EP0557419B1 - Amidoperoxysäure-bleichmittel und parfüm enthaltendes granulares reinigungsmittel oder bleichzusammensetzungen - Google Patents
Amidoperoxysäure-bleichmittel und parfüm enthaltendes granulares reinigungsmittel oder bleichzusammensetzungen Download PDFInfo
- Publication number
- EP0557419B1 EP0557419B1 EP92900440A EP92900440A EP0557419B1 EP 0557419 B1 EP0557419 B1 EP 0557419B1 EP 92900440 A EP92900440 A EP 92900440A EP 92900440 A EP92900440 A EP 92900440A EP 0557419 B1 EP0557419 B1 EP 0557419B1
- Authority
- EP
- European Patent Office
- Prior art keywords
- bleach
- weight
- perfume
- napaa
- methyl
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
Links
- 239000000203 mixture Substances 0.000 title claims abstract description 69
- 239000002304 perfume Substances 0.000 title claims abstract description 68
- 239000007844 bleaching agent Substances 0.000 title claims abstract description 59
- 239000003599 detergent Substances 0.000 title claims abstract description 41
- 238000004061 bleaching Methods 0.000 title claims abstract description 19
- 239000004615 ingredient Substances 0.000 claims abstract description 38
- -1 Exaltex Chemical compound 0.000 claims description 36
- 125000004432 carbon atom Chemical group C* 0.000 claims description 33
- 239000008187 granular material Substances 0.000 claims description 33
- NTPLXRHDUXRPNE-UHFFFAOYSA-N 4-methoxyacetophenone Chemical compound COC1=CC=C(C(C)=O)C=C1 NTPLXRHDUXRPNE-UHFFFAOYSA-N 0.000 claims description 22
- 125000000217 alkyl group Chemical group 0.000 claims description 20
- 229910052708 sodium Inorganic materials 0.000 claims description 20
- 239000011734 sodium Substances 0.000 claims description 20
- 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 claims description 19
- ZCTQGTTXIYCGGC-UHFFFAOYSA-N Benzyl salicylate Chemical compound OC1=CC=CC=C1C(=O)OCC1=CC=CC=C1 ZCTQGTTXIYCGGC-UHFFFAOYSA-N 0.000 claims description 18
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 17
- 239000002245 particle Substances 0.000 claims description 17
- 239000000463 material Substances 0.000 claims description 15
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- 150000002499 ionone derivatives Chemical class 0.000 claims description 10
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- FGQOOHJZONJGDT-UHFFFAOYSA-N vanillin Natural products COC1=CC(O)=CC(C=O)=C1 FGQOOHJZONJGDT-UHFFFAOYSA-N 0.000 claims description 10
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- IAIHUHQCLTYTSF-MRTMQBJTSA-N Fenchyl alcohol Chemical compound C1C[C@]2(C)[C@H](O)C(C)(C)[C@H]1C2 IAIHUHQCLTYTSF-MRTMQBJTSA-N 0.000 claims description 9
- YPZUZOLGGMJZJO-UHFFFAOYSA-N ambrofix Natural products C1CC2C(C)(C)CCCC2(C)C2C1(C)OCC2 YPZUZOLGGMJZJO-UHFFFAOYSA-N 0.000 claims description 9
- YPZUZOLGGMJZJO-LQKXBSAESA-N ambroxan Chemical compound CC([C@@H]1CC2)(C)CCC[C@]1(C)[C@@H]1[C@]2(C)OCC1 YPZUZOLGGMJZJO-LQKXBSAESA-N 0.000 claims description 9
- IAIHUHQCLTYTSF-UHFFFAOYSA-N fenchyl alcohol Natural products C1CC2(C)C(O)C(C)(C)C1C2 IAIHUHQCLTYTSF-UHFFFAOYSA-N 0.000 claims description 9
- 239000004094 surface-active agent Substances 0.000 claims description 9
- GVONPEQEUQYVNH-SNAWJCMRSA-N 2-Methyl-3-(2-pentenyl)-2-cyclopenten-1-one Chemical compound CC\C=C\CC1=C(C)C(=O)CC1 GVONPEQEUQYVNH-SNAWJCMRSA-N 0.000 claims description 8
- 239000001725 2-hexylcyclopent-2-en-1-one Substances 0.000 claims description 8
- WRMNZCZEMHIOCP-UHFFFAOYSA-N 2-phenylethanol Chemical compound OCCC1=CC=CC=C1 WRMNZCZEMHIOCP-UHFFFAOYSA-N 0.000 claims description 8
- 229940062909 amyl salicylate Drugs 0.000 claims description 8
- NUQDJSMHGCTKNL-UHFFFAOYSA-N cyclohexyl 2-hydroxybenzoate Chemical compound OC1=CC=CC=C1C(=O)OC1CCCCC1 NUQDJSMHGCTKNL-UHFFFAOYSA-N 0.000 claims description 8
- NYNCZOLNVTXTTP-UHFFFAOYSA-N ethyl 2-(1,3-dioxoisoindol-2-yl)acetate Chemical compound C1=CC=C2C(=O)N(CC(=O)OCC)C(=O)C2=C1 NYNCZOLNVTXTTP-UHFFFAOYSA-N 0.000 claims description 8
- DGEPZINOUXMMAS-UHFFFAOYSA-N (2,4-dimethylcyclohexyl)methanol Chemical compound CC1CCC(CO)C(C)C1 DGEPZINOUXMMAS-UHFFFAOYSA-N 0.000 claims description 7
- FACFHHMQICTXFZ-UHFFFAOYSA-N 2-(2-phenylimidazo[1,2-a]pyridin-3-yl)ethanamine Chemical compound N1=C2C=CC=CN2C(CCN)=C1C1=CC=CC=C1 FACFHHMQICTXFZ-UHFFFAOYSA-N 0.000 claims description 7
- DNRJTBAOUJJKDY-UHFFFAOYSA-N 2-Acetyl-3,5,5,6,8,8-hexamethyl-5,6,7,8- tetrahydronaphthalene Chemical compound CC(=O)C1=C(C)C=C2C(C)(C)C(C)CC(C)(C)C2=C1 DNRJTBAOUJJKDY-UHFFFAOYSA-N 0.000 claims description 7
- NPBVQXIMTZKSBA-UHFFFAOYSA-N Chavibetol Natural products COC1=CC=C(CC=C)C=C1O NPBVQXIMTZKSBA-UHFFFAOYSA-N 0.000 claims description 7
- 239000005770 Eugenol Substances 0.000 claims description 7
- UVMRYBDEERADNV-UHFFFAOYSA-N Pseudoeugenol Natural products COC1=CC(C(C)=C)=CC=C1O UVMRYBDEERADNV-UHFFFAOYSA-N 0.000 claims description 7
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- ONKNPOPIGWHAQC-UHFFFAOYSA-N galaxolide Chemical compound C1OCC(C)C2=C1C=C1C(C)(C)C(C)C(C)(C)C1=C2 ONKNPOPIGWHAQC-UHFFFAOYSA-N 0.000 claims description 7
- 229940067137 musk ketone Drugs 0.000 claims description 7
- KHWTYGFHPHRQMP-UHFFFAOYSA-N (4-propan-2-ylcyclohexyl)methanol Chemical compound CC(C)C1CCC(CO)CC1 KHWTYGFHPHRQMP-UHFFFAOYSA-N 0.000 claims description 6
- AZUVBPVDRHGGEP-UHFFFAOYSA-N 6a,9a-dimethyl-4,5,7,8,9,9a-hexahydro-6aH-dipyrrolo(2,3-b;3',2',1'-hi)indole Natural products CC(=C)C1CCC(C)=CCCC(C)=CCCC(C)=CC1O AZUVBPVDRHGGEP-UHFFFAOYSA-N 0.000 claims description 6
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 claims description 6
- GLZPCOQZEFWAFX-UHFFFAOYSA-N Geraniol Chemical compound CC(C)=CCCC(C)=CCO GLZPCOQZEFWAFX-UHFFFAOYSA-N 0.000 claims description 6
