, e.g. no more than 55%, or even no more than 45% of the fabric softening compound and at least 10% of the monoester linked component by weight of the fabric softening compound.
A first group of quaternary ammonium compounds (QACs) suitable for use in the present invention is represented by formula (I):
[(CH2)n(TR)]m
I R1-N+-[(CH2)n(OH)]3-m X- (I)
wherein each R is independently selected from a C5-35 alkyl or alkenyl group; R1 represents a Ci-4 alkyl, C2-4 alkenyl or a Ci-4 hydroxyalkyl group; T is generally O- CO. (i.e. an ester group bound to R via its carbon atom), but may alternatively be CO-O (i.e. an ester group bound to R via its oxygen atom); n is a number selected from 1 to 4; m is a number selected from 1 , 2, or 3; and X~ is an anionic counter- ion, such as a halide or alkyl sulphate, e.g. chloride or methylsulphate. Di-esters variants of formula I (i.e. m = 2) are preferred and typically have mono- and tri- ester analogues associated with them. Such materials are particularly suitable for use in the present invention.
Especially preferred agents are di-esters of triethanolamine methylsulphate, otherwise referred to as "TEA ester quats.". Commercial examples include Prapagen TQL, ex Clariant, and Tetranyl AHT-1 , ex Kao, (both di-[hardened tallow ester] of triethanolamine methylsulphate), AT-1 (di-[tallow ester] of triethanolamine methylsulphate), and L5/90 (di-[palm ester] of triethanolamine methylsulphate), both ex Kao, and Rewoquat WE15 (a di-ester of triethanolamine methylsulphate having fatty acyl residues deriving from Ci0-C2O and Ci6-Ci8 unsaturated fatty acids), exWitco Corporation.
The second group of QACs suitable for use in the invention is represented by formula (II):
(R1)3N+-(CH2)n-CH-TR2 X" (H)
CH2TR2
wherein each R1 group is independently selected from Ci-4 alkyl, hydroxyalkyl or C2-4 alkenyl groups; and wherein each R2 group is independently selected from Cs- 2s alkyl or alkenyl groups; and wherein n, T, and X" are as defined above.
Preferred materials of this second group include 1 ,2 ιb/s[tallowoyloxy]-3- trimethylamine propane chloride, 1 ,2 ιb/s[hardened tallowoyloxy]-3-thmethylamine propane chloride, 1 ,2-ιb/s[oleoyloxy]-3-thmethylanrιine propane chloride, and 1 ,2 ib/s[stearoyloxy]-3-thmethylamine propane chloride. Such materials are described in US 4,137,180 (Lever Brothers). Preferably, these materials also comprise an amount of the corresponding mono-ester.
A third group of QACs suitable for use in the invention is represented by formula
(R1)2-N+-[(CH2)n-T-R2]2 X- (III)
wherein each R1 group is independently selected from Ci-4 alkyl, or C2-4 alkenyl groups; and wherein each R2 group is independently selected from C8-28 alkyl or alkenyl groups; and n, T, and X" are as defined above. Preferred materials of this third group include bis(2-tallowoyloxyethyl)dimethyl ammonium chloride and hardened versions thereof.
The iodine value of the quaternary ammonium fabric softening material is from 0 to 60, preferably from 0 to 45, more preferably from 0 to 30, and most preferably from 0 to 20.
Iodine value is defined as the number of grams of iodine absorbed per 100 g of test material. NMR spectroscopy is a suitable technique for determining the iodine value of the softening agents of the present invention, using the method described in Anal. Chem., 34, 1136 (1962) by Johnson and Shoolery and in EP 593,542 (Unilever, 1993).
The non-ester softening compound preferably has the alkyl or alkenyl chain lengths referred to above for the non-ester softening compound.
One preferred type of non-ester softening compound is a quaternary ammonium material represented by formula (IV):-
R1
(IV) R N R X
R2
wherein each R1 group is independently selected from Ci-4 alkyl, hydroxyalkyl or C2-4 alkenyl groups; R2 group is independently selected from C8-28 alkyl or alkenyl groups, and X" is as defined above.
