EP3894532B1 - An encapsulated dye composition and a method for preparation thereof - Google Patents
An encapsulated dye composition and a method for preparation thereof Download PDFInfo
- Publication number
- EP3894532B1 EP3894532B1 EP19812786.2A EP19812786A EP3894532B1 EP 3894532 B1 EP3894532 B1 EP 3894532B1 EP 19812786 A EP19812786 A EP 19812786A EP 3894532 B1 EP3894532 B1 EP 3894532B1
- Authority
- EP
- European Patent Office
- Prior art keywords
- dye
- composition
- clay
- silica
- mixture
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
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- 239000000203 mixture Substances 0.000 title claims description 291
- 238000000034 method Methods 0.000 title claims description 64
- 238000002360 preparation method Methods 0.000 title description 21
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 320
- 239000000975 dye Substances 0.000 claims description 250
- 239000000377 silicon dioxide Substances 0.000 claims description 130
- 239000004927 clay Substances 0.000 claims description 121
- IHZXTIBMKNSJCJ-UHFFFAOYSA-N 3-{[(4-{[4-(dimethylamino)phenyl](4-{ethyl[(3-sulfophenyl)methyl]amino}phenyl)methylidene}cyclohexa-2,5-dien-1-ylidene)(ethyl)azaniumyl]methyl}benzene-1-sulfonate Chemical compound C=1C=C(C(=C2C=CC(C=C2)=[N+](C)C)C=2C=CC(=CC=2)N(CC)CC=2C=C(C=CC=2)S([O-])(=O)=O)C=CC=1N(CC)CC1=CC=CC(S(O)(=O)=O)=C1 IHZXTIBMKNSJCJ-UHFFFAOYSA-N 0.000 claims description 55
- 239000000843 powder Substances 0.000 claims description 55
- 239000000463 material Substances 0.000 claims description 32
- -1 kerolite Inorganic materials 0.000 claims description 31
- 229920003088 hydroxypropyl methyl cellulose Polymers 0.000 claims description 30
- 239000000440 bentonite Substances 0.000 claims description 25
- 229910000278 bentonite Inorganic materials 0.000 claims description 25
- SVPXDRXYRYOSEX-UHFFFAOYSA-N bentoquatam Chemical compound O.O=[Si]=O.O=[Al]O[Al]=O SVPXDRXYRYOSEX-UHFFFAOYSA-N 0.000 claims description 24
- 239000003599 detergent Substances 0.000 claims description 23
- 238000002156 mixing Methods 0.000 claims description 23
- 239000011148 porous material Substances 0.000 claims description 21
- 239000011230 binding agent Substances 0.000 claims description 19
- 230000002209 hydrophobic effect Effects 0.000 claims description 17
- 229910052500 inorganic mineral Inorganic materials 0.000 claims description 16
- 239000011707 mineral Substances 0.000 claims description 16
- 238000002441 X-ray diffraction Methods 0.000 claims description 13
- 230000008569 process Effects 0.000 claims description 13
- 229910052906 cristobalite Inorganic materials 0.000 claims description 12
- 229910052681 coesite Inorganic materials 0.000 claims description 10
- 229910052682 stishovite Inorganic materials 0.000 claims description 10
- 229910052905 tridymite Inorganic materials 0.000 claims description 10
- 229920000642 polymer Polymers 0.000 claims description 9
- GUJOJGAPFQRJSV-UHFFFAOYSA-N dialuminum;dioxosilane;oxygen(2-);hydrate Chemical compound O.[O-2].[O-2].[O-2].[Al+3].[Al+3].O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O GUJOJGAPFQRJSV-UHFFFAOYSA-N 0.000 claims description 7
- 229910052901 montmorillonite Inorganic materials 0.000 claims description 7
- 229910000275 saponite Inorganic materials 0.000 claims description 6
- 239000004094 surface-active agent Substances 0.000 claims description 6
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 5
- 229910052710 silicon Inorganic materials 0.000 claims description 5
- 239000010703 silicon Substances 0.000 claims description 5
- 239000004113 Sepiolite Substances 0.000 claims description 4
- 239000001000 anthraquinone dye Substances 0.000 claims description 4
- VVIVVAIHOWVTHB-UHFFFAOYSA-L disodium;3-[[4-amino-9,10-dioxo-3-[2-sulfonato-4-(2,4,4-trimethylpentan-2-yl)phenoxy]anthracen-1-yl]amino]-2,4,6-trimethylbenzenesulfonate Chemical compound [Na+].[Na+].CC1=CC(C)=C(S([O-])(=O)=O)C(C)=C1NC1=CC(OC=2C(=CC(=CC=2)C(C)(C)CC(C)(C)C)S([O-])(=O)=O)=C(N)C2=C1C(=O)C1=CC=CC=C1C2=O VVIVVAIHOWVTHB-UHFFFAOYSA-L 0.000 claims description 4
- 229910052624 sepiolite Inorganic materials 0.000 claims description 4
- 235000019355 sepiolite Nutrition 0.000 claims description 4
- FJBHGWADYLMEJG-UHFFFAOYSA-M sodium;3-[[4-[[4-(diethylamino)phenyl]-[4-[ethyl-[(3-sulfonatophenyl)methyl]azaniumylidene]cyclohexa-2,5-dien-1-ylidene]methyl]-n-ethylanilino]methyl]benzenesulfonate Chemical compound [Na+].C1=CC(N(CC)CC)=CC=C1C(C=1C=CC(=CC=1)N(CC)CC=1C=C(C=CC=1)S([O-])(=O)=O)=C(C=C1)C=CC1=[N+](CC)CC1=CC=CC(S([O-])(=O)=O)=C1 FJBHGWADYLMEJG-UHFFFAOYSA-M 0.000 claims description 4
- 239000001003 triarylmethane dye Substances 0.000 claims description 4
- UWOFGIXNNCPENM-UHFFFAOYSA-N 3,3-difluoropentan-2-one Chemical compound CCC(F)(F)C(C)=O UWOFGIXNNCPENM-UHFFFAOYSA-N 0.000 claims description 3
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 3
- 125000000129 anionic group Chemical group 0.000 claims description 3
- 239000000987 azo dye Substances 0.000 claims description 3
- VNSBYDPZHCQWNB-UHFFFAOYSA-N calcium;aluminum;dioxido(oxo)silane;sodium;hydrate Chemical compound O.[Na].[Al].[Ca+2].[O-][Si]([O-])=O VNSBYDPZHCQWNB-UHFFFAOYSA-N 0.000 claims description 3
- 125000002091 cationic group Chemical group 0.000 claims description 3
- 229910000271 hectorite Inorganic materials 0.000 claims description 3
- KWLMIXQRALPRBC-UHFFFAOYSA-L hectorite Chemical compound [Li+].[OH-].[OH-].[Na+].[Mg+2].O1[Si]2([O-])O[Si]1([O-])O[Si]([O-])(O1)O[Si]1([O-])O2 KWLMIXQRALPRBC-UHFFFAOYSA-L 0.000 claims description 3
- 229910002027 silica gel Inorganic materials 0.000 claims description 3
- 239000000741 silica gel Substances 0.000 claims description 3
- 239000011734 sodium Substances 0.000 claims description 3
- 229910052708 sodium Inorganic materials 0.000 claims description 3
- VEPOHXYIFQMVHW-XOZOLZJESA-N 2,3-dihydroxybutanedioic acid (2S,3S)-3,4-dimethyl-2-phenylmorpholine Chemical compound OC(C(O)C(O)=O)C(O)=O.C[C@H]1[C@@H](OCCN1C)c1ccccc1 VEPOHXYIFQMVHW-XOZOLZJESA-N 0.000 claims description 2
- PCNDJXKNXGMECE-UHFFFAOYSA-N Phenazine Natural products C1=CC=CC2=NC3=CC=CC=C3N=C21 PCNDJXKNXGMECE-UHFFFAOYSA-N 0.000 claims description 2
- 229960000892 attapulgite Drugs 0.000 claims description 2
- 125000000664 diazo group Chemical group [N-]=[N+]=[*] 0.000 claims description 2
- 229910021485 fumed silica Inorganic materials 0.000 claims description 2
- 125000001434 methanylylidene group Chemical group [H]C#[*] 0.000 claims description 2
- 229910052625 palygorskite Inorganic materials 0.000 claims description 2
- 239000001007 phthalocyanine dye Substances 0.000 claims description 2
- 229910052903 pyrophyllite Inorganic materials 0.000 claims description 2
- IZMJMCDDWKSTTK-UHFFFAOYSA-N quinoline yellow Chemical compound C1=CC=CC2=NC(C3C(C4=CC=CC=C4C3=O)=O)=CC=C21 IZMJMCDDWKSTTK-UHFFFAOYSA-N 0.000 claims description 2
- 239000000454 talc Substances 0.000 claims description 2
- 229910052623 talc Inorganic materials 0.000 claims description 2
- AAAQKTZKLRYKHR-UHFFFAOYSA-N triphenylmethane Chemical compound C1=CC=CC=C1C(C=1C=CC=CC=1)C1=CC=CC=C1 AAAQKTZKLRYKHR-UHFFFAOYSA-N 0.000 claims description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 75
- 238000009472 formulation Methods 0.000 description 41
- 239000012071 phase Substances 0.000 description 35
- 239000002734 clay mineral Substances 0.000 description 34
- 235000012239 silicon dioxide Nutrition 0.000 description 33
- 239000002245 particle Substances 0.000 description 32
- 235000012216 bentonite Nutrition 0.000 description 24
- 229940092782 bentonite Drugs 0.000 description 23
- 239000004615 ingredient Substances 0.000 description 23
- 229910021647 smectite Inorganic materials 0.000 description 21
- 239000004744 fabric Substances 0.000 description 18
- 238000003756 stirring Methods 0.000 description 16
- 238000005538 encapsulation Methods 0.000 description 15
- 238000003860 storage Methods 0.000 description 15
- 238000012360 testing method Methods 0.000 description 15
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 14
- 239000000243 solution Substances 0.000 description 12
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 11
- 239000012153 distilled water Substances 0.000 description 11
- 239000008187 granular material Substances 0.000 description 11
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 10
- 239000011159 matrix material Substances 0.000 description 10
- 229960000907 methylthioninium chloride Drugs 0.000 description 10
- CXKWCBBOMKCUKX-UHFFFAOYSA-M methylene blue Chemical compound [Cl-].C1=CC(N(C)C)=CC2=[S+]C3=CC(N(C)C)=CC=C3N=C21 CXKWCBBOMKCUKX-UHFFFAOYSA-M 0.000 description 9
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 8
- 238000004458 analytical method Methods 0.000 description 7
- 238000005341 cation exchange Methods 0.000 description 7
- 229910052697 platinum Inorganic materials 0.000 description 7
- 238000005406 washing Methods 0.000 description 7
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 6
- 229910000281 calcium bentonite Inorganic materials 0.000 description 6
- 238000010521 absorption reaction Methods 0.000 description 5
- 125000000217 alkyl group Chemical group 0.000 description 5
- SAOKZLXYCUGLFA-UHFFFAOYSA-N bis(2-ethylhexyl) adipate Chemical compound CCCCC(CC)COC(=O)CCCCC(=O)OCC(CC)CCCC SAOKZLXYCUGLFA-UHFFFAOYSA-N 0.000 description 5
- 230000000740 bleeding effect Effects 0.000 description 5
- 150000001875 compounds Chemical class 0.000 description 5
- 239000006185 dispersion Substances 0.000 description 5
- 229910052742 iron Inorganic materials 0.000 description 5
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 4
- 239000004372 Polyvinyl alcohol Substances 0.000 description 4
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 4
- 239000002253 acid Substances 0.000 description 4
- 239000004411 aluminium Substances 0.000 description 4
- 229910052782 aluminium Inorganic materials 0.000 description 4
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 4
- 229910021486 amorphous silicon dioxide Inorganic materials 0.000 description 4
- 238000009835 boiling Methods 0.000 description 4
- 235000014113 dietary fatty acids Nutrition 0.000 description 4
- 239000000194 fatty acid Substances 0.000 description 4
- 229930195729 fatty acid Natural products 0.000 description 4
- KWIUHFFTVRNATP-UHFFFAOYSA-N glycine betaine Chemical compound C[N+](C)(C)CC([O-])=O KWIUHFFTVRNATP-UHFFFAOYSA-N 0.000 description 4
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 4
- 239000011777 magnesium Substances 0.000 description 4
- 229910052749 magnesium Inorganic materials 0.000 description 4
- 229920002689 polyvinyl acetate Polymers 0.000 description 4
- 239000011118 polyvinyl acetate Substances 0.000 description 4
- 229920002451 polyvinyl alcohol Polymers 0.000 description 4
- 230000011514 reflex Effects 0.000 description 4
- 239000013049 sediment Substances 0.000 description 4
- 238000001179 sorption measurement Methods 0.000 description 4
- 238000010186 staining Methods 0.000 description 4
- 229910021532 Calcite Inorganic materials 0.000 description 3
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 3
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 3
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 3
- 239000011575 calcium Substances 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- 229910052593 corundum Inorganic materials 0.000 description 3
- 239000001177 diphosphate Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 150000004665 fatty acids Chemical class 0.000 description 3
- 239000010433 feldspar Substances 0.000 description 3
- 239000011521 glass Substances 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 210000002741 palatine tonsil Anatomy 0.000 description 3
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 3
- 239000004926 polymethyl methacrylate Substances 0.000 description 3
- 239000010453 quartz Substances 0.000 description 3
- 238000012216 screening Methods 0.000 description 3
- FQENQNTWSFEDLI-UHFFFAOYSA-J sodium diphosphate Chemical compound [Na+].[Na+].[Na+].[Na+].[O-]P([O-])(=O)OP([O-])([O-])=O FQENQNTWSFEDLI-UHFFFAOYSA-J 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 235000019818 tetrasodium diphosphate Nutrition 0.000 description 3
- 229910001845 yogo sapphire Inorganic materials 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 238000004438 BET method Methods 0.000 description 2
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 2
- ROSDSFDQCJNGOL-UHFFFAOYSA-N Dimethylamine Chemical compound CNC ROSDSFDQCJNGOL-UHFFFAOYSA-N 0.000 description 2
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 2
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 2
- 206010027146 Melanoderma Diseases 0.000 description 2
- 229910019142 PO4 Inorganic materials 0.000 description 2
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 2
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 2
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 2
- 239000003463 adsorbent Substances 0.000 description 2
- DLHONNLASJQAHX-UHFFFAOYSA-N aluminum;potassium;oxygen(2-);silicon(4+) Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[O-2].[O-2].[O-2].[Al+3].[Si+4].[Si+4].[Si+4].[K+] DLHONNLASJQAHX-UHFFFAOYSA-N 0.000 description 2
- 239000002280 amphoteric surfactant Substances 0.000 description 2
- 239000003945 anionic surfactant Substances 0.000 description 2
- 239000011324 bead Substances 0.000 description 2
- 229960003237 betaine Drugs 0.000 description 2
- 238000004061 bleaching Methods 0.000 description 2
- 229910052791 calcium Inorganic materials 0.000 description 2
- 239000003093 cationic surfactant Substances 0.000 description 2
- 238000012512 characterization method Methods 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 239000003086 colorant Substances 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- ONCZQWJXONKSMM-UHFFFAOYSA-N dialuminum;disodium;oxygen(2-);silicon(4+);hydrate Chemical compound O.[O-2].[O-2].[O-2].[O-2].[O-2].[O-2].[O-2].[O-2].[O-2].[O-2].[O-2].[O-2].[Na+].[Na+].[Al+3].[Al+3].[Si+4].[Si+4].[Si+4].[Si+4] ONCZQWJXONKSMM-UHFFFAOYSA-N 0.000 description 2
- 238000001704 evaporation Methods 0.000 description 2
- 230000008020 evaporation Effects 0.000 description 2
- 239000012065 filter cake Substances 0.000 description 2
- 239000000706 filtrate Substances 0.000 description 2
- 229910052744 lithium Inorganic materials 0.000 description 2
- 229910044991 metal oxide Inorganic materials 0.000 description 2
- 150000004706 metal oxides Chemical class 0.000 description 2
- 238000013508 migration Methods 0.000 description 2
- 230000005012 migration Effects 0.000 description 2