- WSTYNZDAOAEEKG-UHFFFAOYSA-N Mayol Natural products CC1=C(O)C(=O)C=C2C(CCC3(C4CC(C(CC4(CCC33C)C)=O)C)C)(C)C3=CC=C21 WSTYNZDAOAEEKG-UHFFFAOYSA-N 0.000 claims description 6
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 claims description 6
- XMWRWTSZNLOZFN-UHFFFAOYSA-N musk xylene Chemical compound CC1=C(N(=O)=O)C(C)=C(N(=O)=O)C(C(C)(C)C)=C1N(=O)=O XMWRWTSZNLOZFN-UHFFFAOYSA-N 0.000 claims description 6
- MDHYEMXUFSJLGV-UHFFFAOYSA-N phenethyl acetate Chemical compound CC(=O)OCCC1=CC=CC=C1 MDHYEMXUFSJLGV-UHFFFAOYSA-N 0.000 claims description 6
- CZCBTSFUTPZVKJ-UHFFFAOYSA-N rose oxide Chemical compound CC1CCOC(C=C(C)C)C1 CZCBTSFUTPZVKJ-UHFFFAOYSA-N 0.000 claims description 6
- 229910052938 sodium sulfate Inorganic materials 0.000 claims description 6
- 235000011152 sodium sulphate Nutrition 0.000 claims description 6
- OBDUMNZXAIUUTH-UHFFFAOYSA-N tetradec-2-ene Chemical compound CCCCCCCCCCCC=CC OBDUMNZXAIUUTH-UHFFFAOYSA-N 0.000 claims description 6
- QMVPMAAFGQKVCJ-SNVBAGLBSA-N (R)-(+)-citronellol Natural products OCC[C@H](C)CCC=C(C)C QMVPMAAFGQKVCJ-SNVBAGLBSA-N 0.000 claims description 5
- PRNCMAKCNVRZFX-UHFFFAOYSA-N 3,7-dimethyloctan-1-ol Chemical compound CC(C)CCCC(C)CCO PRNCMAKCNVRZFX-UHFFFAOYSA-N 0.000 claims description 5
- GPMLJOOQCIHFET-UHFFFAOYSA-N Rhubafuran Chemical compound C1OC(C)CC1(C)C1=CC=CC=C1 GPMLJOOQCIHFET-UHFFFAOYSA-N 0.000 claims description 5
- 150000004996 alkyl benzenes Chemical class 0.000 claims description 5
- 125000002947 alkylene group Chemical group 0.000 claims description 5
- 229940077388 benzenesulfonate Drugs 0.000 claims description 5
- JGQFVRIQXUFPAH-UHFFFAOYSA-N beta-citronellol Natural products OCCC(C)CCCC(C)=C JGQFVRIQXUFPAH-UHFFFAOYSA-N 0.000 claims description 5
- MIZGSAALSYARKU-UHFFFAOYSA-N cashmeran Chemical compound CC1(C)C(C)C(C)(C)C2=C1C(=O)CCC2 MIZGSAALSYARKU-UHFFFAOYSA-N 0.000 claims description 5
- 235000000484 citronellol Nutrition 0.000 claims description 5
- FJDUDHYHRVPMJZ-UHFFFAOYSA-N nonan-1-amine Chemical compound CCCCCCCCCN FJDUDHYHRVPMJZ-UHFFFAOYSA-N 0.000 claims description 5
- IMRYETFJNLKUHK-SJCJKPOMSA-N (S,S)-traseolide Chemical compound CC1=C(C(C)=O)C=C2[C@@H](C(C)C)[C@H](C)C(C)(C)C2=C1 IMRYETFJNLKUHK-SJCJKPOMSA-N 0.000 claims description 4
- BJLRAKFWOUAROE-UHFFFAOYSA-N 2500-83-6 Chemical compound C12C=CCC2C2CC(OC(=O)C)C1C2 BJLRAKFWOUAROE-UHFFFAOYSA-N 0.000 claims description 4
- GOLORTLGFDVFDW-UHFFFAOYSA-N 3-(1h-benzimidazol-2-yl)-7-(diethylamino)chromen-2-one Chemical compound C1=CC=C2NC(C3=CC4=CC=C(C=C4OC3=O)N(CC)CC)=NC2=C1 GOLORTLGFDVFDW-UHFFFAOYSA-N 0.000 claims description 4
- NGYMOTOXXHCHOC-UHFFFAOYSA-N 3-methyl-5-(2,2,3-trimethylcyclopent-3-en-1-yl)pentan-2-ol Chemical compound CC(O)C(C)CCC1CC=C(C)C1(C)C NGYMOTOXXHCHOC-UHFFFAOYSA-N 0.000 claims description 4
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- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
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- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 2
- 125000002252 acyl group Chemical group 0.000 description 2
- 235000011037 adipic acid Nutrition 0.000 description 2
- 150000001335 aliphatic alkanes Chemical group 0.000 description 2
- 229910052783 alkali metal Inorganic materials 0.000 description 2
- 150000001340 alkali metals Chemical class 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 150000007942 carboxylates Chemical class 0.000 description 2
- FLKPEMZONWLCSK-UHFFFAOYSA-N diethyl phthalate Chemical compound CCOC(=O)C1=CC=CC=C1C(=O)OCC FLKPEMZONWLCSK-UHFFFAOYSA-N 0.000 description 2
- 235000011180 diphosphates Nutrition 0.000 description 2
- BNIILDVGGAEEIG-UHFFFAOYSA-L disodium hydrogen phosphate Chemical compound [Na+].[Na+].OP([O-])([O-])=O BNIILDVGGAEEIG-UHFFFAOYSA-L 0.000 description 2
- 239000012153 distilled water Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- XOHQAXXZXMHLPT-UHFFFAOYSA-N ethyl(phosphonooxy)phosphinic acid Chemical compound CCP(O)(=O)OP(O)(O)=O XOHQAXXZXMHLPT-UHFFFAOYSA-N 0.000 description 2
- 239000004744 fabric Substances 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 229910001385 heavy metal Inorganic materials 0.000 description 2
- 230000036571 hydration Effects 0.000 description 2
- 238000006703 hydration reaction Methods 0.000 description 2
- 230000002209 hydrophobic effect Effects 0.000 description 2
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical class CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 description 2
- 229910003002 lithium salt Inorganic materials 0.000 description 2
- 159000000002 lithium salts Chemical class 0.000 description 2
- YDSWCNNOKPMOTP-UHFFFAOYSA-N mellitic acid Chemical compound OC(=O)C1=C(C(O)=O)C(C(O)=O)=C(C(O)=O)C(C(O)=O)=C1C(O)=O YDSWCNNOKPMOTP-UHFFFAOYSA-N 0.000 description 2
- 229910021645 metal ion Inorganic materials 0.000 description 2
- 235000019799 monosodium phosphate Nutrition 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 229960003540 oxyquinoline Drugs 0.000 description 2
- 235000011007 phosphoric acid Nutrition 0.000 description 2
- 235000002949 phytic acid Nutrition 0.000 description 2
- 229940081066 picolinic acid Drugs 0.000 description 2
- 239000001205 polyphosphate Substances 0.000 description 2
- 235000011176 polyphosphates Nutrition 0.000 description 2
- CYIDZMCFTVVTJO-UHFFFAOYSA-N pyromellitic acid Chemical compound OC(=O)C1=CC(C(O)=O)=C(C(O)=O)C=C1C(O)=O CYIDZMCFTVVTJO-UHFFFAOYSA-N 0.000 description 2
- MCJGNVYPOGVAJF-UHFFFAOYSA-N quinolin-8-ol Chemical compound C1=CN=C2C(O)=CC=CC2=C1 MCJGNVYPOGVAJF-UHFFFAOYSA-N 0.000 description 2
- 239000001632 sodium acetate Substances 0.000 description 2
- 235000017281 sodium acetate Nutrition 0.000 description 2