The compositions may comprise a total amount of from 0.5 wt % to 40 wt % by weight of the fabric softening compounds, preferably from 1.5 wt % to 30 wt %, more preferably from 4 to 25 wt %, most preferably from 10 to 30 wt %, based on the total weight of the composition.
The compositions may alternatively or additionally contain nonionic fabric softening agents such as lanolin and derivatives thereof. A further nonionic fabric softening agent suitable for use in the compositions of the invention is Castor oil, for example, from Now Chemicals.
Lecithins and other phospholipids are also suitable softening compounds.
A further preferred type of softening agent is a sugar polyester. Where present, the sugar polyester is preferably selected from the group consisting of sucrose polyesters, glucose polyesters and cellobiose polyesters, and is most preferably a sucrose polyester.
The sugar polyester may be liquid, soft solid or solid.
The preferred sucrose polyesters for use in the present invention have 2 to 4 hydrocarbon chains per sugar ring, where the hydrocarbon chain has a length of from 12 to 22 carbon atoms. A particularly preferred sucrose polyester is sucrose tetraerucate.
An example of a preferred sucrose polyester is Ryoto Sugar Ester ER290 supplied by Mitsubishi Kagaku Foods Corporation, which is a sucrose tetraerucate and according to the manufacturer's specification is mainly Tetraerucate, Pentaerucate and Hexaerucate and has a HLB value of 2.
The sugar polyester may be pure, or may contain impurities. When present, the impurities are preferably selected from the group consisting of free fatty acid, fatty acid methyl ester, soap, inorganic salts and mixtures thereof.
The most preferred SPEs are commercially available, such as Emanon SCR-PK (ex KAO), which is a palm kernel derived SPE containing mainly C12-C14 with about 20% C18 mono unsaturatation and SPE-THSBO (ex Clahant), which is derived from touch hardened soy bean oil, having mainly C16-C18 chains with about 80% mono and di unsaturation. The average degree of esterification of the above preferred SPEs is from 4.2 to 4.7.
SCR-PK contains up to 20% impurities but SPE-THSBO is pure. SCR-PK contains from 4 to 6 wt% of K soap, 2.5 wt% of free fatty acid, from 10 to 15 wt% of fatty acid methyl ester and less than 1 % of KCI.
The sugar polyester, being non-ionic oil, requires an emulsifier, that is to say, the sugar polyester must be in an emulsified form. The emulsifier is preferably selected from cationic surfactant, anionic surfactant, non-ionic surfactant, and mixtures thereof.
The ultra-fine particles of the invention themselves can act as stabilizer and emulsifier for the nonionic softeners such as sugar polyesters (SPEs). Recently the interest in study of solid particles as emulsifies has been re-awakened (Binks, B. P. Current Opinions in Colloid Interface Science, 2002, 7, 21 ).
Most of recent activities on surface active colloidal particles have focused on very low aspect ratio (spherical) particles. Only recently Alargova et al, Langmuir, 2006, 22, 765-774, have shown that high aspect ratio particles can be used for emulsion stabilisation.
In fabric softening compositions a nonionic stabilising agent may be present. Suitable nonionic stabilising agents may be present such as linear Cs to C22 alcohols alkoxylated with 10 to 20 moles of alkylene oxide, C10 to C20 alcohols, or mixtures thereof. Other stabilising agents include the deflocculating polymers as described in EP 0415698A2 and EP 0458599B1.
Advantageously the nonionic stabilising agent is a linear Cs to C22 alcohol alkoxylated with 10 to 20 moles of alkylene oxide. Preferably, the level of nonionic stabiliser is within the range from 0.1 to 10% by weight, more preferably from 0.5 to 5% by weight, most preferably from 1 to 4% by weight. The mole ratio of the quaternary ammonium compound and/or other cationic softening agent to the nonionic stabilising agent is suitably within the range from 40:1 to about 1 :1 , preferably within the range from 18:1 to about 3:1.