- 239000002736 nonionic surfactant Substances 0.000 description 2
- 229910052652 orthoclase Inorganic materials 0.000 description 2
- 235000021317 phosphate Nutrition 0.000 description 2
- 229910052655 plagioclase feldspar Inorganic materials 0.000 description 2
- 239000011591 potassium Substances 0.000 description 2
- 229910052700 potassium Inorganic materials 0.000 description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
- 229910000280 sodium bentonite Inorganic materials 0.000 description 2
- 229940080314 sodium bentonite Drugs 0.000 description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 description 2
- 239000011780 sodium chloride Substances 0.000 description 2
- 229910052938 sodium sulfate Inorganic materials 0.000 description 2
- 235000011152 sodium sulphate Nutrition 0.000 description 2
- 238000013112 stability test Methods 0.000 description 2
- UIJMHOVIUFGSNF-UHFFFAOYSA-N 2-[dimethyl-[3-(undec-10-enoylamino)propyl]azaniumyl]acetate Chemical compound [O-]C(=O)C[N+](C)(C)CCCNC(=O)CCCCCCCCC=C UIJMHOVIUFGSNF-UHFFFAOYSA-N 0.000 description 1
- YJHSJERLYWNLQL-UHFFFAOYSA-N 2-hydroxyethyl(dimethyl)azanium;chloride Chemical compound Cl.CN(C)CCO YJHSJERLYWNLQL-UHFFFAOYSA-N 0.000 description 1
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- 102000008186 Collagen Human genes 0.000 description 1
- 108010035532 Collagen Proteins 0.000 description 1
- 229920000742 Cotton Polymers 0.000 description 1
- KKCBUQHMOMHUOY-UHFFFAOYSA-N Na2O Inorganic materials [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 description 1
- 239000004677 Nylon Substances 0.000 description 1
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 1
- 229920000388 Polyphosphate Polymers 0.000 description 1
- 238000003991 Rietveld refinement Methods 0.000 description 1
- 239000004115 Sodium Silicate Substances 0.000 description 1
- 229920002334 Spandex Polymers 0.000 description 1
- VBIIFPGSPJYLRR-UHFFFAOYSA-M Stearyltrimethylammonium chloride Chemical compound [Cl-].CCCCCCCCCCCCCCCCCC[N+](C)(C)C VBIIFPGSPJYLRR-UHFFFAOYSA-M 0.000 description 1
- ULUAUXLGCMPNKK-UHFFFAOYSA-N Sulfobutanedioic acid Chemical class OC(=O)CC(C(O)=O)S(O)(=O)=O ULUAUXLGCMPNKK-UHFFFAOYSA-N 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 125000002252 acyl group Chemical group 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 150000001343 alkyl silanes Chemical class 0.000 description 1
- 150000008051 alkyl sulfates Chemical class 0.000 description 1
- 150000001413 amino acids Chemical group 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 150000001491 aromatic compounds Chemical class 0.000 description 1
- 238000010009 beating Methods 0.000 description 1
- YSJGOMATDFSEED-UHFFFAOYSA-M behentrimonium chloride Chemical compound [Cl-].CCCCCCCCCCCCCCCCCCCCCC[N+](C)(C)C YSJGOMATDFSEED-UHFFFAOYSA-M 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000001768 carboxy methyl cellulose Substances 0.000 description 1
- 235000010948 carboxy methyl cellulose Nutrition 0.000 description 1
- 125000002057 carboxymethyl group Chemical group [H]OC(=O)C([H])([H])[*] 0.000 description 1
- 239000008112 carboxymethyl-cellulose Substances 0.000 description 1
- 229940105329 carboxymethylcellulose Drugs 0.000 description 1
- 239000012876 carrier material Substances 0.000 description 1
- WOWHHFRSBJGXCM-UHFFFAOYSA-M cetyltrimethylammonium chloride Chemical compound [Cl-].CCCCCCCCCCCCCCCC[N+](C)(C)C WOWHHFRSBJGXCM-UHFFFAOYSA-M 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 229920001688 coating polymer Polymers 0.000 description 1
- 229920001436 collagen Polymers 0.000 description 1
- 238000004590 computer program Methods 0.000 description 1
- 230000003750 conditioning effect Effects 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 230000001186 cumulative effect Effects 0.000 description 1
- IQDGSYLLQPDQDV-UHFFFAOYSA-N dimethylazanium;chloride Chemical compound Cl.CNC IQDGSYLLQPDQDV-UHFFFAOYSA-N 0.000 description 1
- REZZEXDLIUJMMS-UHFFFAOYSA-M dimethyldioctadecylammonium chloride Chemical compound [Cl-].CCCCCCCCCCCCCCCCCC[N+](C)(C)CCCCCCCCCCCCCCCCCC REZZEXDLIUJMMS-UHFFFAOYSA-M 0.000 description 1
- YGANSGVIUGARFR-UHFFFAOYSA-N dipotassium dioxosilane oxo(oxoalumanyloxy)alumane oxygen(2-) Chemical compound [O--].[K+].[K+].O=[Si]=O.O=[Al]O[Al]=O YGANSGVIUGARFR-UHFFFAOYSA-N 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 239000004664 distearyldimethylammonium chloride (DHTDMAC) Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000000705 flame atomic absorption spectrometry Methods 0.000 description 1
- 230000009969 flowable effect Effects 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 125000005456 glyceride group Chemical group 0.000 description 1
- 150000002334 glycols Chemical class 0.000 description 1
- 230000005661 hydrophobic surface Effects 0.000 description 1
- 239000001866 hydroxypropyl methyl cellulose Substances 0.000 description 1
- 235000010979 hydroxypropyl methyl cellulose Nutrition 0.000 description 1
- UFVKGYZPFZQRLF-UHFFFAOYSA-N hydroxypropyl methyl cellulose Chemical compound OC1C(O)C(OC)OC(CO)C1OC1C(O)C(O)C(OC2C(C(O)C(OC3C(C(O)C(O)C(CO)O3)O)C(CO)O2)O)C(CO)O1 UFVKGYZPFZQRLF-UHFFFAOYSA-N 0.000 description 1
- 229910052900 illite Inorganic materials 0.000 description 1
- 230000003116 impacting effect Effects 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000010348 incorporation Methods 0.000 description 1
- 238000007689 inspection Methods 0.000 description 1
- 239000011872 intimate mixture Substances 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- SUMDYPCJJOFFON-UHFFFAOYSA-N isethionic acid Chemical class OCCS(O)(=O)=O SUMDYPCJJOFFON-UHFFFAOYSA-N 0.000 description 1
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 1
- 229910052622 kaolinite Inorganic materials 0.000 description 1
- 238000004900 laundering Methods 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- HOVAGTYPODGVJG-UHFFFAOYSA-N methyl beta-galactoside Natural products COC1OC(CO)C(O)C(O)C1O HOVAGTYPODGVJG-UHFFFAOYSA-N 0.000 description 1
- 239000004570 mortar (masonry) Substances 0.000 description 1
- 229910052627 muscovite Inorganic materials 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- VGIBGUSAECPPNB-UHFFFAOYSA-L nonaaluminum;magnesium;tripotassium;1,3-dioxido-2,4,5-trioxa-1,3-disilabicyclo[1.1.1]pentane;iron(2+);oxygen(2-);fluoride;hydroxide Chemical compound [OH-].[O-2].[O-2].[O-2].[O-2].[O-2].[F-].[Mg+2].[Al+3].[Al+3].[Al+3].[Al+3].[Al+3].[Al+3].[Al+3].[Al+3].[Al+3].[K+].[K+].[K+].[Fe+2].O1[Si]2([O-])O[Si]1([O-])O2.O1[Si]2([O-])O[Si]1([O-])O2.O1[Si]2([O-])O[Si]1([O-])O2.O1[Si]2([O-])O[Si]1([O-])O2.O1[Si]2([O-])O[Si]1([O-])O2.O1[Si]2([O-])O[Si]1([O-])O2.O1[Si]2([O-])O[Si]1([O-])O2 VGIBGUSAECPPNB-UHFFFAOYSA-L 0.000 description 1
- 229920001778 nylon Polymers 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 230000000737 periodic effect Effects 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 239000001205 polyphosphate Substances 0.000 description 1
- 235000011176 polyphosphates Nutrition 0.000 description 1
- 229920000136 polysorbate Polymers 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 102000004169 proteins and genes Human genes 0.000 description 1
- 108090000623 proteins and genes Proteins 0.000 description 1
- 238000004445 quantitative analysis Methods 0.000 description 1
- 238000011158 quantitative evaluation Methods 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 238000010058 rubber compounding Methods 0.000 description 1
- 239000004576 sand Substances 0.000 description 1
- 150000004760 silicates Chemical class 0.000 description 1
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 1
- 229910052911 sodium silicate Inorganic materials 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000004611 spectroscopical analysis Methods 0.000 description 1
- 239000012798 spherical particle Substances 0.000 description 1
- 150000003871 sulfonates Chemical class 0.000 description 1
- 239000001117 sulphuric acid Substances 0.000 description 1
- 235000011149 sulphuric acid Nutrition 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 230000008961 swelling Effects 0.000 description 1
- 239000003760 tallow Substances 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- SOBHUZYZLFQYFK-UHFFFAOYSA-K trisodium;hydroxy-[[phosphonatomethyl(phosphonomethyl)amino]methyl]phosphinate Chemical compound [Na+].[Na+].[Na+].OP(O)(=O)CN(CP(O)([O-])=O)CP([O-])([O-])=O SOBHUZYZLFQYFK-UHFFFAOYSA-K 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/40—Dyes ; Pigments
-
- 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
- C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
- C11D17/0039—Coated compositions or coated components in the compositions, (micro)capsules
-
- 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
- C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
- C11D17/06—Powder; Flakes; Free-flowing mixtures; Sheets
-
- 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
- C11D3/02—Inorganic compounds ; Elemental compounds
- C11D3/12—Water-insoluble compounds
- C11D3/124—Silicon containing, e.g. silica, silex, quartz or glass beads
-
- 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
- C11D3/02—Inorganic compounds ; Elemental compounds
- C11D3/12—Water-insoluble compounds
- C11D3/124—Silicon containing, e.g. silica, silex, quartz or glass beads
- C11D3/1246—Silicates, e.g. diatomaceous earth
- C11D3/1253—Layer silicates, e.g. talcum, kaolin, clay, bentonite, smectite, montmorillonite, hectorite or attapulgite
- C11D3/126—Layer silicates, e.g. talcum, kaolin, clay, bentonite, smectite, montmorillonite, hectorite or attapulgite in solid compositions
-
- 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
- C11D7/00—Compositions of detergents based essentially on non-surface-active compounds
- C11D7/02—Inorganic compounds
- C11D7/20—Water-insoluble oxides
Definitions
- the present invention relates to an encapsulated dye composition for detergent powder.
- the present invention relates to non-bleeding dye composition encapsulated in a carrier, method for the preparation of said encapsulated dye composition and detergent compositions comprising the same.
- the colored particles used in the detergent powder mostly comprise of the colorant such as dye.
- the use of dye stuff as colored material is associated with flaws. Conventionally used colored particles tend to bleed the dye in the detergent powder and therefore tend to convert the colour of the white powder. This may affect the customer base for that particular detergent powder.
- the dye gets stuck in the fabric and does not shed off the fabric thereby affecting the fabrics.
- US-20110053823 discloses colored speckles comprising a porous material, a releasing agent, and a dye. This patent describes the colored speckles which quickly release color from the porous carrier using releasing agent and provide desirable color to the wash water.
- the releasing agent is selected from the group consisting of salt compounds, sugar compounds, alkoxylated aromatic compounds, glycols, high molecular weight alcohols, solvents having a boiling point above 60°C, and mixtures thereof.
- WO-0210327 discloses colored speckles comprising sodium chloride and colorant. It discloses presence of significant amount of hygroscopic material i.e. sodium chloride (at least 90%) in the matrix. This could cause the bleeding of dye in powder detergent under humidity in storage.
- the present disclosure provides the encapsulated dye composition that does not bleed in the detergent powder and shed off the fabric easily during washing.
- an encapsulated dye composition comprising a dye, a carrier consisting of a mixture of silica and clay and optionally a binder.
- the present invention provides methods for the preparation of the encapsulated dye composition.
- the present invention provides a detergent composition comprising encapsulated dye composition of the present invention.
- a method of laundering fabrics which includes a step of treating the fabrics with encapsulated dye composition of present invention.
- Weight percentages are calculated based upon total weight of the composition, unless otherwise indicated.
- an encapsulated dye composition comprising:
- the encapsulated composition of the present invention further comprises a binder such as a surfactant or a polymer.
- Suitable surfactant includes nonionic, anionic, cationic or amphoteric surfactants.
- suitable nonionic surfactants are polyoxyethylene sorbitan esters, polyoxyethylene sorbitol esters, polyoxyalkylene fatty alcohol ethers, polyoxyalkylene fatty acid esters, alkoxylated glycerides, polyoxyethylene methyl glucoside ester, alkyl polyglucosides, EO-PO blockpolymers or combinations of two or more thereof.
- anionic surfactants are sulfonates of alkylbenzene-sulfonates, alkanesulfonates, olefinsulfonates, alkyl ether sulfate, alkyl sulfate, sulfosuccinates, alkyl phosphates, alkyl ether phosphates, protein fatty acid condensates, perferably collagen hydrolysates modified with fatty acid, amino acid-based surfactants, isethionates, taurides, acyl lactylates, neutralized fatty acids or combinations of two or more thereof.
- cationic surfactants are esterquats, ditallow dimethyl ammonium chloride, C12/14 alkyl dimethyl benzyl ammonium chloride, alkyl dimethyl benzil ammonium chloride, cetyl trimethyl ammonium chloride, stearyl trimethyl ammonium chloride, behenyl trimethyl ammonium chloride alkyl hydroxyethyl dimethyl ammonium chloride, distearyl dimethyl ammonium chloride, dihydrogenated tallow fatty alkyl dimethyl ammonium chloride or combinations of two or more thereof.
- amphoteric surfactants are alkyl amphoacetate, alkyl amidopropyl betaine, alkyl amidopropyl dimethylamine betaine, undecylenamidopropyl betaine, alkyl dimethyl amine oxide.
- polymers examples include cellulosic polymers such as hydroxyl propyl methyl cellulose (HPMC), carboxy methyl cellulose (CMC); polyvinyl alcohol (PVA) polymers:polyvinyl acetate (PVAc) polymer and any combinations thereof.
- HPMC hydroxyl propyl methyl cellulose
- CMC carboxy methyl cellulose
- PVA polyvinyl alcohol
- PVAc polyvinyl acetate
- TiO 2 dispersion may be added to enhance whiteness.
- the binder is hydroxyl propyl methyl cellulose (HPMC).
- the dye is selected from the group consisting of azine dye for example anionic azine dye, cationic phenazine dye; triarylmethane dyes for example triphenyl-methane dye; anthraquinone dye; azo dye, disazo dye; phthalocyanine dye; quinophthalone dye; methine dye; hemicyanine dye; azo/azomethine complex dye; triphendioxazine dye or a mixture thereof.