- AJPJDKMHJJGVTQ-UHFFFAOYSA-M sodium dihydrogen phosphate Chemical compound [Na+].OP(O)([O-])=O AJPJDKMHJJGVTQ-UHFFFAOYSA-M 0.000 description 2
- 229960001922 sodium perborate Drugs 0.000 description 2
- 239000001488 sodium phosphate Substances 0.000 description 2
- 235000011008 sodium phosphates Nutrition 0.000 description 2
- YKLJGMBLPUQQOI-UHFFFAOYSA-M sodium;oxidooxy(oxo)borane Chemical compound [Na+].[O-]OB=O YKLJGMBLPUQQOI-UHFFFAOYSA-M 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 230000006641 stabilisation Effects 0.000 description 2
- 238000011105 stabilization Methods 0.000 description 2
- 239000007858 starting material Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 description 2
- CIOXZGOUEYHNBF-UHFFFAOYSA-N (carboxymethoxy)succinic acid Chemical compound OC(=O)COC(C(O)=O)CC(O)=O CIOXZGOUEYHNBF-UHFFFAOYSA-N 0.000 description 1
- CFPOJWPDQWJEMO-UHFFFAOYSA-N 2-(1,2-dicarboxyethoxy)butanedioic acid Chemical compound OC(=O)CC(C(O)=O)OC(C(O)=O)CC(O)=O CFPOJWPDQWJEMO-UHFFFAOYSA-N 0.000 description 1
- LVVZBNKWTVZSIU-UHFFFAOYSA-N 2-(carboxymethoxy)propanedioic acid Chemical compound OC(=O)COC(C(O)=O)C(O)=O LVVZBNKWTVZSIU-UHFFFAOYSA-N 0.000 description 1
- XYJLPCAKKYOLGU-UHFFFAOYSA-N 2-phosphonoethylphosphonic acid Chemical class OP(O)(=O)CCP(O)(O)=O XYJLPCAKKYOLGU-UHFFFAOYSA-N 0.000 description 1
- XSVSPKKXQGNHMD-UHFFFAOYSA-N 5-bromo-3-methyl-1,2-thiazole Chemical compound CC=1C=C(Br)SN=1 XSVSPKKXQGNHMD-UHFFFAOYSA-N 0.000 description 1
- JQSMFSPOCAZNQP-UHFFFAOYSA-N 6-(nonylamino)-6-oxohexanoic acid Chemical compound CCCCCCCCCNC(=O)CCCCC(O)=O JQSMFSPOCAZNQP-UHFFFAOYSA-N 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 1
- KXDHJXZQYSOELW-UHFFFAOYSA-N Carbamic acid Chemical class NC(O)=O KXDHJXZQYSOELW-UHFFFAOYSA-N 0.000 description 1
- 235000013162 Cocos nucifera Nutrition 0.000 description 1
- 244000060011 Cocos nucifera Species 0.000 description 1
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 description 1
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical class S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 1
- 241000196324 Embryophyta Species 0.000 description 1
- DBVJJBKOTRCVKF-UHFFFAOYSA-N Etidronic acid Chemical class OP(=O)(O)C(O)(C)P(O)(O)=O DBVJJBKOTRCVKF-UHFFFAOYSA-N 0.000 description 1
- IMQLKJBTEOYOSI-GPIVLXJGSA-N Inositol-hexakisphosphate Chemical class OP(O)(=O)O[C@H]1[C@H](OP(O)(O)=O)[C@@H](OP(O)(O)=O)[C@H](OP(O)(O)=O)[C@H](OP(O)(O)=O)[C@@H]1OP(O)(O)=O IMQLKJBTEOYOSI-GPIVLXJGSA-N 0.000 description 1
- 229910000503 Na-aluminosilicate Inorganic materials 0.000 description 1
- 108091005804 Peptidases Proteins 0.000 description 1
- IMQLKJBTEOYOSI-UHFFFAOYSA-N Phytic acid Natural products OP(O)(=O)OC1C(OP(O)(O)=O)C(OP(O)(O)=O)C(OP(O)(O)=O)C(OP(O)(O)=O)C1OP(O)(O)=O IMQLKJBTEOYOSI-UHFFFAOYSA-N 0.000 description 1
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 1
- 239000004353 Polyethylene glycol 8000 Substances 0.000 description 1
- 239000004365 Protease Substances 0.000 description 1
- 102100037486 Reverse transcriptase/ribonuclease H Human genes 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 239000004115 Sodium Silicate Substances 0.000 description 1
- KDYFGRWQOYBRFD-UHFFFAOYSA-N Succinic acid Chemical class OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 1
- 229910021536 Zeolite Inorganic materials 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 229910000288 alkali metal carbonate Inorganic materials 0.000 description 1
- 150000008041 alkali metal carbonates Chemical class 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 125000003342 alkenyl group Chemical group 0.000 description 1
- 125000005210 alkyl ammonium group Chemical group 0.000 description 1
- 125000005192 alkyl ethylene group Chemical class 0.000 description 1
- 125000000304 alkynyl group Chemical group 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 150000001642 boronic acid derivatives Chemical class 0.000 description 1
- KDYFGRWQOYBRFD-NUQCWPJISA-N butanedioic acid Chemical class O[14C](=O)CC[14C](O)=O KDYFGRWQOYBRFD-NUQCWPJISA-N 0.000 description 1
- HXDRSFFFXJISME-UHFFFAOYSA-N butanedioic acid;2,3-dihydroxybutanedioic acid Chemical class OC(=O)CCC(O)=O.OC(=O)C(O)C(O)C(O)=O HXDRSFFFXJISME-UHFFFAOYSA-N 0.000 description 1
- ADKBGLXGTKOWIU-UHFFFAOYSA-N butanediperoxoic acid Chemical compound OOC(=O)CCC(=O)OO ADKBGLXGTKOWIU-UHFFFAOYSA-N 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 239000002738 chelating agent Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 239000012297 crystallization seed Substances 0.000 description 1
- BLBJUGKATXCWET-UHFFFAOYSA-N cyclaprop Chemical compound C12CC=CC2C2CC(OC(=O)CC)C1C2 BLBJUGKATXCWET-UHFFFAOYSA-N 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 229940061607 dibasic sodium phosphate Drugs 0.000 description 1
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
- XPPKVPWEQAFLFU-UHFFFAOYSA-J diphosphate(4-) Chemical compound [O-]P([O-])(=O)OP([O-])([O-])=O XPPKVPWEQAFLFU-UHFFFAOYSA-J 0.000 description 1
- 229910000397 disodium phosphate Inorganic materials 0.000 description 1
- 235000019800 disodium phosphate Nutrition 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- KRHIGIYZRJWEGL-UHFFFAOYSA-N dodecapotassium;tetraborate Chemical class [K+].[K+].[K+].[K+].[K+].[K+].[K+].[K+].[K+].[K+].[K+].[K+].[O-]B([O-])[O-].[O-]B([O-])[O-].[O-]B([O-])[O-].[O-]B([O-])[O-] KRHIGIYZRJWEGL-UHFFFAOYSA-N 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 230000008030 elimination Effects 0.000 description 1
- 238000003379 elimination reaction Methods 0.000 description 1
- 238000005538 encapsulation Methods 0.000 description 1
- 125000004185 ester group Chemical group 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 239000003925 fat Substances 0.000 description 1