The composition can also contain fatty acids, for example Cs to C24 alkyl or alkenyl monocarboxylic acids or polymers thereof. Preferably the fatty acid is non-saponified, more preferably the fatty acid is free, for example oleic acid, lauric acid or tallow fatty acid. The level of fatty acid material is preferably more than 0.1 % by weight, more preferably more than 0.2% by weight. Concentrated compositions may comprise from 0.5 to 20% by weight of fatty acid, more preferably 1 % to 10% by weight. The weight ratio of quaternary ammonium material or other cation ic softening agent to fatty acid material is preferably from 10:1 to 1 :10.
It is also possible to include certain mono-alkyl cationic surfactants which can be used in main-wash compositions for fabrics. Cationic surfactants that may be used include quaternary ammonium salts of the general formula R1 R2R3R4NT X" wherein the R groups are long or short hydrocarbon chains, typically alkyl, hydroxyalkyl or ethoxylated alkyl groups, and X is a counter-ion (for example, compounds in which R1 is a C8-C22 alkyl group, preferably a Cs-Cio or C12-C14 alkyl group, R2 is a methyl group, and R3 and R4, which may be the same or different, are methyl or hydroxyethyl groups); and cationic esters (for example, choline esters).
For aqueous rinse added conditioners the level of cationic or nonionic softener varies from 3 to 30% more preferably from 5 to 25%. In super concentrates the botanical powders can be incorporated in predominately non-aqueous systems containing up to 60% fabric softening actives.
The fabric conditioning compositions of the invention can also contain adjuvants that are normal in the cosmetic, pharmaceutical and/or dermatological field, such as hydrophilic or lipophilic gelling agents, hydrophilic or lipophilic active agents, preserving agents, antioxidants, solvents, fragrances, fillers, screening agents, bactericides, odour absorbers, photobleaches (singlet oxygen or radical type) and
dyestuffs. The amounts of these various adjuvants are those conventionally used in the field under consideration and are, for example, from 0.01 to 20% of the total weight of the composition. Depending on their nature, these adjuvants can be introduced into the fatty phase and/or into the aqueous phase. Examples of suitable biocides for use in the present invention include Proxel (1 ,2- benzisothiazolin-3-one), available from, for example, Univar, Avecia and Uniqema; and Kathon CG (Methylchloroisothiazolinone and Methylisothiazolinone), available from Rhom and Haas.
Substrate
When used in laundering, the substrate may be any substrate onto which it is desirable to deposit the botanical particles and which is subjected to treatment such as a washing or rinsing process.
In particular, the substrate may be a textile fabric.
Treatment
The treatment of the substrate with the composition of the invention can be made by any suitable method such as washing, soaking or rinsing of the substrate but also by direct application such as spraying, rubbing, spotting, smearing, etc.
The treatment may involve contacting the substrate with an aqueous medium comprising the material of the invention.
The treatment may be provided as a spray composition e.g., for domestic (or industrial) application to fabric in a treatment separate from a conventional domestic laundering process. Suitable spray dispensing devices are disclosed in WO 96/15310 (Procter & Gamble) and are incorporated herein by reference.
The compositions of the invention may be used to provide a perfume and/or odour benefit, for example a reduction in malodour, to fabric.
Examples
Embodiments of the invention are now illustrated with reference to the following non-limiting examples. Unless stated otherwise, all proportions are given in weight percent by weight of the total composition.
Example 1 : Preparation of powders for use in the invention
(a) Centrifugal milling
Plant powders having a particle size within the claimed range were prepared using a Retsch ZM1000 Ultra Centrifugal Mill operating at a speed of 10,000 rpm. The mill was fitted with a 24 tooth rotor and a 0.12 mm screen.
To avoid heating of the materials during milling and potential loss or denaturing of the essential oils, they were co-mixed with dry-ice before being fed into the mill.
(b) Size fractionation
The fine powders from the centrifugal milling were then separated into different size fractions using Endecotts Ltd (England) Test Sieve.
Sieves of different aperture sizes were stacked on top of each other and 10 g of the powder placed on the top sieve and the sieve stack placed on a Retsch AS200 Sieve Shaker to allow the powder separation into different size fractions. The Retsch controls were set to shake for 5 minutes with 10 second vibration
intervals at an amplitude of 1.5 mm. The sieve stack was removed and manually tapped a few times between the intervals.