- azine dye for example anionic azine dye, cationic phenazine dye
- triarylmethane dyes for example triphenyl-methane dye
- anthraquinone dye azo dye, disazo dye
- phthalocyanine dye quinophthalone dye
- methine dye hemicyanine dye
- azo/azomethine complex dye triphendioxazine dye or a mixture thereof.
- the dye is selected from the group consisting of Duasyn Acid Violet 4BN-IN (C.I. Acid Violet 17), Duasyn Violet SP-IN (C.I. Direct Violet 66), Duasyn Red N-6B-IN (C.I. Acid Violet 54), Duasyn Violet FBL-IN (C.I. Acid Violet 48), Duasyn Red Violet E2R-IN (C.I. Acid Violet 126) or mixtures of one or several of the afore mentioned dyes.
- Duasyn Acid Violet 4BN-IN C.I. Acid Violet 17
- Duasyn Violet SP-IN C.I. Direct Violet 66
- Duasyn Red N-6B-IN C.I. Acid Violet 54
- Duasyn Violet FBL-IN C.I. Acid Violet 48
- Duasyn Red Violet E2R-IN C.I. Acid Violet 126) or mixtures of one or several of the afore mentioned dyes.
- the silica is at least one selected from a silica gel, pyrogenic silica and precipitated silica.
- the precipitated silica is hydrophilic precipitated silica, hydrophobic precipitated silica or a mixture of both.
- Precipitated silica is typically produced by a precipitation of a sodium silicate with a mineral acid under neutral or slightly alkaline conditions.
- the filter cake of precipitated silica is dried and ground.
- Hydrophilic silica adsorbs water around the dye and hydrophobic silica does not allow water to get into touch with dye.
- the silica is hydrophilic precipitated silica.
- the hydrophilic silica only consists of SiO 2 and does not exhibit any surface modification and is wettable by water.
- the hydrophilic silica has a particle size d50 determined by laser diffraction of at least 50 ⁇ m, preferably at least 70 ⁇ m, mostly preferred at least 90 ⁇ m.
- the precipitated silica is selected from the group consisting of Sipernat ® 22; Sipernat ® 50 from Evonik Industries, Ibersil ® D 100 or Ibersil ® D100P form the IGE Group, Flo-Gard ® SC-72, Flo-Gard ® LPC from PPG.
- the precipitated silica of the inventive formulation is characterized by a high liquid absorption capacity, determined as DOA absorption number of at least 120 ml/100g, preferably at least 140 ml/100g, mostly preferred at least 160 ml/100g precipitated silica.
- DOA is the abbreviation for di-(2-ethylhexyl) adipate ( CAS-number 103-23-1 ).
- the test method is based on ISO 19246 ("Rubber compounding ingredients- Silica - Oil absorption of precipitated silica").
- Hydrophobic silica is not wettable by water and exhibits an organic surface modification created by chemical reactions with reactive alkylsilanes. The existence of such a surface modification can be proven by various analytical methods, e.g. the carbon content in an elemental analyzer following ISO 3262-19.
- the precipitated silica or one of the precipitated silica used in the formulations has a hydrophobic surface.
- the hydrophobic precipitated silica for the inventive formulation is characterized by a particle size d50 determined by laser diffraction (laser diffraction based on ISO 13320) of at least 5 ⁇ m, preferably at least 7 ⁇ m, mostly preferred at least 9 ⁇ m.
- hydrophilic silica is Sipernat ® D17 (d50 ⁇ 10 micron) or Sipernat ® D10 (particle size -d50 ⁇ 6.5 micron, free flowable) or combinations thereof.
- clay refers to both natural clays as well as modified clays. Modified clays in this context refers to natural clays which have been alkaline-activated or acid-activated. As used herein, the terms “clay minerals' or "special clay minerals” refer to natural clays.
- the clay used in the present composition is selected from the group consisting of natural clays comprising bentonite, montmorillonite, beidellite, saponite, hectorite, stevensite, kerolite-saponite, kerolite, talc, pyrophyllite, attapulgite, sepiolite; a mixture of natural silica with a bentonite;any modified clays; and any mixtures thereof.
- the clay is bentonite.
- an encapsulated dye composition comprising:
- the dye is used in the amount in the range of 1% to 30%, based on the total weight of the encapsulated dye composition, preferably 5% to 20%.
- the binder is used in the amount of 1 to 5% based on the total weight of the encapsulated dye composition.
- the silica is used in the amount of 30% to 75% based on the total weight of the encapsulated dye composition.
- the clay is used in the amount of 30% to 75 % based on the total weight of the encapsulated dye composition.
- the carrier has a silica to clay ratio of 1:4 to 4:1.
- the clay consisting of a smectite like a bentonite, beidellite, saponite, hectorite, stevensite, kerolite-saponite,is employed in the natural Ca-form or in a soda activated form.
- natural sodium bentonite is used as clay.
- Especially preferred clays are montmorillonites in the natural or soda activated form or mixtures thereof.
- the clay used is bentonite having cation exchange capacity in the range of 10 meq/100 g to 140 meq/100g.
- the clay used is bentonite having cation exchange capacity in the range of 20 meq/100 g to 130 meq/100g, preferably between 30 meq/100 g to 120 meq/100 g.
- a special clay mineral which consists of a mixture of smectite clay and an amorphous silica phase.
- the clay material is homogenous on a macroscopic scale, i.e.it is an intimate mixture of both phases.
- the special clay mineral used has a very high silicon content which is well above the silicon content of e.g. bentonite.
- the clay mineral does not have such a well ordered structure as layered silicates, e.g. bentonite, but preferably comprises large amounts of amorphous material. Such amorphous material is believed to be formed by amorphous SiO 2 .
- the special clay mineral of the present invention comprises a continuous phase of amorphous silica into which are inserted small platelet-shaped smectite phases.
- the platelets of the smectite phase are homogeneously distributed in the continuous amorphous silica phase and are firmly fixed therein.
- the special clay mineral of the present invention comprises a matrix-like network of amorphous SiO 2 into which very small clay particles are inserted and which may provide good protection of the dye to be encapsulated.
- the clay has more than 10 % of amorphous material as determined by quantitative X-ray diffraction analysis of the mineral phases of the clay material.
- the clay mineral of the present invention has a very high surface area in the range of 180 to 300 m 2 /g, preferably 185 to 280 m 2 /g, and more preferably 190 to 250 m 2 /g as determined by the BET method.
- the clay mineral of the present invention has high total pore volume of more than 0.5 ml/g.
- the clay mineral of the present invention has total pore volume of more than 0.55 ml/g, preferably more than 0.6 ml/g.
- the special clay mineral comprises a matrix of amorphous SiO 2 into which are inserted small particles of smectite minerals.
- the smectite particles are delaminated to a high degree and therefore provide a very high surface area.
- the clay has:
- the clay mineral used comprise a rigid, amorphous SiO 2 matrix into which are inserted very small clay particles or platelets.
- the clay mineral used in the method according to the invention comprises an amorphous phase of at least 10 wt.% of the total clay mineral, preferably at least 20 wt.%, more preferably at least 30 wt.% .
- the amorphous phase forms less than 90 wt.% of the total clay mineral.
- the amorphous phase forms less than 80 wt.% of the clay mineral.
- the clay mineral used in the method of the invention preferably comprises a smectite phase.
- the clay mineral preferably comprises less than 60 wt.%, more preferred less than 50 wt.%, particularly preferred less than 40 wt.% of a smectite phase.
- the smectite phase forms at least 10 wt.%, according to a further embodiment at least 20 wt.% of the clay mineral.
- the ratio of smectite phase to amorphous phase preferably is within a range of 2 to 0.5, more preferred 1.2 to 0.8.
- amorphous phase and the smectite phase further minerals may be present in the clay mineral, preferably within a range of 0.5 to 40 wt.%, more preferred 1 to 30 wt.%, particularly preferred 3 to 20 wt.%.
- Exemplary side minerals are quartz, cristobalite, feldspar and calcite. Other side minerals may also be present.
- the matrix of the clay mineral preferably formed from silica gel dilutes the smectite phase which leads, depending on the fraction of the smectite phase, to a lowering of the signal-to-noise ratio of typical reflections of smectite minerals e.g. the small angle reflections of montmorillonite are effected by the periodic distance between layers of the montmorillonite structure.
- the clay particles fixed in the SiO 2 -matrix are delaminated to a very high degree leading to a strong broadening of the corresponding diffraction peak.
- the amount of amorphous silica phase and smectite clay phase present in the clay mineral can be determined by quantitative X-ray-diffraction analysis. Details of such method are described e.g. in " Hand Book of Clay Science", F. Bergaya, B.K.G. Therry, G. Lagaly (Eds.), Elsevier, Oxford, Amsterdam, 2006, Chapter 12.1: I. Srodon, Identification and Quantitative Analysis of Clay Minerals ; " X-Ray Diffraction and the Identification and Analysis of Clay Minerals", D.M. Moora and R.C. Reaynolds, Oxford University Press, New York, 1997, pp 765 , included herein by reference.
- the XRD-diffractogram of the clay mineral of the present invention exhibit the reflexes which are hardly visible above noise.
- the signal to noise ratio for reflexes of the clay mineral in particular the smectite phase, is close to 1, preferably in the range of 1 to 1.2.
- the sharp reflexes may be visible in the diffractogram originating from impurities in the clay mineral, e.g. quartz. Such reflexes are not considered for determination of the signal/noise ratio.
- the clay mineral of the present invention which does not or does hardly show a 001 reflection indicating the layer distance within the crystal structure of bentonite particles.
- Hardly visible means that the signal-to-noise ratio of the 001 reflection of the smectite particles is preferably less than 1.2, particularly preferred is within a range of 1.0 to 1.1.
- the clay mineral has a sediment volume in water after 1 hour of less than 15 ml/2g, more preferred of less than 10 ml/2g and most preferred of less than 7 ml/2g.
- the clay mineral of the present invention in particular when mined from a natural source, preferably has a cation exchange capacity of more than 40 meq/100 g, particularly preferred of more than 45 meq/100 g and is most preferred selected within a range of 44 to 120 meq/100 g.
- high activity bleaching earth obtained by extracting a clay mineral with boiling strong acid is characterized by a very low cation exchange capacity of usually less than 40 meq/100 g and in most cases of less than 30 meq/100g.
- the modified clay used in the method according to the invention therefore can clearly be distinguished from such high performance bleaching earth.
- the clay of the present invention is characterized by a high content of SiO 2 determined after complete disintegration of the clay being above 62 wt.%, preferably above 64 wt.%, especially preferred above 66 wt.%.
- silicon other preferred metals or metal oxides may be contained in the clay. All percentages refer to a dry clay material dried to constant weight at 105°C.
- the clay preferably has a low aluminium content of, calculated as Al 2 O 3 , less than 15 wt.%, more preferred of less than 10 wt.%.
- the aluminium content, calculated as Al 2 O 3 according to an embodiment is more than 2 wt.%, according to a further embodiment more than 4 wt.%.
- the clay contains magnesium, calculated as MgO, in an amount of less than 7 wt.%, preferably of less than 6 wt.%, particularly preferred less than 5 wt.%. In one embodiment, the magnesium content is at least 2 wt.%
- the clay contains iron, calculated as Fe 2 O 3 , in amount of less than 8 wt.%.
- the iron content, calculated as Fe 2 O 3 may be less than 6 wt.% and according to a still further embodiment may be less than 5 wt.%.
- the clay may contain iron, calculated as Fe 2 O 3 , in an amount of at least 1 wt.%, and according to a still further embodiment in an amount of at least 2 wt.%.
- the present invention provides encapsulation of shading dyes comprising forming an encapsulation matrix consisting of mixture of silica for example hydrophilic silica or hydrophobic silica, clay, dye and binding agent for example surfactant or polymers to obtain stable encapsulated dye composition.
- the present invention provides method for the preparation of the encapsulated dye composition.
- the resulting encapsulated dye matrix is not bleeding the dye in powder detergent. Thus, it is not impacting white powder detergent color.
- the encapsulated dye is released in water as desired during the washing cycle.
- the method for preparation of encapsulated dye composition comprises
- the process comprises encapsulation of shading dye Duasyn Acid Violet 4BN-IN (C.I. Acid Violet 17), Duasyn Violet SP-IN (C.I. Direct Violet 66), Duasyn Red N-6B-IN (C.I. Acid Violet 54), Duasyn Violet FBL-IN (C.I. Acid Violet 48), Duasyn Red Violet E2R-IN (C.I. Acid Violet 126) or mixtures of one or several of the afore mentioned dye.
- Duasyn Acid Violet 4BN-IN C.I. Acid Violet 17
- Duasyn Violet SP-IN C.I. Direct Violet 66
- Duasyn Red N-6B-IN C.I. Acid Violet 54
- Duasyn Violet FBL-IN C.I. Acid Violet 48
- Duasyn Red Violet E2R-IN C.I. Acid Violet 126) or mixtures of one or several of the afore mentioned dye.
- the dye is suspended in water or used as press cake and is blended or absorbed on silica and bentonite blends to achieve white dye encapsulated powder.
- the process for preparation of encapsulated dye composition comprises mixing about 5-20% of dye with binder for example 1-5% of polymer or surfactant and blending this mixture with silica for example Sipernat ® D17 optionally followed by addition of about 5 to 30% of silica for example Ibersil ® D100P. The mixture is then blended thoroughly and the binder is added.
- the clay bentonites for example 20-40% of Laundrosil DGA and EXM 0242 is added to the blended mixture which will absorb on the shading dye loaded silica particles to give the encapsulated dye composition. This process involves manual/physical mixing of all the ingredients.
- the process for preparation of encapsulated dye composition comprises fluidized bed coating process to obtain encapsulated matrix of at least one suitable dye, silica, bentonite and binders which provides spherical particles having particle size of ⁇ 500 micron.
- dye is mixed with silica for example Sipernat ® 22 and clay in required composition, followed by addition of water to make dough. The dough is then extruded using extruder and spheronised to prepare granules.
- the spheronised granules are further coated using Fluidized Bed Processer with suitable binding or coating polymers such as Hydroxy Propyl Methyl Cellulose (HPMC), Carboxy methyl cellulolse (CMC), Polyvinyl alcohol (PVA), polyvinyl acetate (PVAc), and optionally TiO 2 dispersion for whiteness.
- suitable binding or coating polymers such as Hydroxy Propyl Methyl Cellulose (HPMC), Carboxy methyl cellulolse (CMC), Polyvinyl alcohol (PVA), polyvinyl acetate (PVAc), and optionally TiO 2 dispersion for whiteness.
- the encapsulated dye composition comprises a carrier consisting of a mixture of silica and clay, a dye encapsulated in the carrier and optionally a binder.
- the encapsulated dye of the present disclosure is found to be stable and did not leave stains on the fabric during the washing.
- the encapsulated dye composition when used in the detergent powder does not bleed into the powder and therefore it does not affect the white color of the detergent powder. Additionally, the encapsulated dye composition is released in water within few seconds with gentle stirring and can be easily shed off the clothes during washing.
- the present invention provides a laundry detergent composition
- encapsulated dye composition comprising carrier consisting of a mixture of silica and clay; and at least one dye encapsulated in the carrier.
- the present invention provides a detergent composition comprising encapsulated dye composition comprising:
- the test of the clay material was performed in the same way as described for the test bentonite. On the basis of the spent methylene blue solution was calculated the inner surface of the clay material. According to this method 381 mg methylene blue/g clay correspond to a content of 100 % montmorillonite.