- 235000019197 fats Nutrition 0.000 description 1
- 125000005313 fatty acid group Chemical group 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 239000012065 filter cake Substances 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 235000021588 free fatty acids Nutrition 0.000 description 1
- 229940083124 ganglion-blocking antiadrenergic secondary and tertiary amines Drugs 0.000 description 1
- 230000002070 germicidal effect Effects 0.000 description 1
- 125000005456 glyceride group Chemical group 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- 125000001165 hydrophobic group Chemical group 0.000 description 1
- 239000003752 hydrotrope Substances 0.000 description 1
- 239000005457 ice water Substances 0.000 description 1
- 238000010348 incorporation Methods 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 239000002563 ionic surfactant Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 239000004310 lactic acid Substances 0.000 description 1
- 235000014655 lactic acid Nutrition 0.000 description 1
- 238000004900 laundering Methods 0.000 description 1
- INHCSSUBVCNVSK-UHFFFAOYSA-L lithium sulfate Inorganic materials [Li+].[Li+].[O-]S([O-])(=O)=O INHCSSUBVCNVSK-UHFFFAOYSA-L 0.000 description 1
- XKPJKVVZOOEMPK-UHFFFAOYSA-M lithium;formate Chemical compound [Li+].[O-]C=O XKPJKVVZOOEMPK-UHFFFAOYSA-M 0.000 description 1
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
- 239000011976 maleic acid Substances 0.000 description 1
- 125000005341 metaphosphate group Chemical group 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 229940045641 monobasic sodium phosphate Drugs 0.000 description 1
- 229910000403 monosodium phosphate Inorganic materials 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- MGFYIUFZLHCRTH-UHFFFAOYSA-N nitrilotriacetic acid Chemical class OC(=O)CN(CC(O)=O)CC(O)=O MGFYIUFZLHCRTH-UHFFFAOYSA-N 0.000 description 1
- 235000019645 odor Nutrition 0.000 description 1
- 230000009965 odorless effect Effects 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 235000019198 oils Nutrition 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 239000005486 organic electrolyte Substances 0.000 description 1
- MPQXHAGKBWFSNV-UHFFFAOYSA-N oxidophosphanium Chemical class [PH3]=O MPQXHAGKBWFSNV-UHFFFAOYSA-N 0.000 description 1
- 239000012188 paraffin wax Chemical class 0.000 description 1
- 238000003921 particle size analysis Methods 0.000 description 1
- LQPLDXQVILYOOL-UHFFFAOYSA-I pentasodium;2-[bis[2-[bis(carboxylatomethyl)amino]ethyl]amino]acetate Chemical compound [Na+].[Na+].[Na+].[Na+].[Na+].[O-]C(=O)CN(CC([O-])=O)CCN(CC(=O)[O-])CCN(CC([O-])=O)CC([O-])=O LQPLDXQVILYOOL-UHFFFAOYSA-I 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- XYFCBTPGUUZFHI-UHFFFAOYSA-O phosphonium Chemical compound [PH4+] XYFCBTPGUUZFHI-UHFFFAOYSA-O 0.000 description 1
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 1
- 239000000467 phytic acid Substances 0.000 description 1
- 229940068041 phytic acid Drugs 0.000 description 1
- 229920001495 poly(sodium acrylate) polymer Polymers 0.000 description 1
- 229920005646 polycarboxylate Polymers 0.000 description 1
- 235000019446 polyethylene glycol 8000 Nutrition 0.000 description 1
- 229940085678 polyethylene glycol 8000 Drugs 0.000 description 1
- 229920006324 polyoxymethylene Polymers 0.000 description 1
- 238000010791 quenching Methods 0.000 description 1
- 230000000171 quenching effect Effects 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000007127 saponification reaction Methods 0.000 description 1
- 150000004760 silicates Chemical class 0.000 description 1
- 238000005549 size reduction Methods 0.000 description 1
- 235000012217 sodium aluminium silicate Nutrition 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 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
- MWNQXXOSWHCCOZ-UHFFFAOYSA-L sodium;oxido carbonate Chemical compound [Na+].[O-]OC([O-])=O MWNQXXOSWHCCOZ-UHFFFAOYSA-L 0.000 description 1
- 239000002689 soil Substances 0.000 description 1
- 239000002195 soluble material Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000012798 spherical particle Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 230000001180 sulfating effect Effects 0.000 description 1
- 150000003871 sulfonates Chemical class 0.000 description 1
- 150000003462 sulfoxides Chemical class 0.000 description 1
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 1
- 239000000375 suspending agent Substances 0.000 description 1
- 229940095064 tartrate Drugs 0.000 description 1
- RBTVSNLYYIMMKS-UHFFFAOYSA-N tert-butyl 3-aminoazetidine-1-carboxylate;hydrochloride Chemical compound Cl.CC(C)(C)OC(=O)N1CC(N)C1 RBTVSNLYYIMMKS-UHFFFAOYSA-N 0.000 description 1
- 150000000000 tetracarboxylic acids Chemical class 0.000 description 1
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 1
- 229940001496 tribasic sodium phosphate Drugs 0.000 description 1
- 229910000406 trisodium phosphate Inorganic materials 0.000 description 1
- 235000019801 trisodium phosphate Nutrition 0.000 description 1
- 238000003828 vacuum filtration Methods 0.000 description 1
- 239000003643 water by type Substances 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
- 239000002888 zwitterionic surfactant Substances 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
- C11D3/50—Perfumes
-
- 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
- C11D3/39—Organic or inorganic per-compounds
- C11D3/3945—Organic per-compounds
Definitions
- This invention relates to granular detergent or bleaching compositions containing amidoperoxyacid bleach and selected perfume ingredients which have improved stability when in direct contact with the bleach.