Some aromatic botanical powders became heavily agglomerated during the milling process. This made size fractionation by shaking impractical. However the powder could be brushed through the sieves with ease to allow separation into different size ranges.
Table 1 gives two examples of the size fractions that remained on each sieve from 10g of the starting powder.
Table 1 : Weight fractions remaining on the sieve from 10g of starting powder after 30 minutes of shaking (for ginger) and by brushing (for cardamom).
In all the following particle deposition experiments the < 45 μm size fractions were used.
Example 2: Softener compositions 1 to 4 comprising herbs and spices, according to the invention
Fabric conditioner compositions 1 to 4 in Table 2 containing herbs and spices according to the invention.
Table 2: Fabric softening of compositions 1 to 4
* Ginger, cardamom, and lavender pulverized and size fractionated as described above. Lavender 70%, chamomile 30%.
** The Ayurvedic blend comprising Liquorice 15%, Cinnamon 5%, Ginger 15%,
Orange peel 20%, Cardamom 40%, Cloves 5%.
** TEA quat is a cationic softener based on thethanolamine with tallow or hard tallow chains and 15% IPA as solvent.
*** Emanon SCR-PK is Sucrose Poly Ester softening oil derived from palm kernel oil.
Example 3: Evaluation of deposition of powders onto fabrics
To evaluate the deposition of the ultra-fine plant particles from a cationic softening solution during the rinse a Linitester was used, which simulates the tumbling action of an automatic washing machine on a scale of 100 ml.
The level of deposition of the particles from a rinse solution can be quantified by measuring the turbidity, or light transmission, of the rinse solution before and after the solution is contacted with the fabrics. Light transmission or turbidity measurements for this purpose cannot be conducted in the presence of cationic softeners because of their inherent milkiness. To simulate the cationic conditions of the rinse environment we therefore relied on a transparent micellar solution of a cationic surfactant (CTAC) and followed the procedure outlined below:-
1. Each Linitester pot was charged with 100 g of a solution comprising:-
• Cetylthmethylammonium chloride (CTAC) cationic surfactant (0.025g),
• Deposition polymer (from a polymer solution prepared earlier) (0.002 g), and
• Botanical powder (0.015 g).
2. The Linitester temperature was set to 400C.
3. After 5 minutes (i.e. before deposition) a 5 ml sample was taken for light transmission measurement.
4. A 20 x 20 cm2 fabric monitor was added to the pot.
5. The Linitester was then run for 20 minutes. 6. At end of run, the fabric was removed, spun and line dried.
7. A second 5 ml sample (i.e. after deposition) was withdrawn for transmission measurement.
8. The samples were analyzed on a spectrometer for percent transmission at 560nm.
Table 3 below summarizes the deposition from the rinse solution for mint particles < 45 μm in the presence of 3 different deposition polymers. Deposition is expressed as a percentage of the total amount of added particles in the solution.
To convert the % transmission to % deposition, a calibration curve was obtained for % transmission as a function of micropowder concentration.
Table 3: Deposition of mint particles onto cotton, polycotton and polyester in the presence of Softgel BDA, Locust Bean Gum and Polymer JR from rinse solutions containing 0.002 % polymeric deposition aids.
% Transmission at λ = 560 nm measured using a Hewlett Packard 8453 UVA/is
Spectrometer.
Softgel BDA (Avebe) is a cationic potato starch with low, 0.05%, degree of substitution (charge).
Ucare polymer JR-30M (Amerchol) is a cationic hydroxyethyl cellulose with a 1.5-
2.2% degree of substitution.
LBG (Sigma) is a non-ionic locust bean gum polysaccharide.
The level of delivery from the rinse solution simulating the washing machine condition is surprisingly good from the cationic solution alone compared to water. The polymers have improved the deposition except for polyester where the high charged density JR polymer has improved deposition over and above that of control CTAC.
Surprisingly LBG has improved the deposition on cotton and polycotton (positively charged substrates in CTAC) most likely through its affinity and recognition of cellulose units.
The wet monitors had a strong smell of the deposited particles which on drying had a faint remnant. On synthetics like polyester this was sufficient to mask the dusty vinegar smell of polyester fabric to a pleasant smell.