- a vacuum cleaner connected with the sieve aspirates over a suction slit circling under the perforated sieve bottom all particles being finer than the inserted sieve being covered on top with an acrylic glass cover and leaves the coarser particles on the sieve.
- the experimental procedure was as follows: Depending on the product, between 5 and 25 g of air dried material was weighed in and was put on the sieve. Subsequently, the acrylic glass cover was put on the sieve and the machine was started. During air jet screening, the screening process can be facilitated by beating on the acrylic glass cover using the rubber hammer. Exhaustion time was between 1 and 5 minutes. The calculation of the dry screening residue in % is as follows: actual weight multiplied with 100 and divided by the initial weight.
- a calibrated 1l glass cylinder cut at the 1000 ml mark was weighed.
- the sample was poured into the cylinder in a single step such that the cylinder is completely filled and a cone was formed on top of the cylinder.
- the cone was removed with help of a ruler and material adhering to the outside of the cylinder was removed.
- the filled cylinder was weighed again and the apparent weight was obtained by subtracting the weight of the empty cylinder.
- Bentonite 1 Laundrosil ® DGA powder
- Bentonite 2 is a natural calcium/sodium bentonite (EX 0242, from Clariant). Both bentonites powder exhibit a dry sieve residue of less than 15 wt.% on sieve, with a mesh size of 45 ⁇ m.
- EX 0242 calcium/sodium bentonite
- Clay 3-5 (Clays with High content of SiO 2 / Mixed phase of bentonite and natural Silica) is provided in below table.
- Clay 3 is sold under the brand name Tonsil ® Supreme 118 FF.
- Table 2 Clay 3 4 5 Dry sieve residue on 45 ⁇ m (%) 49 55 5.2 Dry sieve residue on 63 ⁇ m (%) 35 40 38 apparent weight (g/l) 292 468 -- Methylene blue adsorption (mg/g sample) 106 152 179 Moisture content (%) 8 13 12 pH (10 wt.% in water) 7.6 9 8.1 cation exchange capacity (meq/100 g) 52 44 53.3 BET surface (m 2 /g) 208.4 238 248 micropore area (m 2 /g) 32.1 40 15 external surface (m 2 /g) 176.3 198 233 micropore volume (cm 3 /g) 0.016 0.02 0.01 cumulative pore volume (BJH) for pore diameter 1.7 - 300 nm (cm
- the quantitative X-ray diffraction analysis shows presence of smectite clay in clay 1 and 2 which are used in the method according to the invention.
- the dyes used for making encapsulated dye composition are listed in below table: Colour Index Name Chemical class Trade Name C.I. Acid Violet 17 Triaryl methane dye Duasyn Acid Violet 4BN-IN C.I. Direct Violet 66 Diazo dye Duasyn Violet SP-IN C.I. Acid Violet 54 Azo Dye Duasyn Red N-6B-IN C.I. Acid Violet 48 Anthraquinone Dye Duasyn Violet FBL-IN C.I. Acid Violet 126 Anthraquinone Dye Duasyn Red Violet E2R-IN
- silica used in the present invention having the properties as listed in the below table: Silica Name Supplier Properties Hydrophilic/ Hydrophobic Particle Size, d(50) ⁇ m DOA Absorption, ml/100g Tamped Density, g/l Sipernat ® 22 Evonik Hydrophilic 120 240 245 Sipernat ® D 17 Evonik Hydrophobic 10 - 150 Ibersil ® D 100 P IQESII S.A. Hydrophilic 200 245 230-280
- the encapsulated dye composition was a violet color formulation comprising -10% Duasyn Acid Violet 4BN-IN.
- the encapsulated dye composition was a violet color formulation comprising ⁇ 5% Duasyn Acid Violet 4BN-IN.
- the dye composition was a violet color formulation comprising ⁇ 1.2 % Duasyn Acid Violet 4BN-IN.
- Composition 1 is a composition of Composition 1:
- Composition 2 is a composition of Composition 2:
- the so obtained dye composition was a violet color formulation comprising 2% dye. It was observed that the color becomes more intense after storage at 45°C within a week. Formulation was found to release dye within few seconds in water with gentle stirring.
- Composition 3 is a composition of Composition 3:
- the so obtained dye composition was a violet color formulation comprising 5% dye. It was observed that the color becomes more intense after storage at 45°C within a week. Formulation was found to release dye within few seconds in water with gentle stirring.
- Composition 4 is a composition having Composition 4:
- the so obtained dye composition was a white color formulation comprising -0.5% dye, which was found to be stable at room temperature (RT) and at 45°C on storage for 2 months. Formulation was found to release dye within few seconds in water with gentle stirring.
- Composition 5 is a composition of Composition 5:
- the so obtained dye composition was a white color formulation comprising ⁇ 6% dye, which was found to be stable at RT and at 45°C on storage for 2 months. Formulation was found to release dye within few seconds in water with gentle stirring.
- composition 6 is a composition of Composition 6:
- the so obtained dye composition was a white color formulation comprising -0.6% dye, which was found to be stable at RT and at 45°C on storage for 2 months. Formulation was found to release dye within few seconds in water with gentle stirring.
- Composition 7 is a composition of Composition 7:
- the so obtained dye composition was a white color formulation comprising ⁇ 5% dye, which was found to be stable at RT and at 45°C on storage for 2 months. Formulation was found to release dye within few seconds in water with gentle stirring.
- Composition 8 is a composition of Composition 8:
- the so obtained dye composition was a white color formulation comprising -0.5% dye and was found to be stable at RT and at 45°C on storage for 2 months. Formulation was found to release dye within few seconds in water with gentle stirring.
- composition 9 is a composition of Composition 9:
- the so obtained dye composition was a white color formulation comprising ⁇ 7% dye, which was found to be stable at RT and at 45°C on storage for 2 months. Formulation was found to release dye within few seconds in water with gentle stirring.
- Composition 10 is a composition of Composition 10:
- the so obtained dye composition was a white color formulation comprising -10% dye, which was found to be stable at RT and at 45°C on storage for 2 months. Formulation was found to release dye within few seconds in water with gentle stirring.
- Composition 11 is a composition of Composition 11:
- the so obtained dye composition was a white color formulation comprising -10% dye, which was found to be stable at RT and at 45°C upon storage for 2 months. Formulation was found to release dye within few seconds in water with gentle stirring.
- the same formulation could be prepared using Duasyn Violet FBL-IN, Duasyn Red Violet E2R-IN or mixtures of two or three dyes mentioned in this example.
- Composition 12 The encapsulated dye composition is prepared using Fluidized Bed Process. Ingredients g % Phase A: Carrier Ibersil ® D 100 P 200 40 Clay 1 Laundrosil ® DGApowder 100 20 Clay 2 EXM 0242 ® 100 20 Phase B: Dye premix in water Duasyn Acid Violet 4BN-IN 100 20 Coating solution for Fluidized Bed Processing HPMC 4 TiO 2 (Viscofil White ARCL 30) in water 10
- Dye premix containing 100g of Duasyn Acid Violet 4BN-IN dye in water was mixed with a mixture of 200g of Ibersil ® D 100 P (Silicon Dioxide, Hydrophilic Silica with bigger particle size, d (50): ⁇ 200micron), 100g of Clay 1 Laundrosil ® DGA-powder (soda activated bentonite) and 100g of Clay 2 EX ® 0242 (natural Ca-bentonite) in Stephen mixer to obtain a mixture/dough cake.
- the mixture/dough cake was extruded through an extruder to obtain extrudates.
- the extrudates were spheronized to obtain granules. Obtained granules were further dried at 45°C in oven to remove any moisture.
- the granules were coated with the binder to obtain the encapsulated dye composition.
- the above Table shows the final composition of the encapsulated dye composition 12.
- Composition 13 is a composition of Composition 13:
- the so obtained dye composition was found to be a white color formulation comprising -18% Dye.
- the mixing was done manually for encapsulation.
- the dye composition was found to be stable at RT and at 45°C on storage for 2 months.
- the formulation was found to release dye within few seconds in water with gentle stirring.
- the dye composition was found stable in strength testing.
- Duasyn Acid Violet 4BN-IN for the premix
- Duasyn Violet SP-IN, Duasyn Red N-6B-IN, Duasyn Violet FBL-IN or Duasyn Red Violet E2R-IN or a mixture of two or several of the afore mentioned dye can be used for the preparation of the formulation mentioned in this example.
- composition 14 is a composition of Composition 14:
- Phase A Carrier Sipernat ® 22 68 34 Clay 1 Laundrosil DGA ® -powder 40 20 Clay 2 EXM 0242 ® 40 20 Phase B: Dye Premix Duasyn Violet SP-IN 40 20 HPMC 12 6 Total 200 100
- phase B dye premix containing Duasyn Violet SP-IN and HPMC
- Sipernat ® 22 Silicon Dioxide, Hydrophilic Silica
- Clay 1 Laundrosil DGA ® -powder silica
- Clay 2 EXM 0242 ® silica
- Stephen mixer 40g of Clay 1 Laundrosil DGA ® -powder (soda activated bentonite)
- Clay 2 EXM 0242 ® in Stephen mixer to obtain a mixture/dough cake.
- the mixture/dough cake was extruded through an extruder to obtain extrudates.
- the extrudates were spheronized to obtain granules. Obtained granules were further dried at 45°C in oven.
- the dye composition was found to be violet colored granules, which were found to be stable at RT and at 45°C storage for 2 months.
- the formulation was found to release dye within few seconds in water with gentle stirring.
- the dye composition was found to be stable in strength testing and no dye staining on cloth piece after washing.
- Similar formulations can be prepared with the shading dyes Duasyn Acid Violet 4BN-IN, Duasyn Red N-6B-IN, Duasyn Violet FBL-IN, Duasyn Red Violet E2R-IN or a mixture of two or several of the afore mentioned dyes.
- Dye premix containing Duasyn Acid Violet 4BN-IN in water was mixed with a mixture of Ibersil ® D 100 P (Silicon Dioxide, Hydrophilic Silica with bigger particle size, d (50): ⁇ 200micron), Laundrosil DGA-powder and EXM 0242 (bentonite/Clay) in Stephen mixer to obtain a mixture/dough cake.
- the mixture/dough cake was extruded through an extruder to obtain extrudates.
- the extrudates were spheronized to obtain granules. Obtained granules were further dried at 45°C in oven to remove any moisture.
- the granules were coated with HPMC and Viscofil White ARCL 30 to obtain the encapsulated dye composition.
- the final composition of the encapsulated dye is given in the above Table.
- the so obtained dye composition was off white color HPMC coated beads, which were found to be stable at RT and at 50°C on storage for 2 months.
- the formulation was found to release dye within few seconds in water with gentle stirring.
- Comparable Formulations can be prepared using Duasyn Violet SP-IN or Duasyn Red N-6B-IN, Duasyn Violet FBL-IN or Duasyn Red Violet E2R-IN or a mixture of two or several of the fore mentioned dyes.
- compositions of present invention are tested for their effects which are discussed as below.
- Open dish stability test was carried out to test the bleeding character of the encapsulated dye composition.
- the encapsulated dye composition was mixed with the white detergent powder and the resulting powder was kept in a petri dish and was left in the open environment for up to 2 months at room temperature and elevated temperature to check bleeding.
- the encapsulated dye compositions of the present invention prepared according to the above examples were used for the strength testing.
- the encapsulated sample was added to the powder detergent or components such as sodium sulfate.
- the sample was exposed to shear mimicking conditions of mixing dye with powder detergent.
- the sample was further observed after strength testing for migration of dye in powder detergent/sodium sulfate.
- the encapsulated dye composition of the present invention prepared according to the above examples were used for the dye staining test by conventional methods on the required fabrics such as woven polyester fabric, woven polycotton fabric, woven cotton CN-II fabric, elastane/nylon fabric.
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Description
- The present invention relates to an encapsulated dye composition for detergent powder. In particular the present invention relates to non-bleeding dye composition encapsulated in a carrier, method for the preparation of said encapsulated dye composition and detergent compositions comprising the same.
- Incorporation of the colored pigments in the detergent powder has increased for the past few years. The colored particles enhance the appearance of the detergent powder, as well as may have effect on the fabric conditioning.
- The colored particles used in the detergent powder mostly comprise of the colorant such as dye. The use of dye stuff as colored material is associated with flaws. Conventionally used colored particles tend to bleed the dye in the detergent powder and therefore tend to convert the colour of the white powder. This may affect the customer base for that particular detergent powder.
- Additionally, the dye gets stuck in the fabric and does not shed off the fabric thereby affecting the fabrics.
-
US-20110053823 discloses colored speckles comprising a porous material, a releasing agent, and a dye. This patent describes the colored speckles which quickly release color from the porous carrier using releasing agent and provide desirable color to the wash water. The releasing agent is selected from the group consisting of salt compounds, sugar compounds, alkoxylated aromatic compounds, glycols, high molecular weight alcohols, solvents having a boiling point above 60°C, and mixtures thereof. -
WO-0210327 - To overcome the disadvantages associated with the prior art, the present disclosure provides the encapsulated dye composition that does not bleed in the detergent powder and shed off the fabric easily during washing.
- According to an aspect the invention provides an encapsulated dye composition comprising a dye, a carrier consisting of a mixture of silica and clay and optionally a binder.
- In another aspect the present invention provides methods for the preparation of the encapsulated dye composition.
- According to another aspect the present invention provides a detergent composition comprising encapsulated dye composition of the present invention. According to another aspect the present invention provides a method of laundering fabrics which includes a step of treating the fabrics with encapsulated dye composition of present invention.
- For the purposes of the following detailed description, it is to be understood that the invention may assume various alternative variations and step sequences, except where expressly specified to the contrary.
- Thus, before describing the present invention in detail, it is to be understood that this invention is not limited to particularly exemplified process parameters that may of course, vary. It is also to be understood that the terminology used herein is for the purpose of describing particular embodiments of the invention only, and is not intended to limit the scope of the invention in any manner.
- The use of examples anywhere in this specification including examples of any terms discussed herein is illustrative only, and in no way limits the scope and meaning of the invention or of any exemplified term. Likewise, the invention is not limited to various embodiments given in this specification.
- Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention pertains.
- Weight percentages (wt.% or %wt) herein are calculated based upon total weight of the composition, unless otherwise indicated.
- It must be noted that, as used in this specification and the appended claims, the singular forms "a," "an" and "the" include plural referents unless the content clearly dictates otherwise.
- The terms "preferred" and "preferably" refer to embodiments of the invention that may afford certain benefits, under certain circumstances. However, other embodiments may also be preferred, under the same or other circumstances.
- Furthermore, the recitation of one or more preferred embodiments does not imply that other embodiments are not useful, and is not intended to exclude other embodiments from the scope of the invention.
- As used herein, the terms "comprising" "including," "having," "containing," "involving," and the like are to be understood to be open-ended, i.e., to mean including but not limited to.
- In one aspect of the present invention, there is provided an encapsulated dye composition comprising:
- a) a carrier material consisting of a mixture of silica and clay; and
- b) at least one dye entrapped in the carrier.
- The encapsulated composition of the present invention further comprises a binder such as a surfactant or a polymer. Suitable surfactant includes nonionic, anionic, cationic or amphoteric surfactants. Examples of suitable nonionic surfactants are polyoxyethylene sorbitan esters, polyoxyethylene sorbitol esters, polyoxyalkylene fatty alcohol ethers, polyoxyalkylene fatty acid esters, alkoxylated glycerides, polyoxyethylene methyl glucoside ester, alkyl polyglucosides, EO-PO blockpolymers or combinations of two or more thereof.