- a complete perfume containing the stable perfume ingredients is sprayed directly onto the granular detergent or bleaching composition containing the amidoperoxyacid bleach.
- the compositions are preferably used for cleaning laundry, but can also be used for cleaning or bleaching hard surfaces.
- Perfumes are a desirable part of the laundry process. They are used to cover up the chemical odors of the cleaning ingredients and provide an aesthetic benefit to the wash process and, preferably, the cleaned fabrics. Perfumes are often added directly to laundry compositions, such as by spraying the perfume onto finished compositions. However, perfumes are, in general, volatile and many perfume ingredients can be destroyed or damaged by contact with cleaning ingredients, especially alkali and bleaches. To minimize direct contact between perfume and bleach components in laundry compositions, bleaches are sometimes admixed after perfume spray-on. Even this does not avoid oxidation of perfumes by bleaches, particularly when reactive bleaches such as peroxyacids are present, at least partly because of perfume mobility in granular detergent compositions.
- European Patent Application 332,259 published September 13, 1989, discloses granular detergent or bleaching compositions containing peroxyacid bleach, including amidoperoxyacids, and perfumed silica particles which separate and protect the perfume from oxidation by the bleach.
- JP-A-60,023,498 discloses compositions containing percarbonate bleach and selected perfume components.
- JP-A-60,245,699 discloses compositions containing monopersulphate bleach and selected perfumes.
- JP-A-63,275,697 discloses compositions containing inorganic peroxide bleach and selected perfumes.
- the present invention relates to granular detergent or bleaching compositions comprising, by weight:
- the granular detergent or bleaching compositions of the present invention comprise amidoperoxyacid bleach and selected perfume ingredients which have improved stability when in direct contact with the bleach, such as happens when a complete perfume containing the stable perfume ingredients is sprayed directly onto the composition containing the bleach or prior to the addition of the bleach.
- the present compositions have improved amidoperoxyacid bleach stability due to the low reactivity with perfume ingredients.
- the granular detergent or bleaching compositions of the present invention comprise from about 1% to about 75%, preferably from about 2% to about 60%, more preferably from about 3% to about 50%, by weight of an amidoperoxyacid bleach of the formula wherein R1 is an alkyl group containing from about 6 to about 12 carbon atoms, and R is an alkylene containing from 1 to about 6 carbon atoms.
- R1 is an alkyl group containing from about 8 to about 10 carbon atoms
- R is an alkylene group containing from about 2 to about 4.
- Bleach granules for use by themselves or as an additive for granular detergent compositions preferably contain from about 20% to about 70%, more preferably from about 30% to about 60%, by weight of the amidoperoxyacid bleach.
- Fully formulated granular detergents preferably contain from about 2% to about 10%, more preferably from about 3% to about 6%, by weight of the amidoperoxyacid bleach.
- a preferred amidoperoxyacid herein is the mono n onyl a mide of p eroxy s uccinic a cid ("NAPSA"). Most preferred is the mono n onyl a mide of p eroxy a dipic a cid (“NAPAA"). Another name for NAPAA is 6-(nonylamino)-6-oxo-caproic acid. The chemical formula for NAPAA is: The molecular weight of NAPAA is 287.4.
- Example I of U.S. Patent 4,686,063 contains a description of the synthesis of NAPSA, from column 8, line 40 to Column 9, line 5, and NAPAA, from column 9, line 15 to column 9, line 65.
- the reaction is quenched with water, filtered, washed with water to remove some excess sulfuric acid (or other strong acid with which the peroxyacid was made), and filtered again.
- the amidoperoxyacid wet cake thus obtained is contacted with a phosphate buffer solution at a pH between about 3.5 and 6, preferably between about 4 and 5. It has been found that if the pH of the amidoperoxyacid wet cake is raised too high, the amidoperoxyacid is dissolved, but if the pH is too low, the amidoperoxyacid is unstable. Without meaning to be bound by theory, it is believed that to stabilize the amidoperoxyacid, the strong acidity remaining from the sulfuric acid (or other strong acid) with which the peroxyacid is made must be neutralized without at the same time destroying the weak acid which is the peroxyacid. A buffer accomplishes this purpose.
- phosphate buffer but not acetate or water washing, stabilizes the amidoperoxyacid. Since water washing to the same pH does not achieve the same effect as the phosphate buffer wash, it is theorized that some of the phosphate remains in the wet cake after contact with the phosphate buffer, which also helps storage stability. This is further borne out by the fact that phosphate buffer washing followed by water washing results in the peroxyacid having less stability than phosphate buffer washing alone.
- the phosphate buffer is preferably orthophosphate or pyrophosphate in a concentration range of from about 0.01 M (moles/liter) to about 1 M. Most preferred is a 0.10 M solution of orthophosphates. These can be selected from the group consisting of H3PO4 (phosphoric acid), NaH2PO4 (monobasic sodium phosphate), Na2HPO4 (dibasic sodium phosphate), and Na3PO4 (tribasic sodium phosphate), so that the final solution has a pH of between about 3.5 and 6, preferably between about 4 and 5. Other salts such as potassium can be employed. Examples of phosphate buffer solution compositions can be found in Buffers for DH and Metal Ion Control by D.D. Perrin and Boyd Dempsey (Chapman & Hall, 1974).