Claims
1. A fabric conditioning composition, which comprises:
a) at least one cationic or nonionic softening agent, b) a powder of botanical origin, and c) an optional polymeric deposition aid,
wherein the powder of botanical origin has a particle size of from 0.1 to 100 μm, preferably from 0.5 to 50 and most preferably from 1 to 45 μm.
2. A composition according to claim 1 , wherein the powder of botanical origin is selected from tubers, fruits, flowers, flower parts (calyx, stamen, etc), seeds, beans, pods, pith, woods, barks, stalks, stems, leaves, roots, rhizomes, husks, skins, rinds and mixtures thereof.
3. A composition according to claim 2, wherein the powder is selected from vanilla bean powder, ginger powder, cinnamon powder, cocoa powder, clove powder, cardamom powder, coriander powder, cumin powder, caraway powder, dill powder, turmeric powder, coffee bean powder, tea leaf powder, tea-tree powder, blackberry leaf powder, Lemon balm leaf powder, herb powders, chamomile powder, fennel powder, lime rind powder, lemon rind powder, grapefruit rind powder, tangerine rind powder, mandarin rind powder, lemon grass powder, apple pomace powder, Lemon myrtle powder, red clover powder, liquorice powder, chili powder, cyanine powder and mixtures thereof.
4. A composition according to claim 3, wherein the herbs are selected from rosemary, thyme, sweet bay, sage, tarragon, mint, basil, balm, lemon verbena, red bergamot, marjoram, lavender and oregano.
5. A composition according to claim 1 or claim 2, wherein the powder is selected from ginseng powder, rice husk flour, wheat husk flour, buckwheat husk flour and mixtures thereof.
6. A composition according to any claim 1 or claim 2, wherein the powder is an exfoliating agents selected from oat kernel flour, rice, rice bran flour and mixtures thereof.
7. A composition according to any preceding claim, wherein the powder of botanical origin is present in an amount of from 0.1 to 10 wt %, preferably from 0.3 to 5 wt %, most preferably from 0.5 to 3 wt % by weight of the total composition.
8. A composition according to any preceding claim, wherein the botanical powder is in native state, aged, matured, fermented or roasted.
9. A composition according to any preceding claim, wherein the polymeric deposition aid is present at a level of from 0.01 to 5 % by total weight of the composition.
10. A composition according to any preceding claim in which the polymeric deposition agent is a modified natural polymer or a synthetic polymer.
11. A composition according to claim 10, wherein the modified natural polymer is selected from the group consisting of cationic starches, cationic guars, cationic cellulose, and nonionic locust bean gums (LBGs).
12. A composition according to claim 11 , wherein the cationic starch is a cationically modified potato starch.
13. A composition according to claim 10, wherein the synthetic polymer is selected from the group consisting of polyethylene oxide (PEO), polyethylene imine (PEI), poly (acrylate), poly (acrylamide), polyethylene terephthalate-polyoxyethylene terephthalate (PET/POET) polymers and mixtures thereof.
14. A composition according to any preceding claim, wherein the cationic softening agent is a quaternary ammonium compound.
15. A composition according to claim 14, wherein the quaternary ammonium compound is an ester-linked triethanolamine (TEA) quaternary ammonium compound comprising a mixture of mono-, di- and tri-ester linked components.
16. A process for treating fabric comprising the step of treating a fabric article with a composition as defined in any preceding claim.
17. A method of preparing a composition as defined by any one of claims 1 to 15, comprising the step of pulverizing the powder of botanical origin to a particle size of from 0.1 to 100 μm, preferably from 0.5 to 50 and most preferably from 1 to 45 μm.