- Examples of anionic surfactants are sulfonates of alkylbenzene-sulfonates, alkanesulfonates, olefinsulfonates, alkyl ether sulfate, alkyl sulfate, sulfosuccinates, alkyl phosphates, alkyl ether phosphates, protein fatty acid condensates, perferably collagen hydrolysates modified with fatty acid, amino acid-based surfactants, isethionates, taurides, acyl lactylates, neutralized fatty acids or combinations of two or more thereof.
- Examples of cationic surfactants are esterquats, ditallow dimethyl ammonium chloride, C12/14 alkyl dimethyl benzyl ammonium chloride, alkyl dimethyl benzil ammonium chloride, cetyl trimethyl ammonium chloride, stearyl trimethyl ammonium chloride, behenyl trimethyl ammonium chloride alkyl hydroxyethyl dimethyl ammonium chloride, distearyl dimethyl ammonium chloride, dihydrogenated tallow fatty alkyl dimethyl ammonium chloride or combinations of two or more thereof.
- Examples of amphoteric surfactants are alkyl amphoacetate, alkyl amidopropyl betaine, alkyl amidopropyl dimethylamine betaine, undecylenamidopropyl betaine, alkyl dimethyl amine oxide.
- Examples of polymers are cellulosic polymers such as hydroxyl propyl methyl cellulose (HPMC), carboxy methyl cellulose (CMC); polyvinyl alcohol (PVA) polymers:polyvinyl acetate (PVAc) polymer and any combinations thereof. Optionally TiO2 dispersion may be added to enhance whiteness.
- In an embodiment of the present invention, the binder is hydroxyl propyl methyl cellulose (HPMC).
- In an embodiment of the present invention, the dye is selected from the group consisting of azine dye for example anionic azine dye, cationic phenazine dye; triarylmethane dyes for example triphenyl-methane dye; anthraquinone dye; azo dye, disazo dye; phthalocyanine dye; quinophthalone dye; methine dye; hemicyanine dye; azo/azomethine complex dye; triphendioxazine dye or a mixture thereof.
- In an embodiment the dye is selected from the group consisting of Duasyn Acid Violet 4BN-IN (C.I. Acid Violet 17), Duasyn Violet SP-IN (C.I. Direct Violet 66), Duasyn Red N-6B-IN (C.I. Acid Violet 54), Duasyn Violet FBL-IN (C.I. Acid Violet 48), Duasyn Red Violet E2R-IN (C.I. Acid Violet 126) or mixtures of one or several of the afore mentioned dyes.
- In an embodiment, the silica is at least one selected from a silica gel, pyrogenic silica and precipitated silica.
- In an embodiment the precipitated silica is hydrophilic precipitated silica, hydrophobic precipitated silica or a mixture of both. Precipitated silica is typically produced by a precipitation of a sodium silicate with a mineral acid under neutral or slightly alkaline conditions. For the final application the filter cake of precipitated silica is dried and ground. Hydrophilic silica adsorbs water around the dye and hydrophobic silica does not allow water to get into touch with dye.
- In an embodiment of the present invention, the silica is hydrophilic precipitated silica.
- The hydrophilic silica only consists of SiO2 and does not exhibit any surface modification and is wettable by water.
- In a preferred embodiment of the present invention, the hydrophilic silica has a particle size d50 determined by laser diffraction of at least 50 µm, preferably at least 70 µm, mostly preferred at least 90 µm.
- The precipitated silica is selected from the group consisting of Sipernat® 22; Sipernat® 50 from Evonik Industries, Ibersil® D 100 or Ibersil® D100P form the IGE Group, Flo-Gard® SC-72, Flo-Gard® LPC from PPG. The precipitated silica of the inventive formulation is characterized by a high liquid absorption capacity, determined as DOA absorption number of at least 120 ml/100g, preferably at least 140 ml/100g, mostly preferred at least 160 ml/100g precipitated silica. DOA is the abbreviation for di-(2-ethylhexyl) adipate (CAS-number 103-23-1). The test method is based on ISO 19246 ("Rubber compounding ingredients- Silica - Oil absorption of precipitated silica").
- Hydrophobic silica is not wettable by water and exhibits an organic surface modification created by chemical reactions with reactive alkylsilanes. The existence of such a surface modification can be proven by various analytical methods, e.g. the carbon content in an elemental analyzer following ISO 3262-19. In an embodiment the precipitated silica or one of the precipitated silica used in the formulations has a hydrophobic surface.
- The hydrophobic precipitated silica for the inventive formulation is characterized by a particle size d50 determined by laser diffraction (laser diffraction based on ISO 13320) of at least 5 µm, preferably at least 7 µm, mostly preferred at least 9 µm.
- In an embodiment the hydrophilic silica is Sipernat® D17 (d50 ~10 micron) or Sipernat® D10 (particle size -d50 ~6.5 micron, free flowable) or combinations thereof.
- As used herein, the term "clay" refers to both natural clays as well as modified clays. Modified clays in this context refers to natural clays which have been alkaline-activated or acid-activated. As used herein, the terms "clay minerals' or "special clay minerals" refer to natural clays.
- In an embodiment the clay used in the present composition is selected from the group consisting of natural clays comprising bentonite, montmorillonite, beidellite, saponite, hectorite, stevensite, kerolite-saponite, kerolite, talc, pyrophyllite, attapulgite, sepiolite; a mixture of natural silica with a bentonite;any modified clays; and any mixtures thereof..
- In an embodiment of the present invention, the clay is bentonite.
- In another aspect of the present disclosure, there is provided an encapsulated dye composition comprising:
- a) a carrier consisting of a mixture of silica and clay
- b) a binder and
- c) dye
- In an embodiment, the dye is used in the amount in the range of 1% to 30%, based on the total weight of the encapsulated dye composition, preferably 5% to 20%.
- In an embodiment, the binder is used in the amount of 1 to 5% based on the total weight of the encapsulated dye composition.
- In an embodiment, the silica is used in the amount of 30% to 75% based on the total weight of the encapsulated dye composition.
- In an embodiment, the clay is used in the amount of 30% to 75 % based on the total weight of the encapsulated dye composition.
- In an embodiment, the carrier has a silica to clay ratio of 1:4 to 4:1.
- In an embodiment the present invention provides an encapsulated dye composition comprising:
- a) a carrier comprising 30% to 75% by weight of silica and 20% to 40% by weight of clay
- b) 1 to 5% by weight of binder and
- c) 1 to 20% by weight of dye
- The clay consisting of a smectite like a bentonite, beidellite, saponite, hectorite, stevensite, kerolite-saponite,is employed in the natural Ca-form or in a soda activated form.
- In another embodiment natural sodium bentonite is used as clay. Especially preferred clays are montmorillonites in the natural or soda activated form or mixtures thereof.
- In an embodiment the clay used is bentonite having cation exchange capacity in the range of 10 meq/100 g to 140 meq/100g.
- In an embodiment the clay used is bentonite having cation exchange capacity in the range of 20 meq/100 g to 130 meq/100g, preferably between 30 meq/100 g to 120 meq/100 g.
- In an embodiment a special clay mineral is used, which consists of a mixture of smectite clay and an amorphous silica phase. The clay material is homogenous on a macroscopic scale, i.e.it is an intimate mixture of both phases.
- The special clay mineral used has a very high silicon content which is well above the silicon content of e.g. bentonite. The clay mineral does not have such a well ordered structure as layered silicates, e.g. bentonite, but preferably comprises large amounts of amorphous material. Such amorphous material is believed to be formed by amorphous SiO2.
- The special clay mineral of the present invention comprises a continuous phase of amorphous silica into which are inserted small platelet-shaped smectite phases. The platelets of the smectite phase are homogeneously distributed in the continuous amorphous silica phase and are firmly fixed therein.
- The special clay mineral of the present invention comprises a matrix-like network of amorphous SiO2 into which very small clay particles are inserted and which may provide good protection of the dye to be encapsulated.
- In one embodiment, the clay has more than 10 % of amorphous material as determined by quantitative X-ray diffraction analysis of the mineral phases of the clay material.
- In one embodiment, the clay mineral of the present invention has a very high surface area in the range of 180 to 300 m2/g, preferably 185 to 280 m2/g, and more preferably 190 to 250 m2/g as determined by the BET method.
- In an embodiment the clay mineral of the present invention has high total pore volume of more than 0.5 ml/g.
- In an embodiment the clay mineral of the present invention has total pore volume of more than 0.55 ml/g, preferably more than 0.6 ml/g.
- Inventors believe, the large pore volume of the clay mineral allows rapid access of the dye particles or molecules to the pores, in which they are protected. The special clay mineral comprises a matrix of amorphous SiO2 into which are inserted small particles of smectite minerals. The smectite particles are delaminated to a high degree and therefore provide a very high surface area.
- In one embodiment, the clay has:
- a. a surface area of more than 120m2/g;
- b. a total pore volume of more than 0.35 ml/g;
- c. a silicon content, calculated as SiO2, of at least 60 wt.%.
- Through the large pores provided in the clay mineral, which are in particular situated in the SiO2-matrix, a rapid access of the dye to the clay particles inserted in the SiO2-matrix is possible throughout the absorption process as the clay material does hardly swell during adsorption of dye.
- In an embodiment the clay mineral used comprise a rigid, amorphous SiO2 matrix into which are inserted very small clay particles or platelets.
- Preferably, the clay mineral used in the method according to the invention comprises an amorphous phase of at least 10 wt.% of the total clay mineral, preferably at least 20 wt.%, more preferably at least 30 wt.% .
- In an embodiment of the invention, the amorphous phase forms less than 90 wt.% of the total clay mineral.
- In another embodiment of the invention, the amorphous phase forms less than 80 wt.% of the clay mineral.
- Besides the amorphous phase, the clay mineral used in the method of the invention preferably comprises a smectite phase. The clay mineral preferably comprises less than 60 wt.%, more preferred less than 50 wt.%, particularly preferred less than 40 wt.% of a smectite phase.
- According to an embodiment of the invention, the smectite phase forms at least 10 wt.%, according to a further embodiment at least 20 wt.% of the clay mineral.
- In an embodiment the ratio of smectite phase to amorphous phase preferably is within a range of 2 to 0.5, more preferred 1.2 to 0.8.
- Besides the amorphous phase and the smectite phase further minerals may be present in the clay mineral, preferably within a range of 0.5 to 40 wt.%, more preferred 1 to 30 wt.%, particularly preferred 3 to 20 wt.%. Exemplary side minerals are quartz, cristobalite, feldspar and calcite. Other side minerals may also be present.
- In accordance with the present invention, the matrix of the clay mineral, preferably formed from silica gel dilutes the smectite phase which leads, depending on the fraction of the smectite phase, to a lowering of the signal-to-noise ratio of typical reflections of smectite minerals e.g. the small angle reflections of montmorillonite are effected by the periodic distance between layers of the montmorillonite structure. Further, the clay particles fixed in the SiO2-matrix are delaminated to a very high degree leading to a strong broadening of the corresponding diffraction peak.
- The amount of amorphous silica phase and smectite clay phase present in the clay mineral can be determined by quantitative X-ray-diffraction analysis. Details of such method are described e.g. in "Hand Book of Clay Science", F. Bergaya, B.K.G. Therry, G. Lagaly (Eds.), Elsevier, Oxford, Amsterdam, 2006, Chapter 12.1: I. Srodon, Identification and Quantitative Analysis of Clay Minerals; "X-Ray Diffraction and the Identification and Analysis of Clay Minerals", D.M. Moora and R.C. Reaynolds, Oxford University Press, New York, 1997, pp 765, included herein by reference.
- For application of this method to the analysis of mineral samples, one can refer to e.g. D.K. McCarthy "Quantitative Mineral Analysis of Clay-bearing Mixtures", in: "The Reynolds Cup" Contest. IUCr CPD Newsletter, 27, 2002, 12- 16.
- The quantitative determination of the different minerals in unknown samples is done by commercially available software, e.g. "Seifert AutoQuan" available from Seifert/GE Inspection Technologies, Ahrensburg, Germany.
- The XRD-diffractogram of the clay mineral of the present invention exhibit the reflexes which are hardly visible above noise.
- In an embodiment of the present invention, the signal to noise ratio for reflexes of the clay mineral, in particular the smectite phase, is close to 1, preferably in the range of 1 to 1.2. However, the sharp reflexes may be visible in the diffractogram originating from impurities in the clay mineral, e.g. quartz. Such reflexes are not considered for determination of the signal/noise ratio.
- In an embodiment, the clay mineral of the present invention, which does not or does hardly show a 001 reflection indicating the layer distance within the crystal structure of bentonite particles. Hardly visible means that the signal-to-noise ratio of the 001 reflection of the smectite particles is preferably less than 1.2, particularly preferred is within a range of 1.0 to 1.1.
- Preferably the clay mineral has a sediment volume in water after 1 hour of less than 15 ml/2g, more preferred of less than 10 ml/2g and most preferred of less than 7 ml/2g.
- In an embodiment the clay mineral of the present invention, in particular when mined from a natural source, preferably has a cation exchange capacity of more than 40 meq/100 g, particularly preferred of more than 45 meq/100 g and is most preferred selected within a range of 44 to 120 meq/100 g.
- In an embodiment high activity bleaching earth obtained by extracting a clay mineral with boiling strong acid is characterized by a very low cation exchange capacity of usually less than 40 meq/100 g and in most cases of less than 30 meq/100g.
- The modified clay used in the method according to the invention therefore can clearly be distinguished from such high performance bleaching earth.
- In an embodiment the clay of the present invention is characterized by a high content of SiO2 determined after complete disintegration of the clay being above 62 wt.%, preferably above 64 wt.%, especially preferred above 66 wt.%. Besides silicon other preferred metals or metal oxides may be contained in the clay. All percentages refer to a dry clay material dried to constant weight at 105°C.
- The claypreferably has a low aluminium content of, calculated as Al2O3, less than 15 wt.%, more preferred of less than 10 wt.%. The aluminium content, calculated as Al2O3, according to an embodiment is more than 2 wt.%, according to a further embodiment more than 4 wt.%.
- In an embodiment the clay contains magnesium, calculated as MgO, in an amount of less than 7 wt.%, preferably of less than 6 wt.%, particularly preferred less than 5 wt.%. In one embodiment, the magnesium content is at least 2 wt.%
- In an embodiment the clay contains iron, calculated as Fe2O3, in amount of less than 8 wt.%. According to a further embodiment, the iron content, calculated as Fe2O3, may be less than 6 wt.% and according to a still further embodiment may be less than 5 wt.%. According to a further embodiment, the clay may contain iron, calculated as Fe2O3, in an amount of at least 1 wt.%, and according to a still further embodiment in an amount of at least 2 wt.%.
- In an embodiment the present invention provides encapsulation of shading dyes comprising forming an encapsulation matrix consisting of mixture of silica for example hydrophilic silica or hydrophobic silica, clay, dye and binding agent for example surfactant or polymers to obtain stable encapsulated dye composition.
- In another aspect the present invention provides method for the preparation of the encapsulated dye composition.
- The resulting encapsulated dye matrix is not bleeding the dye in powder detergent. Thus, it is not impacting white powder detergent color. The encapsulated dye is released in water as desired during the washing cycle.
- The method for preparation of encapsulated dye composition comprises
- a) mixing the dye with the binder to obtain a mixture.
- b) blending the mixture with silica and clay as carrier to obtain the encapsulated dye composition.
- In an embodiment the process comprises encapsulation of shading dye Duasyn Acid Violet 4BN-IN (C.I. Acid Violet 17), Duasyn Violet SP-IN (C.I. Direct Violet 66), Duasyn Red N-6B-IN (C.I. Acid Violet 54), Duasyn Violet FBL-IN (C.I. Acid Violet 48), Duasyn Red Violet E2R-IN (C.I. Acid Violet 126) or mixtures of one or several of the afore mentioned dye.