- the amidoperoxyacid can be contacted with the phosphate buffer solution.
- the amidoperoxyacid wet cake is placed in enough of the phosphate buffer to cover it, and the combination is slowly stirred for a period of time sufficient to assure thorough contact with the wet cake.
- Suction filtration is then preferably applied to remove the solution.
- the wet cake can then be air dried overnight.
- less phosphate buffer solution of a stronger concentration could be used.
- a 0.1 M phosphate buffer solution is preferred since it provides more volume and, when mixed with the wet cake, thorough contact and easier stirring than, for example, a 0.5 M solution.
- Another preferred way of contacting the wet cake with the buffer is to pour the buffer over the wet cake and then apply vacuum filtration.
- the filtered wet cake could be placed on a fluid bed for final drying before it is incorporated into the final detergent composition or bleaching agent.
- the phosphate buffer wash should be done before the amidoperoxyacid has decomposed.
- the product has decomposed when there is so little amidoperoxyacid remaining that it is no longer an effective bleach.
- the activity of the amidoperoxyacid can be measured by the available oxygen. Generally, the higher the AvO is, the better the peroxyacid will bleach.
- amidoperoxyacid can be added to the amidoperoxyacid before incorporation into the final product.
- boric acid an exotherm control agent disclosed in U.S. Patent 4,686,063, Burns, issued August 11, 1987 and incorporated herein, can be mixed with the amidoperoxyacid (which has been washed in phosphate buffer) in about a 2:1 peracid:boric acid ratio.
- the phosphate buffer washed amidoperoxyacid can also be mixed with appropriate amounts of dipicolinic acid and tetrasodium pyrophosphate, a chelating stabilization system.
- the phosphate buffer washed amidoperoxyacid be formed into granules, dried, and used either separately or as part of a granular detergent composition.
- the granules can be comprised of from about 1% to about 75% of the phosphate buffer washed amidoperoxyacid, preferably from about 20% to about 70%, more preferably from about 30% to about 60% of NAPSA or NAPAA; from 0% to about 25% of an exotherm control agent, preferably from about 5% to about 15% of boric acid if present; from 0 to about 10% of C11 ⁇ 13 linear alkylbenzene sulfonate or C14 ⁇ 15 alkyl sulfate, preferably from about 2% to about 7% of C11 ⁇ 13 linear alkylbenzene sulfonate; from about 20% to about 70%, preferably from about 30% to about 60%, sulfate; and from 0 to about 20% of a chelating agent, preferably from about 0.02% to about 0.10%
- Chelants can optionally be included in the phosphate buffer before contact with the wet cake. Without wishing to be bound by theory, it is believed that adding the chelants in this way improves their effectiveness by more evenly distributing the chelants throughout the wet cake.
- Suitable chelants for use herein are: carboxylates, such as ethylene diamine tetraacetate (EDTA) and diethylene triamine pentaacetate (DTPA); polyphosphates, such as sodium acid pyrophosphate (SAPP), tetrasodium pyrophosphate (TSPP), and sodium tripolyphosphate (STPP); phosphonates, such as ethylhydroxydiphosphonate (Dequest® 2010) and other sequestering agents sold under the Dequest® trade name; and combinations of the above.
- Other sequestering agents for use herein are dipicolinic acid, picolinic acid, and 8-hydroxyquinoline, and combinations thereof.
- amidoperoxyacid herein can be used in a granular detergent composition or in a separate granular bleaching composition. It is more preferred that the amidoperoxyacid be incorporated into a granular laundry detergent composition. It is most preferred that the amidoperoxyacid be NAPSA or NAPAA and be formed into granules (after the phosphate buffer wash and drying) which are then incorporated into a granular laundry detergent composition.
- bleach granules comprising three ingredients: NAPAA, bleach-stable surfactant, and a hydratable, NAPAA-compatible material.
- NAPAA can be prepared by, for example, first reacting NAAA (monononyl amide of adipic acid), sulfuric acid, and hydrogen peroxide. The reaction product is quenched by addition to ice water followed by filtration, washing with distilled water, and final suction filtration to recover the wet cake. Washing can be continued until the pH of the filtrate is neutral.
- NAAA nononyl amide of adipic acid
- sulfuric acid sulfuric acid
- hydrogen peroxide hydrogen peroxide
- NAPAA agglomerates are desired herein to increase the amount of effective bleach which is in the wash solution and thereby improve bleaching/cleaning of fabrics in the wash.
- This is particularly useful in a hard water wash, i.e. wash water with more than about 6 grains of hardness, because hardness, specifically calcium ions, has been seen to interfere with available oxygen (AvO) from NAPAA with larger particle size.
- AvO available oxygen
- the calcium ions in the hard water surround large NAPAA particles, i.e. greater than about 300 ⁇ m, and interfere with the dissolution of the NAPAA, and that the smaller (about 0.1-260 ⁇ m) NAPAA particles dissolve rapidly in the wash water with minimal interference from the hardness ions.
- Small NAPAA particles are preferably recovered by quenching in water with high shear applied, e.g. rapid stirring, during addition of the NAPAA solution to water. Other known means of achieving small particle size may be used as appropriate.
- the NAPAA is then rinsed with water to remove excess sulfuric acid.
- the average particle size of the NAPAA herein is 0.1 to 260 ⁇ m and is in large part a function of the amount of shear applied. Even better solubility in harder water can be achieved, though, with a NAPAA average particle size of between about 1 and 160 ⁇ m.
- the average particle size is preferably from about 5 to 100 ⁇ m, and most preferably from about 5 to about 40 ⁇ m.
- NAPAA filter cake herein is preferably washed twice in phosphate buffer. It has been found that two successive phosphate buffer washes lend optimal stability to NAPAA. It is also highly preferred that the NAPAA pH (10% solids in water) be between about 4.2 and 4.75. Surprisingly, this pH results in more thermally stable particles.
- the bleach granules of this invention also include from about 1 to 40 weight % bleach-stable detergent surfactant selected from the group consisting of anionics, nonionics, zwitterionics and ampholytics and combinations thereof. From about 2 to 25 weight % bleach-stable detergent surfactant is preferred and about 2 to 7 weight % is most preferred.
- Anionic surfactant is preferred and salts of C11 ⁇ 13 linear alkyl benzene sulfonate and/or C12 ⁇ 16 alkyl sulfate are more preferred. Sodium C12 ⁇ 13 linear alkyl benzene sulfonate is most preferred.