18. Use of a composition as defined in any one of claims 1 to 15 to provide a perfume and/or odour benefit to fabric.
Priority Applications (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| PL09756758T PL2366011T3 (en) | 2008-12-16 | 2009-11-26 | Improvements relating to fabric treatment compositions |
| EP09756758A EP2366011B1 (en) | 2008-12-16 | 2009-11-26 | Improvements relating to fabric treatment compositions |
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| EP08171732 | 2008-12-16 | ||
| PCT/EP2009/065893 WO2010069733A1 (en) | 2008-12-16 | 2009-11-26 | Improvements relating to fabric treatment compositions |
| EP09756758A EP2366011B1 (en) | 2008-12-16 | 2009-11-26 | Improvements relating to fabric treatment compositions |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| EP2366011A1 true EP2366011A1 (en) | 2011-09-21 |
| EP2366011B1 EP2366011B1 (en) | 2013-02-20 |
Family
ID=40568440
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| EP09756758A Not-in-force EP2366011B1 (en) | 2008-12-16 | 2009-11-26 | Improvements relating to fabric treatment compositions |
Country Status (8)
| Country | Link |
|---|---|
| EP (1) | EP2366011B1 (en) |
| CN (1) | CN102317427B (en) |
| AR (1) | AR074747A1 (en) |
| BR (1) | BRPI0922529A2 (en) |
| ES (1) | ES2406058T3 (en) |
| PL (1) | PL2366011T3 (en) |
| WO (1) | WO2010069733A1 (en) |
| ZA (1) | ZA201103931B (en) |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP5961915B2 (en) * | 2011-03-11 | 2016-08-03 | 高砂香料工業株式会社 | Coffee extract |
| CN104804890A (en) * | 2014-01-25 | 2015-07-29 | 无锡市拓普科技开发中心 | Decontaminating and deoiling agent for fabric dyeing |
| KR101637473B1 (en) * | 2014-02-25 | 2016-07-08 | 주식회사 엘지생활건강 | Fabric softener composition |
| CN104762811B (en) * | 2015-03-26 | 2017-01-25 | 海门市金麒麟红木投资发展有限公司 | Special natural softener for textiles and preparation method for special natural softener |
| WO2017107819A1 (en) * | 2015-12-22 | 2017-06-29 | Rhodia Operations | Compositions comprising quat and polysaccharides |
Family Cites Families (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CA2015736A1 (en) * | 1989-05-11 | 1990-11-11 | Diane G. Schmidt | Perfume particles for use in cleaning and conditioning compositions |
| US5898026A (en) * | 1989-09-22 | 1999-04-27 | Colgate Palmolive Company | Liquid crystal compositions |
| US5840669A (en) * | 1997-06-20 | 1998-11-24 | Gem Energy Industry Limited | Herbal dry cleaning powder composition |
| ES2320415T3 (en) * | 2000-12-21 | 2009-05-22 | Unilever N.V. | CLEANING COMPOSITIONS. |
| GB0202017D0 (en) * | 2002-01-29 | 2002-03-13 | Unilever Plc | Detergent compositions |
| GB0228354D0 (en) * | 2002-12-05 | 2003-01-08 | Unilever Plc | Detergent compositions |
| CN1667110A (en) * | 2004-03-09 | 2005-09-14 | 王旭 | Plant type environmental protection washing powder |
| GB0514716D0 (en) * | 2005-07-19 | 2005-08-24 | Unilever Plc | Process to form fabric softening particle,particle obtained and its use |
| MX2008014851A (en) * | 2006-06-19 | 2008-12-01 | Unilever Nv | Laundry composition. |
-
2009
- 2009-11-26 BR BRPI0922529A patent/BRPI0922529A2/en active Search and Examination
- 2009-11-26 ES ES09756758T patent/ES2406058T3/en active Active
- 2009-11-26 CN CN200980156838.7A patent/CN102317427B/en not_active Expired - Fee Related
- 2009-11-26 EP EP09756758A patent/EP2366011B1/en not_active Not-in-force
- 2009-11-26 PL PL09756758T patent/PL2366011T3/en unknown
- 2009-11-26 WO PCT/EP2009/065893 patent/WO2010069733A1/en not_active Ceased
- 2009-12-15 AR ARP090104865A patent/AR074747A1/en not_active Application Discontinuation
-
2011
- 2011-05-27 ZA ZA2011/03931A patent/ZA201103931B/en unknown
Non-Patent Citations (1)
| Title |
|---|
| See references of WO2010069733A1 * |
Also Published As
| Publication number | Publication date |
|---|---|
| PL2366011T3 (en) | 2013-08-30 |
| CN102317427B (en) | 2014-08-27 |
| EP2366011B1 (en) | 2013-02-20 |
| WO2010069733A1 (en) | 2010-06-24 |
| AR074747A1 (en) | 2011-02-09 |
| CN102317427A (en) | 2012-01-11 |
| ZA201103931B (en) | 2012-08-29 |
| BRPI0922529A2 (en) | 2016-08-09 |
| ES2406058T3 (en) | 2013-06-05 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| EP2366012B1 (en) | Improvements relating to fabric treatment compositions | |
| EP2038391A1 (en) | Washing, cleaning and care products | |
| CN106661513A (en) | Method for preparing stable composition with perfume | |
| EP2366011B1 (en) | Improvements relating to fabric treatment compositions | |
| JP2009507111A (en) | Consumer products with changing fragrance patterns | |
| EP2616582A2 (en) | Fabric softener compositions and methods of manufacture thereof | |
| CN104837977A (en) | Fabric conditioning composition | |
| DE102007019369A1 (en) | Photocatalytic material-containing particles | |