- In another embodiment the dye is suspended in water or used as press cake and is blended or absorbed on silica and bentonite blends to achieve white dye encapsulated powder.
- Typically, the process for preparation of encapsulated dye composition comprises mixing about 5-20% of dye with binder for example 1-5% of polymer or surfactant and blending this mixture with silica for example Sipernat® D17 optionally followed by addition of about 5 to 30% of silica for example Ibersil® D100P. The mixture is then blended thoroughly and the binder is added. The clay bentonites for example 20-40% of Laundrosil DGA and EXM 0242 is added to the blended mixture which will absorb on the shading dye loaded silica particles to give the encapsulated dye composition. This process involves manual/physical mixing of all the ingredients.
- In another embodiment the process for preparation of encapsulated dye composition comprises fluidized bed coating process to obtain encapsulated matrix of at least one suitable dye, silica, bentonite and binders which provides spherical particles having particle size of ~ 500 micron. Preferably, dye is mixed with silica for example Sipernat ® 22 and clay in required composition, followed by addition of water to make dough. The dough is then extruded using extruder and spheronised to prepare granules. The spheronised granules are further coated using Fluidized Bed Processer with suitable binding or coating polymers such as Hydroxy Propyl Methyl Cellulose (HPMC), Carboxy methyl cellulolse (CMC), Polyvinyl alcohol (PVA), polyvinyl acetate (PVAc), and optionally TiO2 dispersion for whiteness.
- In accordance with the present invention the encapsulated dye composition comprises a carrier consisting of a mixture of silica and clay, a dye encapsulated in the carrier and optionally a binder. The encapsulated dye of the present disclosure is found to be stable and did not leave stains on the fabric during the washing.
- Surprisingly, the encapsulated dye composition, when used in the detergent powder does not bleed into the powder and therefore it does not affect the white color of the detergent powder. Additionally, the encapsulated dye composition is released in water within few seconds with gentle stirring and can be easily shed off the clothes during washing.
- In another aspect the present invention provides a laundry detergent composition comprising encapsulated dye composition comprising carrier consisting of a mixture of silica and clay; and at least one dye encapsulated in the carrier.
- In another aspect the present invention provides a detergent composition comprising encapsulated dye composition comprising:
- a) a carrier comprising 30% to 75% by weight of silica and 20% to 40% by weight of clay
- b) 1 to 5% by weight of binder and
- c) 1 to 20% by weight of dye
- The following examples are provided to better illustrate the present invention and are not to be interpreted in any way as limiting the scope of the invention. All specific compositions, materials, and methods described below, in whole or in part, fall within the scope of the invention. These specific compositions, materials, and methods are not intended to limit the invention, but merely to illustrate specific embodiments falling within the scope of the invention. One skilled in the art may develop equivalent compositions, materials, and methods without the exercise of inventive capacity and without departing from the scope of the invention. It will be understood that many variations can be made in the procedures herein described while still remaining within the bounds of the invention. It is the intention of the inventors that such variations are included within the scope of the invention.
- Following examples disclose various encapsulated dye composition of the present invention and comparative dye compositions as comparative examples.
- Materials and methods:
Different clays used in the present invention were characterized as follows. - The physical features used to characterize the adsorbents were ddetermined as follows:
- (i) Specific surface and pore volume:
Specific surface and pore volume was determined by the BET-method (single-point method using nitrogen, according to DIN 66131) with an automatic nitrogen-porosimeter of Micrometrics, type ASAP 2010. The pore volume was determined using the BJH-method (E.P. Barrett, L.G. Joyner, P.P. Hienda, J. Am. Chem. Soc. 73 (1951) 373). Pore volumes of defined ranges of pore diameter were measured by summing up incremental pore volumina, which were determined from the adsorption isotherm according BJH. The total pore volume refers to pores having a diameter of 2 to 350 nm. The measurements provide as additional parameters the micropore surface, the external surface and the micropore volume. Micropores refer to pores having a pore diameter of up to 2 nm according to Pure & Applied Chem. Vol. 51, 603 - 619 (1985). - (ii) Humidity:
The amount of water present in the clay material at a temperature of 105°C was determined according to DIN/ISO-787/2. - (iii) Silicate analysis/Analysis of the chemical composition (expressed in terms of SiO2 and metal oxides):
- a) Sample disintegration: A 10 g sample of the clay material was comminuted to obtain a fine powder which was dried in an oven at 105°C until constant weight. About 1.4 g of the dried sample was deposited in a platinum bowl and the weight is determined with a precision of 0.001 g. Then the sample was mixed with a 4 to 6-fold excess (weight) of a mixture of sodium carbonate and potassium carbonate (1:1). The mixture was placed in the platinum bowl into a Simon-Müller-oven and molten for 2 to 3 hours at a temperature of 800 - 850°C. The platinum bowl was taken out of the oven and cooled to room temperature. The solidified melt was dissolved in distilled water and transferred into a beaker. Then concentrated hydrochloride acid was carefully added. After evolution of gas has ceased the water was evaporated such that a dry residue was obtained. The residue was dissolved in 20 ml of concentrated hydrochloric acid followed by evaporation of the liquid. The process of dissolving in concentrated hydrochloric acid and evaporation of the liquid was repeated one time. The residue was then moistened with 5 to 10 ml of aqueous hydrochloric acid (12 %). About 100 ml of distilled water was added and the mixture was heated. To remove insoluble SiO2, the sample was filtered and the residue remaining on the filter paper was thoroughly washed with hot hydrochloric acid (12 %) and distilled water until no chlorine was detected in the filtrate. The clay material was totally disintegrated. After dissolution of the solids the compounds were analyzed and quantified by specific methods, e.g. ICP
- b) Determination of the SiO2 content
The SiO2 was incinerated together with the filter paper and the residue was weighed. - c) Determination of aluminium, iron, calcium and magnesium
The filtrate was transferred into a calibrated flask and distilled water was added until the calibration mark. The amount of aluminium, iron, calcium and magnesium in the solution was determined by FAAS. - c) Determination of potassium, sodium and lithium
A 500 mg sample was weighed in a platinum bowl with a precision of 0.1 mg. The sample was moistened with about 1 to 2 ml of distilled water and then four drops of concentrated sulphuric acid were added. About 10 to 20 ml of concentrated hydrofluoric acid was added and the liquid phase evaporated to dryness in a sand bath. This process was repeated three times. Finally H2SO4 was added to the dry residue and the mixture was evaporated to dryness on an oven plate. The platinum bowl was calcined and, after cooling to room temperature, 40 ml of distilled water and 5 ml hydrochloric acid (18 %) was added to the residue and the mixture was heated to boiling. The solution was transferred into a calibrated 250 ml flask and water was added up to the calibration mark. The amount of sodium, potassium and lithium in the solution was determined by EAS.
- (iv) Loss on ignition
In a calcined and weighed platinum bowl, about 0.1 g of a sample was deposited weighed in a precision of 0.1 mg. The sample was calcined for 2 hours at 1000°C in an oven. Then the platinum bowl was transferred to an exsiccator and weighed. - (v) Ion Exchange capacity
The clay material to be tested was dried at 150°C for two hours. Then the dried material was allowed to react under reflux with a large excess of aqueous NH4Cl solution for 1 hour. After standing at room temperature for 16 hours, the material was filtered. The filter cake was washed, dried, and ground, and the NH4 content in the clay material was determined by the Kjedahl method. The amount and kind of the exchanged metal ions was determined by ICP-spectroscopy. - g) Determination of the sediment volume:
A graduated 100 ml glass cylinder was filled with 100 ml of distilled water or with an aqueous solution of 1 % sodium carbonate and 2 % trisodium polyphosphate. 2 g of the compound to be analyzed was placed on the water surface in portions of about 0.1 to 0.2 g. After sinking down of a portion, the next portion of the compound was added. After adding 2 g of the compound to be analyzed the cylinder was held at room temperature for one hour. Then the sediment volume (ml/2g) was read from the graduation. - h) Determination of montmorillonite proportion by methylene blue adsorption Preparation of a tetrasodium diphosphate solution
5.41 g tetrasodium diphosphate was weighed with a precision of 0.001 g in a calibrated 1000 ml flask and the flask was filled up to the calibration mark with distilled water and shaken repeatedly. - Preparation of a 0.5 % methylene blue solution:
In a 2000 ml beaker, 125 g methylene blue was dissolved in about 1500 ml distilled water. The solution was decanted and then distilled water was added up to a volume of 25 l. - 0.5 g moist test bentonite having a known inner surface were weighed in an Erlenmeyer flask with a precision of 0.001 g. 50 ml tetrasodium diphosphate solution were added and the mixture was heated to boiling for 5 minutes. After cooling to room temperature, 10 ml H2SO4 (0.5 m) and 80 to 95 % of the expected consumption of methylene blue solution were added. With a glass stick a drop of the suspension was transferred to a filter paper. A blue-black spot was formed surrounded by a colourless corona. Further methylene blue solution was added in portions of 1 ml and the drop test was repeated until the corona surrounding the blue-black spot shows a slightly blue colour, i.e. the added methylene blue was no longer adsorbed by the test bentonite.
- The test of the clay material was performed in the same way as described for the test bentonite. On the basis of the spent methylene blue solution was calculated the inner surface of the clay material. According to this method 381 mg methylene blue/g clay correspond to a content of 100 % montmorillonite.
- Through a sieve cloth, a vacuum cleaner connected with the sieve aspirates over a suction slit circling under the perforated sieve bottom all particles being finer than the inserted sieve being covered on top with an acrylic glass cover and leaves the coarser particles on the sieve.
- The experimental procedure was as follows: Depending on the product, between 5 and 25 g of air dried material was weighed in and was put on the sieve. Subsequently, the acrylic glass cover was put on the sieve and the machine was started. During air jet screening, the screening process can be facilitated by beating on the acrylic glass cover using the rubber hammer. Exhaustion time was between 1 and 5 minutes. The calculation of the dry screening residue in % is as follows: actual weight multiplied with 100 and divided by the initial weight.
- A calibrated 1l glass cylinder cut at the 1000 ml mark was weighed. By a powder funnel the sample was poured into the cylinder in a single step such that the cylinder is completely filled and a cone was formed on top of the cylinder. The cone was removed with help of a ruler and material adhering to the outside of the cylinder was removed. The filled cylinder was weighed again and the apparent weight was obtained by subtracting the weight of the empty cylinder.
- 1 to 2 g of clay sample was dry ground by hand in an agate mortar and then passed through a 20 µm sieve. This process was repeated until the entire sample passed the sieve. For the X-ray diffraction measurement a Siemens D5000 equipment was used. The following measuring conditions were employed:
Sample holder Plastic, "top loading", Ø = 25 mm Thickness of the powder layer 1 mm X-ray tube Cu Kα: 40 kV/40mA Diffraction angles 2 - 80 ° (2 θ) Measuring time 3 sec per step Slits Primary and secondary divergence slits of 1 mm - Qualitative evaluation of the diffractograms (assignment of the mineral phase was done with a computer program "EVA" by Bruker AXS GmbH, Karlsruhe and according to the publication of Brindley & Brown (1980): Crystal structures of clay minerals and their x-ray identification. - Mineralogical Society No. 5, 495.
- The quantitative evaluation was made according to the Rietveld method as described above.
- Characterization data:
The clay 1 and 2 namely Bentonite 1 ( Laundrosil® DGA powder) is produced from Bentonite 2 by alkaline activation) and the clay, Bentonite 2 is a natural calcium/sodium bentonite (EX 0242, from Clariant). Both bentonites powder exhibit a dry sieve residue of less than 15 wt.% on sieve, with a mesh size of 45 µm. The following tables show the typical properties of the Bentonite 1 and 2.Table 1 Bentonite 1 Bentonite 2 Montmorillonite content, determined with the Methylene-blue method [%] 78 75 Cation exchange capacity [meq/100 g] 72 76 Fraction of monovalent ions of the total cation exchange capacity 100 20 Swelling volume in distilled water[ml/2 g) > 15 11 Side mineral content determined by X-ray diffraction See below See below Quarz < 1 wt.% < 1 wt.% Cristobalite < 5 wt.% < 5 wt.% Feldspar < 12 wt.% < 12 wt.% - Characterization details of Clay 3-5 (Clays with High content of SiO2/ Mixed phase of bentonite and natural Silica) is provided in below table. Clay 3 is sold under the brand name Tonsil® Supreme 118 FF.
Table 2 Clay 3 4 5 Dry sieve residue on 45 µm (%) 49 55 5.2 Dry sieve residue on 63 µm (%) 35 40 38 apparent weight (g/l) 292 468 -- Methylene blue adsorption (mg/g sample) 106 152 179 Moisture content (%) 8 13 12 pH (10 wt.% in water) 7.6 9 8.1 cation exchange capacity (meq/100 g) 52 44 53.3 BET surface (m2/g) 208.4 238 248 micropore area (m2/g) 32.1 40 15 external surface (m2/g) 176.3 198 233 micropore volume (cm3/g) 0.016 0.02 0.01 cumulative pore volume (BJH) for pore diameter 1.7 - 300 nm (cm3/g) 0.825 0.623 0.777 average pore diameter (BJH) (nm) 16.4 10.0 55 sediment volume (ml/2g) 5.5 3 4 - The chemical composition of the adsorbents in clay is summarized in table 3.
Table 3 Clay 3 4 5 SiO2 70.6 wt.% 69.4 wt.% 69.4 wt.% Fe2O3 2.8 wt.% 3.4 wt.% 3.4 wt.% Al2O3 9.8 wt.% 9.9 wt.% 9.9 wt.% MgO 4.1 wt.% 3.1 wt.% 3.1 wt.% CaO 1.4 wt.% 2.5 wt.% 2.5 wt.% K2O 1.5 wt.% 1.3 wt.% 1.3 wt.% Na2O 0.26 wt.% 0.94 wt.% 0.94 wt.% TiO2 0.25 wt.% 0.38 wt.% 0.38 wt.% SO3 -- -- -- Loi (1000 °C) 7.9 wt.% 8.1 wt.% 8.1 wt.% - X-ray diffraction
- X-ray diffraction measurements of clay were made according to the general description for the method. The results of quantitative mineral phase determination by X-ray diffraction are listed in table 4.
- The quantitative X-ray diffraction analysis shows presence of smectite clay in clay 1 and 2 which are used in the method according to the invention.
- In addition various side minerals can be found, like sepiolite for clay 1, orthoclase, plagioclase (other feldspars) and calcite. The X-ray diffraction shows the presence of more than 30 % of amorphous material for both clays. In clay 2 the amorphous phase is almost present in the same concentration as the smectite (ratio 100:95), whereas in clay 1 the ratio of smectite to amorphous material is 100:85.
- The dyes used for making encapsulated dye composition are listed in below table:
Colour Index Name Chemical class Trade Name C.I. Acid Violet 17 Triaryl methane dye Duasyn Acid Violet 4BN-IN C.I. Direct Violet 66 Diazo dye Duasyn Violet SP-IN C.I. Acid Violet 54 Azo Dye Duasyn Red N-6B-IN C.I. Acid Violet 48 Anthraquinone Dye Duasyn Violet FBL-IN C.I. Acid Violet 126 Anthraquinone Dye Duasyn Red Violet E2R-IN - The silica used in the present invention having the properties as listed in the below table:
Silica Name Supplier Properties Hydrophilic/ Hydrophobic Particle Size, d(50) µm DOA Absorption, ml/100g Tamped Density, g/l Sipernat® 22 Evonik Hydrophilic 120 240 245 Sipernat® D 17 Evonik Hydrophobic 10 - 150 Ibersil® D 100 P IQESII S.A. Hydrophilic 200 245 230-280 -
Ingredients g % SIPERNAT® 22 8.0 80 Dye premix: Duasyn Acid Violet 4BN-IN 1.0 10 water 1.0 10 Total: 10 100 - Method: 8.0g of Sipernat® 22 (Silicon Dioxide, hydrophilic Silica) and 2g of dye premix containing 1 g of Duasyn Acid Violet 4BN-IN and 1 g of water was mixed manually to obtain the encapsulated dye composition.