- Detergent surfactants useful herein are listed in U.S. Patents 3,664,961, Norris, issued May 23, 1972, and 3,929,678, Laughlin et al, issued December 30, 1975, both incorporated herein by reference. The following are representative examples of detergent surfactants useful in the present compositions.
- Water-soluble salts of the higher fatty acids are useful anionic surfactants in the compositions herein.
- Soaps can be made by direct saponification of fats and oils or by the neutralization of free fatty acids.
- Particularly useful are the sodium and potassium salts of the mixtures of fatty acids derived from coconut oil and tallow, i.e., sodium or potassium tallow and coconut soap.
- Useful anionic surfactants also include the water-soluble salts, preferably the alkali metal, ammonium and alkylolammonium salts, of organic sulfuric reaction products having in their molecular structure an alkyl group containing from about 10 to about 20 carbon atoms and a sulfonic acid or sulfuric acid ester group.
- alkyl is the alkyl portion of acyl groups.
- this group of synthetic surfactants are the sodium and potassium alkyl sulfates, especially those obtained by sulfating the higher alcohols (C8-C18 carbon atoms) such as those produced by reducing the glycerides of tallow or coconut oil; and the sodium and potassium alkylbenzene sulfonates in which the alkyl group contains from about 9 to about 15 carbon atoms, in straight chain or branched chain configuration, e.g., those of the type described in U.S. Patents 2,220,099 and 2,477,383.
- Especially valuable are linear straight chain alkylbenzene sulfonates in which the average number of carbon atoms in the alkyl group is from about 11 to 13, abbreviated as C11 ⁇ 13LAS.
- anionic surfactants herein are the sodium alkyl glyceryl ether sulfonates, especially those ethers of higher alcohols derived from tallow and coconut oil; sodium coconut oil fatty acid monoglyceride sulfonates and sulfates; sodium or potassium salts of alkyl phenol ethylene oxides ether sulfates containing from about 1 to about 10 units of ethylene oxide per molecule and wherein the alkyl groups contain from about 8 to about 12 carbon atoms; and sodium or potassium salts of alkyl ethylene oxide ether sulfates containing about 1 to about 10 units of ethylene oxide per molecule and wherein the alkyl group contains from about 10 to about 20 carbon atoms.
- Other useful anionic surfactants herein include the water-soluble salts of esters of alpha-sulfonated fatty acids containing from about 6 to 20 carbon atoms in the fatty acid group and from about 1 to 10 carbon atoms in the ester group; water-soluble salts of 2-acyloxyalkane-1-sulfonic acids containing from about 2 to 9 carbon atoms in the acyl group and from about 9 to about 23 carbon atoms in the alkane moiety; water-soluble salts of olefin and paraffin sulfonates containing from about 12 to 20 carbon atoms; and beta-alkyloxy alkane sulfonates containing from about 1 to 3 carbon atoms in the alkyl group and from about 8 to 20 carbon atoms in the alkane moiety.
- Water-soluble nonionic surfactants are also useful in the compositions of the invention.
- Such nonionic materials include compounds produced by the condensation of alkylene oxide groups (hydrophilic in nature) with an organic hydrophobic compound, which may be aliphatic or alkyl aromatic in nature.
- the length of the polyoxyalkylene group which is condensed with any particular hydrophobic group can be readily adjusted to yield a water-soluble compound having the desired degree of balance between hydrophilic and hydrophobic elements.
- Suitable nonionic surfactants include the polyethylene oxide condensates of alkyl phenols, e.g., the condensation products of alkyl phenols having an alkyl group containing from about 6 to 15 carbon atoms, in either a straight chain or branched configuration, with from 3 to 12 moles of ethylene oxide per mole of alkyl phenol.
- Preferred nonionics are the water-soluble and water-dispersible condensation products of aliphatic alcohols containing from 8 to 22 carbon atoms, in either straight chain or branched configuration, with from 3 to 12 moles of ethylene oxide per mole of alcohol.
- Particularly preferred are the condensation products of alcohols having an alkyl group containing from about 9 to 15 carbon atoms with from about 4 to 8 moles of ethylene oxide per mole of alcohol.
- Semi-polar nonionic surfactants include water-soluble amine oxides containing one alkyl moiety of from about 10 to 18 carbon atoms and two moieties selected from the group of alkyl and hydroxyalkyl moieties of from about 1 to about 3 carbon atoms; water-soluble phosphine oxides containing one alkyl moiety of about 10 to 18 carbon atoms and two moieties selected from the group consisting of alkyl groups and hydroxyalkyl groups containing from about 1 to 3 carbon atoms; and water-soluble sulfoxides containing one alkyl moiety of from about 10 to 18 carbon atoms and a moiety selected from the group consisting of alkyl and hydroxyalkyl moieties of from about 1 to 3 carbon atoms.
- Ampholytic surfactants include derivatives of aliphatic or aliphatic derivatives of heterocyclic secondary and tertiary amines in which the aliphatic moiety can be straight chain or branched and wherein one of the aliphatic substituents contains from about 8 to 18 carbon atoms and at least one aliphatic substituent contains an anionic water-solubilizing group.
- Zwitterionic surfactants include derivatives of aliphatic, quaternary, ammonium, phosphonium, and sulfonium compounds in which one of the aliphatic substituents contains from about 8 to 18 carbon atoms.
- the bleach granules herein also comprise from about 10 to 95 weight % hydratable, NAPAA-compatible material.
- the material preferably has a pH below about 8.0, most preferably below about 7.0. These can be selected from the group consisting of sodium sulfate, sodium acetate, sodium perborate, sodium phosphate, sodium acid phosphite, lithium formate, lithium sulfate, zinc nitrate, and combinations thereof.
- bleach granules comprise from about 20 to 70, most preferably 30 to 50, weight % of the above hydratable, NAPAA-compatible material. Materials to be avoided contain heavy metals such as iron and halides.
- hydratable materials are useful in processing the bleach granules of this invention and they add integrity to the final bleach granule.
- An appropriate method for forming these bleach granules is described in U.S. Patent 4,091,544, Hutchins, issued May 30, 1978, incorporated herein. That process involves allowing the mixture to be formed into spherical particles, flakes, ribbons or other desired configuration. The chosen forms are then cooled to a temperature sufficiently low so that the hydratable material is hydrated. To remove the unwanted waters of hydration and free water the material is heated to a temperature which allows the water to be driven off but will not cause the forms to soften and stick together. This process allows for the elimination of the need for further size reduction and the associated dust. Other known methods of forming granules or agglomerates may be used as appropriate.
- boric acid an exotherm control agent
- peroxygen bleaching compounds can be stabilized by addition of exotherm control agents, particularly boric acid.