| CN104837976B (en) | Esterquat compositions having high triesterquat content | |
| AU2021315589B2 (en) | Fabric softening compositions | |
| EP1468068B1 (en) | Conditioning agent for protecting textiles | |
| EP4392524A1 (en) | Highly-branched cyclic dextrins as malodor control agents | |
| DE10039100A1 (en) | Deodorant textile treatment agent | |
| WO2002062934A1 (en) | Conditioning agent | |
| JP2008519779A (en) | Geranionitrile alternative | |
| CN1954059B (en) | Oily starch granules that release beneficial additives to the vehicle | |
| CN104837975B (en) | Ester quat compositions with high three ester quats content | |
| DE10203192A1 (en) | Liquid conditioner and substrate impregnated with conditioner, used in textile drying process, contains fluff-reducing component, preferably cellulose, hydrogel or acrylic polymer | |
| US20200048589A1 (en) | Garment laundering system | |
| JPH1036897A (en) | Concentrated liquid detergent composition | |
| DE102004019752A1 (en) | Aroma agents comprises at least metallically smelling aroma substance and/or contents that liberate aroma substances at least during application and/or after application, where the content, after release, spreads a metallic smell | |
| CN108350391B (en) | Compositions and methods for treating substrates | |
| BR112021020182B1 (en) | USE OF A COMPOSITION | |
| DE102006031897A1 (en) | Washing-, caring- or cleaning agent, useful for the cosmetic treatment of human body and for treating textiles and hard surfaces, and for refreshing air, comprises light-active bleaching agent containing titanium dioxide | |
| CN109963930A (en) | Glycerol ethoxylates as active ingredients in cosmetic stain removal |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PUAI | Public reference made under article 153(3) epc to a published international application that has entered the european phase |
Free format text: ORIGINAL CODE: 0009012 |
|
| 17P | Request for examination filed |
Effective date: 20110614 |
|
| AK | Designated contracting states |
Kind code of ref document: A1 Designated state(s): AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HR HU IE IS IT LI LT LU LV MC MK MT NL NO PL PT RO SE SI SK SM TR |
|
| DAX | Request for extension of the european patent (deleted) | ||
| GRAP | Despatch of communication of intention to grant a patent |
Free format text: ORIGINAL CODE: EPIDOSNIGR1 |
|
| GRAS | Grant fee paid |
Free format text: ORIGINAL CODE: EPIDOSNIGR3 |
|
| GRAA | (expected) grant |
Free format text: ORIGINAL CODE: 0009210 |
|
| AK | Designated contracting states |
Kind code of ref document: B1 Designated state(s): AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HR HU IE IS IT LI LT LU LV MC MK MT NL NO PL PT RO SE SI SK SM TR |
|
| REG | Reference to a national code |
Ref country code: GB Ref legal event code: FG4D |
|
| REG | Reference to a national code |
Ref country code: CH Ref legal event code: EP |
|
| REG | Reference to a national code |
Ref country code: AT Ref legal event code: REF Ref document number: 597577 Country of ref document: AT Kind code of ref document: T Effective date: 20130315 |
|
| REG | Reference to a national code |
Ref country code: IE Ref legal event code: FG4D |
|
| REG | Reference to a national code |
Ref country code: DE Ref legal event code: R096 Ref document number: 602009013472 Country of ref document: DE Effective date: 20130418 |
|
| REG | Reference to a national code |
Ref country code: ES Ref legal event code: FG2A Ref document number: 2406058 Country of ref document: ES Kind code of ref document: T3 Effective date: 20130605 |
|
| REG | Reference to a national code |
Ref country code: AT Ref legal event code: MK05 Ref document number: 597577 Country of ref document: AT Kind code of ref document: T Effective date: 20130220 |
|
| REG | Reference to a national code |
Ref country code: NL Ref legal event code: VDEP Effective date: 20130220 |
|
| REG | Reference to a national code |
Ref country code: LT Ref legal event code: MG4D |
|
| PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: NO Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20130520 Ref country code: IS Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20130620 Ref country code: SE Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20130220 Ref country code: LT Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20130220 Ref country code: BG Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20130520 Ref country code: AT Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20130220 |
|
| PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: GR Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20130521 Ref country code: PT Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20130620 Ref country code: LV Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20130220 Ref country code: FI Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20130220 Ref country code: SI Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20130220 Ref country code: BE Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20130220 |