- The encapsulated dye composition was a violet color formulation comprising -10% Duasyn Acid Violet 4BN-IN.
-
Ingredients g % SIPERNAT® 22 9.0 90 Dye premix: Duasyn Acid Violet 4BN-IN 0.5 5 water 0.5 5 Total: 10 100 - Method: 9.0g of Sipernat® 22 (Silicon Dioxide, hydrophilic Silica) and 1g of dye premix containing 0.5 g of Duasyn Acid Violet 4BN-IN and 0.5 g of water was mixed manually to obtain encapsulated dye composition.
- The encapsulated dye composition was a violet color formulation comprising ~5% Duasyn Acid Violet 4BN-IN.
-
Ingredients g % SIPERNAT® 22 4 40 Dye premix: Duasyn Acid Violet 4BN-IN 0.12 1.2 water 5.88 58.8 Total: 10 100 - Method: 4.0g of Sipernat® 22 (Silicon Dioxide, Hydrophilic Silica) and 6g of dye premix containing Duasyn Acid Violet 4BN-IN dye and water was mixed manually to obtain the encapsulated dye composition.
- The dye composition was a violet color formulation comprising ~1.2 % Duasyn Acid Violet 4BN-IN.
-
Ingredients g % SIPERNAT® 22 7.5 75 Dye premix: Duasyn Acid Violet 4BN-IN 1.5 15 HPMC 0.36 3.6 water 0.64 6.4 Total 10 100 - Method: 7.5g of Sipernat® 22 (Silicon Dioxide, Hydrophilic Silica) and 2.5g of dye premix containing Duasyn Acid Violet 4BN-IN, HPMC and water were mixed manually to obtain the encapsulated dye composition. The so obtained dye composition was a violet color formulation.
-
Ingredients g % SIPERNAT® 22 8.33 83.3 Dye premix: Duasyn Acid Violet 4BN-IN 1.0 10 HPMC 0.24 2.4 water 0.43 4.3 Total 10 100 - Method: 8.33g of Sipernat® 22 (Silicon Dioxide, Hydrophilic Silica) and 1.67g of dye premix containing Duasyn Acid Violet 4BN-IN, HPMC and water were mixed manually to obtain the encapsulated dye composition. The so obtained dye composition was a violet color formulation.
-
Ingredients g % SIPERNAT® 22 8.76 87.6 Dye premix: Duasyn Acid Violet 4BN-IN 1.0 10 HPMC 0.24 2.4 Total 10 100 - Method: 8.76g of Sipernat® 22 (Silicon Dioxide, Hydrophilic Silica) and 1.24g of dye premix containing Duasyn Acid Violet 4BN-IN, HPMC were mixed manually and dried at 90°C for 1 day (to make it moisture free) to obtain the encapsulated dye composition. The so obtained dye composition was a faint violet color formulation.
-
Ingredients g % SIPERNAT® 22 9.38 93.8 Dye Premix : Duasyn Acid Violet 4BN-IN 0.5 5 HPMC 0.12 1.2 Total 10 100 - Method : 9.38g of Sipernat® 22 (Silicon Dioxide, Hydrophilic Silica) and dye premix containing Duasyn Acid Violet 4BN-IN and HPMC were mixed manually and dried at 90°C for 1 day (to make it moisture free) to obtain the encapsulated dye composition. The so obtained dye composition had faint violet color.
- The following examples are dye compositions prepared according to the present invention:
-
Ingredients g % Sipernat® 22 4 40 Clay 1 (Laundrosil® DGA powder): 1 10 Clay 2 (EXM 0242) 1 10 Duasyn Acid Violet 4BN-IN 5% Aq. Dispersion: Duasyn Acid Violet 4BN-IN 0.2 2 Water 3.8 38 Total: 10 100 - Method: 4g of Sipernat® 22 (Silicon Dioxide, Hydrophilic Silica), 1g of Clay 1 Laundrosil® DGA powder(soda activated bentonite) and Clay 2 EXM 0242 (natural calcium-bentonite) were mixed to obtain a first mixture. The so obtained first mixture was blended with 4g of 5% aq. dispersion of Duasyn Acid Violet 4BN-IN to obtain the encapsulated dye composition. During preparation, the mixing was done manually for encapsulation. The so obtained dye composition was violet color formulation comprising 2% dye. It was observed that the color becomes more intense after storage at 45°C within a week. Formulation was found to release dye within few seconds in water with gentle stirring.
-
Ingredients g % Sipernat® 22 4 40 Duasyn Acid Violet 4BN-IN (5% Aq.): Duasyn Acid Violet 4BN-IN 0.2 2 Water 3.8 38 Clay 1 Laundrosil® DGA powder 1 10 Clay 2 EXM 0242 1 10 Total 10 100% - Method: 4g of Sipernat® 22 (Silicon Dioxide, Hydrophilic Silica) and 4g of 5% aq. dispersion of Duasyn Acid Violet 4BN-IN were mixed to obtain a first mixture. The so obtained first mixture was blended with 1g of Clay 1 Laundrosil® DGA powder (soda activated bentonite) to obtain second mixture. Second mixture was mixed with 1g of Clay 2 EXM 0242 (natural calcium-bentonite) to obtain the encapsulated dye composition.
- During preparation, the mixing was done manually for encapsulation. The so obtained dye composition was a violet color formulation comprising 2% dye. It was observed that the color becomes more intense after storage at 45°C within a week. Formulation was found to release dye within few seconds in water with gentle stirring.
-
Ingredients g % Sipernat® D 17 3 30 Dye premix: Duasyn Acid Violet 4BN-IN 0.5 5 water 0.5 5 Ibersil® D 100 P 2 20 Clay1(Laundrosil ® DGA powder 4 40 Total 10 100 - Method: 3g of Sipernat® D 17 (Silicon Dioxide, Hydrophobic Silica) and 1g of dye premix containing Duasyn Acid Violet 4BN-IN and water were mixed to obtain a first mixture. The so obtained first mixture was blended with 2g of Ibersil® D 100 P (Silicon Dioxide, Hydrophilic Silica with bigger particle size, d (50):~ 200 micron) to obtain second mixture. Second mixture was mixed with 4g of Clay 1 (soda activated bentonite, Laundrosil®DGA powder) to obtain the encapsulated dye composition.
- During preparation, the mixing was done manually for encapsulation. The so obtained dye composition was a violet color formulation comprising 5% dye. It was observed that the color becomes more intense after storage at 45°C within a week. Formulation was found to release dye within few seconds in water with gentle stirring.
-
Ingredients g % Sipernat® D 17 2 20 Dye premix: Duasyn Acid Violet 4BN-IN 0.05 0.5 water 0.05 0.5 Ibersil® D 100 P 3 30 Clay 1 (Laundrosil® DGA powder 4.9 49 Total 10 100% - Method: 2g of Sipernat® D 17 (Silicon Dioxide, Hydrophobic Silica) and 0.1g of dye premix containing Duasyn Acid Violet 4BN-IN and water were mixed to obtain a first mixture. The so obtained first mixture was blended with 3g of Ibersil® D 100 P (Silicon Dioxide, Hydrophilic Silica with bigger particle size, d (50):~ 200 micron) to obtain second mixture. Second mixture was mixed with 4.9 g Clay 1 Laundrosil® DGA powder (soda activated bentonite) to obtain the encapsulated dye composition.
- During preparation, the mixing was done manually for encapsulation. The so obtained dye composition was a white color formulation comprising -0.5% dye, which was found to be stable at room temperature (RT) and at 45°C on storage for 2 months. Formulation was found to release dye within few seconds in water with gentle stirring.
-
Ingredients g % Sipernat® D 17 3 30 Dye premix: Duasyn Acid Violet 4BN-IN 0.6 6 Water 0.4 4 Ibersil® D 100 P 2 20 Clay 1(Laundrosil® DGApowder 4 40 Total 10 100 - Method: 3g of Sipernat® D 17 (Silicon Dioxide, Hydrophobic Silica) and 1g of dye premix containing Duasyn Acid Violet 4BN-IN and water were mixed to obtain a first mixture. The so obtained first mixture was blended with 2g of Ibersil® D 100 P (Silicon Dioxide, Hydrophilic Silica with bigger particle size, d (50):~ 200micron) to obtain second mixture. Second mixture was mixed with 4g Clay 1 Laundrosil® DGA powder (soda activated bentonite) to obtain the encapsulated dye composition.
- During preparation, the mixing was done manually for encapsulation. The so obtained dye composition was a white color formulation comprising ~6% dye, which was found to be stable at RT and at 45°C on storage for 2 months. Formulation was found to release dye within few seconds in water with gentle stirring.
-
Ingredients g % Sipernat® D 17 2 20 Dye premix: Duasyn Acid Violet 4BN-IN 0.06 0.6 water 0.04 0.4 Ibersil® D 100 P 3 30 Clay 1 (Laundrosil® DGA powder 4.9 49 Total 10 100% - Method: 2g of Sipernat® D 17 (Silicon Dioxide, Hydrophobic Silica) and 0.1g of dye premix containing Duasyn Acid Violet 4BN-IN (Triaryl methane dye) and water were mixed to obtain a first mixture. The so obtained first mixture was blended with 3g of Ibersil® D 100 P (Silicon Dioxide, Hydrophilic Silica with bigger particle size, d(50):~200micron) to obtain a second mixture. Second mixture was mixed with 4.9g Clay 1 (soda activated bentonite, Laundrosil® DGA powder) to obtain the encapsulated dye composition.
- During preparation, the mixing was done manually for encapsulation. The so obtained dye composition was a white color formulation comprising -0.6% dye, which was found to be stable at RT and at 45°C on storage for 2 months. Formulation was found to release dye within few seconds in water with gentle stirring.
-
Ingredients g % Sipernat® D 17 3 30 Dye premix: Duasyn Acid Violet 4BN-IN 0.25 2.5 Duasyn Violet SP-IN 0.25 2.5 water 0.5 5 Ibersil® D 100 P 2 20 Clay 1(Laundrosil® DGA powder 4 40 Total 10 100 - Method: 3g of Sipernat® D 17 (Silicon Dioxide, Hydrophobic Silica) and 1g of dye premix containing 1:1 ratio of Duasyn Acid Violet 4BN-IN and Duasyn Violet SP-IN along with water were mixed to obtain a first mixture. The so obtained first mixture was blended with 2g of Ibersil® D 100 P (Silicon Dioxide, Hydrophilic Silica with bigger particle size, d (50):~ 200micron) to obtain second mixture. Second mixture was mixed with 4g Clay 1 (Laundrosil® DGA powder (soda activated bentonite) to obtain the encapsulated dye composition.
- During preparation, the mixing was done manually for encapsulation. The so obtained dye composition was a white color formulation comprising ~5% dye, which was found to be stable at RT and at 45°C on storage for 2 months. Formulation was found to release dye within few seconds in water with gentle stirring.
-
Ingredients g % Sipernat® D 17 2 20 Dye premix: Duasyn Acid Violet 4BN-IN 0.025 0.25 Duasyn Violet SP-IN (1:1) 0.025 0.25 water 0.05 0.5 Ibersil® D 100 P 3 30 Clay 1(Laundrosil® DGA® powder 4.9 49 Total 100 - Method: 2g of Sipernat® D 17 (Silicon Dioxide, Hydrophobic Silica) and 0.1g of dye premix containing 1:1 ratio of Duasyn Acid Violet 4BN-IN and Duasyn Violet SP-IN in water were mixed to obtain a first mixture. The so obtained first mixture was blended with 3g of Ibersil® D 100 P (Silicon Dioxide, Hydrophilic Silica with bigger particle size, d (50):~ 200micron) to obtain a second mixture. Second mixture was mixed with 4.9g Clay 1 Laundrosil® DGA powder (soda activated bentonite) to obtain the encapsulated dye composition.
- During preparation, the mixing was done manually for encapsulation. The so obtained dye composition was a white color formulation comprising -0.5% dye and was found to be stable at RT and at 45°C on storage for 2 months. Formulation was found to release dye within few seconds in water with gentle stirring.
-
Ingredients g % Dye premix: Duasyn Violet 4BN-IN 0.7 7 HPMC 0.25 2.5 water 2.05 20.5 Sipernat® D17 0.5 5 Ibersil® D 100 P 3 30 Mixture of Clay 2 EXM 0242 and Clay 1(Laundrosil® DGApowder 3.5 35 Total 10 100 - Method: 3g of dye premix containing Duasyn Violet 4BN-IN, HPMC and water were blended with Sipernat® D 17 to obtain a first mixture. The so obtained first mixture was blended with 3g of Ibersil® D 100 P (Silicon Dioxide, Hydrophilic Silica with bigger particle size, d (50):~ 200micron) to obtain second mixture. Second mixture was mixed with 3.5g blend of Clay 2 EXM 0242 (natural calcium-bentonite) and Clay 1 (Laundrosil® DGA powder (soda activated bentonite) to obtain the encapsulated dye composition.
- During preparation, the mixing was done manually for encapsulation. The so obtained dye composition was a white color formulation comprising ~7% dye, which was found to be stable at RT and at 45°C on storage for 2 months. Formulation was found to release dye within few seconds in water with gentle stirring.
-
Ingredients g % Dye premix: Duasyn Violet SP-IN 1 10 HPMC 0.25 2.5 Water 1.75 17.5 Sipernat® D17 0.5 5 Ibersil® D 100 P 3 30 Clay 2 EXM 0242 and Clay 1 (Laundrosil® DGA powder 3.5 35 Total 10 100% - Method: 3g of dye premix containing Duasyn Violet SP-IN, HPMC and water were blended with Sipernat D® 17 (Silicon Dioxide, Hydrophobic Silica from Evonik Industries) to obtain a first mixture. First mixture was mixed with 3g of Ibersil® D 100 P (Silicon Dioxide, Hydrophilic Silica with bigger particle size, d (50):~ 200micron) to obtain a second mixture. Second mixture was mixed with 3.5g blend of Clay 2 (EXM 0242) (natural calcium-bentonite) and Clay 1 Laundrosil® DGA-powder (soda activated bentonite) to obtain the encapsulated dye composition.
- During preparation, the mixing was done manually for encapsulation. The so obtained dye composition was a white color formulation comprising -10% dye, which was found to be stable at RT and at 45°C on storage for 2 months. Formulation was found to release dye within few seconds in water with gentle stirring.
-
Ingredients g % Dye premix: Duasyn Red N-6B-IN 1 10 HPMC 0.25 2.5 water 1.75 17.5 Ibersil® D 100 P 3 30 Clay 2 EXM 0242® and Clay 1 Laundrosil® DGApowder 4 40 Total 10 100 - Method: 3g of dye premix containing Duasyn Red N-6B-IN, HPMC and water were blended with Sipernat D® 17 (Silicon Dioxide, Hydrophobic Silica from Evonik Industries) to obtain a first mixture. The so obtained first mixture was blended with 3g of Ibersil® D 100 P (Silicon Dioxide, Hydrophilic Silica with bigger particle size, d (50):~ 200micron) to obtain second mixture. Second mixture was mixed with 4g blend of Clay 2 EXM 0242 (natural calcium-bentonite) and Clay 1 Laundrosil® DGA powder® (soda activated bentonite) to obtain the encapsulated dye composition.
- During preparation, the mixing was done manually for encapsulation. The so obtained dye composition was a white color formulation comprising -10% dye, which was found to be stable at RT and at 45°C upon storage for 2 months. Formulation was found to release dye within few seconds in water with gentle stirring. The same formulation could be prepared using Duasyn Violet FBL-IN, Duasyn Red Violet E2R-IN or mixtures of two or three dyes mentioned in this example.
- Composition 12: The encapsulated dye composition is prepared using Fluidized Bed Process.
Ingredients g % Phase A: Carrier Ibersil® D 100 P 200 40 Clay 1 Laundrosil® DGApowder 100 20 Clay 2 EXM 0242® 100 20 Phase B: Dye premix in water Duasyn Acid Violet 4BN-IN 100 20 Coating solution for Fluidized Bed Processing HPMC 4 TiO2 (Viscofil White ARCL 30) in water 10 - Method: Dye premix containing 100g of Duasyn Acid Violet 4BN-IN dye in water was mixed with a mixture of 200g of Ibersil® D 100 P (Silicon Dioxide, Hydrophilic Silica with bigger particle size, d (50):~ 200micron), 100g of Clay 1 Laundrosil® DGA-powder (soda activated bentonite) and 100g of Clay 2 EX® 0242 (natural Ca-bentonite) in Stephen mixer to obtain a mixture/dough cake. The mixture/dough cake was extruded through an extruder to obtain extrudates. The extrudates were spheronized to obtain granules. Obtained granules were further dried at 45°C in oven to remove any moisture. The granules were coated with the binder to obtain the encapsulated dye composition. The above Table shows the final composition of the encapsulated dye composition 12.
- It was observed that the off white HPMC coated beads of the dye composition was stable at RT and at 45°C for 2 months. The formulation was found to release dye within few seconds in water with gentle stirring and no dye staining on cloth piece after washing.
-
Ingredients g % Ibersil® D 100 P 4.02 40.2 Dye Premix Duasyn Acid Violet 4BN-IN 1.8 18 HPMC 0.18 1.8 Clay 3 (Tonsil Supreme® 118 FF) 2 20 Clay 1 Laundrosil® DGA-powder 2 20 Total 10 100 - Method: 4.02g of Ibersil® D 100 P (Silicon Dioxide, Hydrophilic Silica with bigger particle size, d (50):~ 200micron) and 3g dye premix containing Duasyn Acid Violet 4BN-IN and HPMC were mixed to obtain a first mixture. The so obtained first mixture was blended with 2g of Clay 3 Tonsil Supreme® 118 FF to obtain second mixture. Second mixture was mixed with 2g Clay 1 Laundrosil® DGA-powder (soda activated bentonite) to obtain the encapsulated dye composition. Encapsulated dye sample was further dried at 80-90°C for 1 day for complete moisture removal.
- The so obtained dye composition was found to be a white color formulation comprising -18% Dye. The mixing was done manually for encapsulation. The dye composition was found to be stable at RT and at 45°C on storage for 2 months. The formulation was found to release dye within few seconds in water with gentle stirring. The dye composition was found stable in strength testing. Instead of using Duasyn Acid Violet 4BN-IN for the premix, alternatively Duasyn Violet SP-IN, Duasyn Red N-6B-IN, Duasyn Violet FBL-IN or Duasyn Red Violet E2R-IN or a mixture of two or several of the afore mentioned dye can be used for the preparation of the formulation mentioned in this example.
-
Ingredients g % Phase A: Carrier Sipernat® 22 68 34 Clay 1 Laundrosil DGA® -powder 40 20 Clay 2 EXM 0242® 40 20 Phase B: Dye Premix Duasyn Violet SP-IN 40 20 HPMC 12 6 Total 200 100 - Method: 52g of phase B, dye premix containing Duasyn Violet SP-IN and HPMC, was mixed with a mixture of 68g of Sipernat® 22 (Silicon Dioxide, Hydrophilic Silica), 40g of Clay 1 Laundrosil DGA®-powder (soda activated bentonite) and 40g of Clay 2 EXM 0242® in Stephen mixer to obtain a mixture/dough cake. The mixture/dough cake was extruded through an extruder to obtain extrudates. The extrudates were spheronized to obtain granules. Obtained granules were further dried at 45°C in oven.
- The dye composition was found to be violet colored granules, which were found to be stable at RT and at 45°C storage for 2 months. The formulation was found to release dye within few seconds in water with gentle stirring. The dye composition was found to be stable in strength testing and no dye staining on cloth piece after washing. Similar formulations can be prepared with the shading dyes Duasyn Acid Violet 4BN-IN, Duasyn Red N-6B-IN, Duasyn Violet FBL-IN, Duasyn Red Violet E2R-IN or a mixture of two or several of the afore mentioned dyes.
- Composition 15: The encapsulated dye composition is prepared using Fluidized Bed Process.
Ingredients g % Phase A: Carrier Ibersil® D 100 P 199.5 38 Laundrosil® DGA-powder 99.75 19 EXM 0242 99.75 19 Phase B: Dye premix Duasyn Acid Violet 4BN-IN 99.75 19 Coating HPMC 5.25 1 Viscofil White ARCL 30 21 4 Total = 525 100 - Method: Dye premix containing Duasyn Acid Violet 4BN-IN in water was mixed with a mixture of Ibersil® D 100 P (Silicon Dioxide, Hydrophilic Silica with bigger particle size, d (50):~ 200micron), Laundrosil DGA-powder and EXM 0242 (bentonite/Clay) in Stephen mixer to obtain a mixture/dough cake. The mixture/dough cake was extruded through an extruder to obtain extrudates. The extrudates were spheronized to obtain granules. Obtained granules were further dried at 45°C in oven to remove any moisture. The granules were coated with HPMC and Viscofil White ARCL 30 to obtain the encapsulated dye composition. The final composition of the encapsulated dye is given in the above Table.
- The so obtained dye composition was off white color HPMC coated beads, which were found to be stable at RT and at 50°C on storage for 2 months. The formulation was found to release dye within few seconds in water with gentle stirring.
- Comparable Formulations can be prepared using Duasyn Violet SP-IN or Duasyn Red N-6B-IN, Duasyn Violet FBL-IN or Duasyn Red Violet E2R-IN or a mixture of two or several of the fore mentioned dyes.
- Various formulations of the compositions of present invention are tested for their effects which are discussed as below.
- Method: Open dish stability test was carried out to test the bleeding character of the encapsulated dye composition. The encapsulated dye composition was mixed with the white detergent powder and the resulting powder was kept in a petri dish and was left in the open environment for up to 2 months at room temperature and elevated temperature to check bleeding.
- Result: It was observed that even after four weeks, the white powder did not change its color and there was no migration of the dye from the encapsulated dye composition. Thus, the encapsulated dye composition was found to be stable.
- Method: The encapsulated dye compositions of the present invention prepared according to the above examples were used for the strength testing. The encapsulated sample was added to the powder detergent or components such as sodium sulfate. The sample was exposed to shear mimicking conditions of mixing dye with powder detergent. The sample was further observed after strength testing for migration of dye in powder detergent/sodium sulfate.
- Result: It was observed that dye material was not migrating in powder detergent after performing the strength testing and white powder was not changing its original color.
- Method: The encapsulated dye composition of the present invention prepared according to the above examples were used for the dye staining test by conventional methods on the required fabrics such as woven polyester fabric, woven polycotton fabric, woven cotton CN-II fabric, elastane/nylon fabric.
- Result: It was observed that no stains were left after the washing cycle on the fabric material. Thus, the encapsulated dye composition was found to be washed out easily from the fabric.
Mineral Phase (wt.%) | Clay 4 | Clay 5 |
Smectite | 40 | 40 |
Illite / Muscovite | Traces | n.d. |
Kaolinite | n.d. | 1 |
Sepiolite | 11 | n.d. |
Quartz | Traces | 1 |
Orthoclase | 12 | 8 |
Plagioclase (different) | 3 | 11 |
Calcite | Traces | 1 |
Amorphous material | 34 | 38 |
Claims (18)
- An encapsulated dye composition comprising:a) carrier consisting of a mixture of silica and clay; andb) at least one dye encapsulated in the carrier.
- The composition as claimed in claim 1 further comprising a binder.
- The composition as claimed in claim 1, wherein said dye is selected from anionic azine dye or cationic phenazine dye, triaryl-methane dye, triphenyl-methane dye, anthraquinone dye, azo dye, disazo dye, phthalocyanine dye, quinophthalone dye, methine dye, hemicyanine dye, azo/azomethine complex dye, triphendioxazine dye or any mixtures thereof.
- The composition as claimed in claim 3, wherein the dye is selected from the group consisting of Duasyn Acid Violet 4BN-IN (C.I. Acid Violet 17), Duasyn Violet SP-IN (C.I. Direct Violet 66), Duasyn Red N-6B-IN (C.I. Acid Violet 54), Duasyn Violet FBL-IN (C.I. Acid Violet 48), Duasyn Red Violet E2R-IN (C.I. Acid Violet 126) or mixtures of one or several of the afore mentioned dyes.
- The composition as claimed in claim 1, wherein the carrier has a ratio of silica to clay of from 1:4 to 4:1.
- The composition as claimed in claim 1, wherein said clay is selected from the group consisting of natural clays comprising bentonite, montmorillonite, beidellite, saponite, hectorite, stevensite, kerolite-saponite, kerolite, talc, pyrophyllite, attapulgite, sepiolite; a mixture of natural silica with a bentonite;any modified clays; and any mixtures thereof.
- The composition as claimed in claim 6, wherein the clay contains a natural or sodium activated bentonite or a mixture containing both.
- The composition as claimed in claim 1, wherein said clay has:a. a surface area of more than 120 m2/g;b. a total pore volume of more than 0.35 ml/g;c. a silicon content, calculated as SiO2, of at least 60 wt.%.
- The composition as claimed in claim 8, wherein said clay has more than 10 % of amorphous material as determined by quantitative X-ray diffraction analysis of the mineral phases of the clay material.
- The composition as claimed in claim 1, wherein the silica is selected from the group consisting of silica gel, a pyrogenic silica or a precipitated silica or mixtures thereof.
- The composition as claimed in claim 10, wherein the silica is a precipitated silica.
- The composition as claimed in claim 11, wherein the precipitated silica is a hydrophilic precipitated silica or a hydrophobic precipitated silica or a mixture of both.
- The composition as claimed in claim 2, wherein said binder is a surfactant or a polymer.
- The composition as claimed in claim 13, wherein said polymer is hydroxyl propyl methyl cellulose.
- A method for preparing an encapsulated dye composition comprising mixing at least one dye, silica, clay and binder manually to obtain dye composition encapsulated in the carrier comprising the steps ofa) mixing a dye with a binder to obtain a first mixture;b) blending the mixture with a portion of hydrophobic silica to obtain a second mixture;c) mixing the second mixture with a portion of hydrophilic silica to obtain a third mixture; andd) blending the third mixture with a portion of clay to obtain the encapsulated dye composition.
- The process as claimed in claim 15 wherein encapsulated dye composition is obtained in the powder form or in granular form.
- Laundry detergent composition comprising encapsulated dye composition comprising carrier consisting of a mixture of silica and clay; and at least one dye encapsulated in the carrier.
- A detergent composition comprising encapsulated dye composition, wherein said dye composition comprising:a carrier consisting of 30% to 75% by weight of silica and 20% to 40% by weight of clay;1 to 5% by weight of binder; and1 to 20% by weight of dye.
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
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EP18211210.2A EP3666869A1 (en) | 2018-12-10 | 2018-12-10 | An encapsulated dye composition and a method for preparation thereof |
PCT/EP2019/083471 WO2020120225A1 (en) | 2018-12-10 | 2019-12-03 | An encapsulated dye composition and a method for preparation thereof |
Publications (2)
Publication Number | Publication Date |
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EP3894532A1 EP3894532A1 (en) | 2021-10-20 |
EP3894532B1 true EP3894532B1 (en) | 2024-03-27 |
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EP18211210.2A Ceased EP3666869A1 (en) | 2018-12-10 | 2018-12-10 | An encapsulated dye composition and a method for preparation thereof |
EP19812786.2A Active EP3894532B1 (en) | 2018-12-10 | 2019-12-03 | An encapsulated dye composition and a method for preparation thereof |
Family Applications Before (1)
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EP18211210.2A Ceased EP3666869A1 (en) | 2018-12-10 | 2018-12-10 | An encapsulated dye composition and a method for preparation thereof |
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EP (2) | EP3666869A1 (en) |
CN (1) | CN113166686A (en) |
BR (1) | BR112021011064A8 (en) |
WO (1) | WO2020120225A1 (en) |
Family Cites Families (13)
Publication number | Priority date | Publication date | Assignee | Title |
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CA2327453A1 (en) * | 1999-12-04 | 2001-06-04 | Henkel Kommanditgesellschaft Auf Aktien | Laundry detergents and cleaning products |
US20040018955A1 (en) * | 2000-01-12 | 2004-01-29 | Jean Wevers | Pro-perfume composition |
GB0018774D0 (en) | 2000-07-31 | 2000-09-20 | Unilever Plc | Coloured speckle composition and particulate laundry detergent compositions containing it |
EP1352951A1 (en) * | 2002-04-11 | 2003-10-15 | The Procter & Gamble Company | Detergent granule comprising a nonionic surfactant and a hydrotrope |
WO2007080553A2 (en) * | 2006-01-12 | 2007-07-19 | The Procter & Gamble Company | Cleaning implement with erodible foam substrate and controlled release system of active agent |
US20110143989A1 (en) * | 2006-04-14 | 2011-06-16 | Petkus Matthew M | Laundry article |
EP2245133B1 (en) * | 2008-01-10 | 2012-05-23 | Unilever Plc, A Company Registered In England And Wales under company no. 41424 of Unilever House | Granules |
US8535392B2 (en) * | 2008-11-25 | 2013-09-17 | Milliken & Company | Solid polymeric colorant compositions |
EP2277982B1 (en) * | 2009-07-17 | 2012-01-18 | Clariant Finance (BVI) Limited | Color changing cleansing composition |
US8318652B2 (en) * | 2009-08-25 | 2012-11-27 | Milliken & Company | Colored speckles comprising a porous carrier and a releasing agent layer |
US8470760B2 (en) * | 2010-05-28 | 2013-06-25 | Milliken 7 Company | Colored speckles for use in granular detergents |
BR112014030734A2 (en) * | 2012-06-08 | 2017-06-27 | Amcol International Corp | visually contrasting aesthetic particles having increased water solubility, particularly useful for combination with granular or powder compositions |
EP3202713B1 (en) * | 2014-10-02 | 2021-06-16 | JGC Catalysts and Chemicals Ltd. | Porous silica-based particles, method for producing same, and cleansing cosmetic material including porous silica-based particles |
-
2018
- 2018-12-10 EP EP18211210.2A patent/EP3666869A1/en not_active Ceased
-
2019
- 2019-12-03 EP EP19812786.2A patent/EP3894532B1/en active Active
- 2019-12-03 WO PCT/EP2019/083471 patent/WO2020120225A1/en unknown
- 2019-12-03 BR BR112021011064A patent/BR112021011064A8/en unknown
- 2019-12-03 CN CN201980081168.0A patent/CN113166686A/en active Pending
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WO2020120225A1 (en) | 2020-06-18 |
EP3666869A1 (en) | 2020-06-17 |
BR112021011064A2 (en) | 2021-08-31 |
EP3894532A1 (en) | 2021-10-20 |
BR112021011064A8 (en) | 2023-03-07 |
CN113166686A (en) | 2021-07-23 |
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