|
| REG | Reference to a national code |
Ref country code: PL Ref legal event code: T3 |
|
| PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: HR Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20130220 |
|
| PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: CZ Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20130220 Ref country code: RO Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20130220 Ref country code: SK Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20130220 Ref country code: NL Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20130220 Ref country code: EE Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20130220 Ref country code: DK Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20130220 |
|
| PLBE | No opposition filed within time limit |
Free format text: ORIGINAL CODE: 0009261 |
|
| STAA | Information on the status of an ep patent application or granted ep patent |
Free format text: STATUS: NO OPPOSITION FILED WITHIN TIME LIMIT |
|
| 26N | No opposition filed |
Effective date: 20131121 |
|
| PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: PL Payment date: 20131104 Year of fee payment: 5 |
|
| REG | Reference to a national code |
Ref country code: DE Ref legal event code: R097 Ref document number: 602009013472 Country of ref document: DE Effective date: 20131121 |
|
| REG | Reference to a national code |
Ref country code: CH Ref legal event code: PL |
|
| PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: MC Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20130220 Ref country code: LI Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20131130 Ref country code: CH Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20131130 |
|
| REG | Reference to a national code |
Ref country code: IE Ref legal event code: MM4A |
|
| PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: IE Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20131126 |
|
| PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: SM Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20130220 |
|
| PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: CY Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20130220 |
|
| PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: MK Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20130220 Ref country code: LU Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20131126 Ref country code: HU Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT; INVALID AB INITIO Effective date: 20091126 |
|
| PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: MT Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20130220 |
|
| REG | Reference to a national code |
Ref country code: FR Ref legal event code: PLFP Year of fee payment: 7 |
|
| PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: PL Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20141126 |
|
| REG | Reference to a national code |
Ref country code: FR Ref legal event code: PLFP Year of fee payment: 8 |
|
| REG | Reference to a national code |
Ref country code: FR Ref legal event code: PLFP Year of fee payment: 9 |
|
| PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: DE Payment date: 20181120 Year of fee payment: 10 |
|
| PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: ES Payment date: 20181218 Year of fee payment: 10 Ref country code: IT Payment date: 20181126 Year of fee payment: 10 Ref country code: FR Payment date: 20181123 Year of fee payment: 10 Ref country code: GB Payment date: 20181120 Year of fee payment: 10 Ref country code: TR Payment date: 20181113 Year of fee payment: 10 |
|
| REG | Reference to a national code |
Ref country code: DE Ref legal event code: R119 Ref document number: 602009013472 Country of ref document: DE |
|
| GBPC | Gb: european patent ceased through non-payment of renewal fee |
Effective date: 20191126 |
|
| PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: GB Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20191126 Ref country code: FR Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20191130 Ref country code: DE Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20200603 Ref country code: IT Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20191126 |
|
| REG | Reference to a national code |
Ref country code: ES Ref legal event code: FD2A Effective date: 20210601 |
|
| PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: ES Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20191127 |
|
| PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: TR Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20191126 |