- boric acid When the present NAPAA-containing bleach granules are incorporated in a granular detergent composition, leaving out boric acid results in improved thermal stability when compared to the same granules containing boric acid. This difference in stability is marked in bleach granules comprising about 25 weight % NAPAA. It is therefore preferred herein not to include boric acid in the NAPAA bleach granules.
- chelants which are optionally not included herein, are: carboxylates, such as ethylene diamine tetraacetate (EDTA) and diethylene triamine pentaacetate (DTPA); polyphosphates, such as sodium acid pyrophosphate (SAPP), tetrasodium pyrophosphate (TSPP), and sodium tripolyphosphate (STPP); phosphonates, such as ethylhydroxydiphosphonate (Dequest® 2010) and other sequestering agents sold under the Dequest® trade name; dipicolinic acid, picolinic acid, and 8-hydroxyquinoline, and combinations thereof.
- carboxylates such as ethylene diamine tetraacetate (EDTA) and diethylene triamine pentaacetate (DTPA)
- polyphosphates such as sodium acid pyrophosphate (SAPP), tetrasodium pyrophosphate (TSPP), and sodium tripolyphosphate (STPP)
- phosphonates such as ethylhydroxydi
- the bleach granules herein are effective bleaching agents and are stable in solution and in product, expecially in preferred form, i.e. without boric acid or additional chelants, and where NAPAA has been phosphate buffer washed and brought to a pH between about 3.5 and 6 before addition to the bleach granule.
- compositions of the present invention also comprise from about 0.1% to about 2%, preferably from about 0.2% to about 1%, preferably from about 0.25% to about 0.75%, by weight of a perfume comprising at least about 60% by weight of perfume ingredients selected from the group consisting of amyl salicylate, anisaldehyde, benzyl salicylate, butyl cinnamic aldehyde, citronellol, cyclohexyl salicylate, eugenol, Exaltex, tricyclodecenyl acetate, geraniol, Herbavert, ionone beta, ionone gamma methyl, keone, methyl cedrylone, Methyl cyclogeraniate, rose oxide DL, patchouli, phenyl ethyl alcohol, terpineol, Tonalid, Undecavertol, vanillin, Ylang Oliffac 765, Ambretone, Linacsol, Me
- perfumes herein comprise at least about 60% by weight of perfume ingredients selected from the group consisting of amyl salicylate, anisaldehyde, benzyl salicylate, cyclohexyl salicylate, eugenol, Exaltex, Herbavert, ionone beta, keone, Methyl cyclogeraniate, Tonalid, vanillin, Ylang Oliffac 765, Linacsol, Trepanol, Dihydroterpineol T, Mayol, Ambrox asphalt, Parmantheme, LRG 201, paramethoxy acetophenone, musk ketone, Galaxolide 50, Sinocitryl, dimethyl octanol, musk xylol, Cashmeran, Clonal, Camekol DH, Rhubafuran V-9042, Marenil (N), tonkalactone, iso jasmone, Dihydrofloralol, Nardorosol,
- perfume ingredients include Exaltex, Methyl cyclogeraniate, vanillin, Ylang Oliffac 765, Trepanol, Ambrox asphalt, paramethoxy acetophenone, Sinocitryl, Clonal, Camekol DH, iso jasmone, Dihydrofloralol, Nardorosol, fenchyl alcohol, and tridecene-2-nitrile. These ingredients have a stability grade of 9B or higher after three months.
- Preferred perfume ingredients for use herein are those having a stability grade of 7B or higher after six months, as described in Example I. These include amyl salicylate, anisaldehyde, benzyl salicylate, citronellol, cyclohexyl salicylate, eugenol, Exaltex, ionone beta, methyl cedrylone, patchouli, Tonalid, vanillin, Trepanol, Grisalva, Ambrox asphalt, Parmantheme, coumarin, LRG 201, paramethoxy acetophenone, musk ketone, Galaxolide 50, Traseolide 70, Sinocitryl, musk xylol, Clonal, Sandalore, Marenil (N), clove oil, Exaltolide, iso jasmone, Nardorosol, fenchyl alcohol, B napthyl methyl ether, and tridecene-2-nitrile.
- the more preferred ingredients have a stability grade of 8B or higher after six months.
- these include benzyl salicylate, cyclohexyl salicylate, ionone beta, vanillin, Ambrox asphalt, LRG 201, paramethoxy acetophenone, musk ketone, Sinocitryl, Marenil (N), Nardorosol, fenchyl alcohol, and tridecene-2-nitrile.
- the most preferred ingredients have a stability grade of 9B or higher after six months. These are vanillin, paramethoxy acetophenone, Sinocitryl, and tridecene-2-nitrile.
- perfume materials herein are those which are generally considered unstable in the presence of peroxyacid bleaches, yet have stability grades of 7B or higher after three months, as reported in Example I. These include amyl salicylate, benzyl salicylate, citronellol, eugenol, tricyclodecenyl acetate, methyl cedrylone, and tricyclo decenyl propionate.
- Particularly perfumes herein comprise at least about 65%, preferably at least about 70%, and more preferably at least about 75% by weight of the above stable perfume ingredients.
- the bleach granules herein are preferably included in a granular detergent composition or bleaching composition.
- the preferred granular detergent composition comprises from about 2 to 50, preferably about 5 to 25, weight % bleach granules according to the above description, from about 5 to 50 weight % detergent surfactant, which is described above, and from about 10 to 60 weight % detergency builder.
- the bleaching composition preferably comprises from about 10 to 100 weight % of the present bleach granules.
- Water-soluble inorganic or organic electrolytes are suitable detergency builders.
- the builder can also be water-insoluble calcium ion exchange materials; non-limiting examples of suitable water-soluble, inorganic detergent builders include: alkali metal carbonates, borates, phosphates, bicarbonates and silicates. Specific examples of such salts include sodium and potassium tetraborates, bicarbonates, carbonates, orthophosphates, pyrophosphates, tripolyphosphates and metaphosphates.
- suitable organic alkaline detergency builders include: (1) water-soluble amino carboxylates and aminopolyacetates, for example, nitrilotriacetates, glycinates, ethylenediaminetetraacetates, N-(2-hydroxyethyl)nitrilodiacetates and diethylenetriaminepentaacetates; (2) water-soluble salts of phytic acid, for example, sodium and potassium phytates; (3) water-soluble polyphosphonates, including sodium, potassium and lithium salts of ethane-1-hydroxy-1, 1-diphosphonic acid; sodium, potassium, and lithium salts of ethylene diphosphonic acid; and the like; (4) water-soluble polycarboxylates such as the salts of lactic acid, succinic acid, malonic acid, maleic acid, citric acid, carboxymethyloxysuccinic acid, tartrate mono- and disuccinates (ether linked), oxydisuccinate, 2-oxa-1,1,3-propane tricarboxylic
- a water-soluble material capable of forming a water-soluble reaction product with water hardness cations preferably in combination with a crystallization seed which is capable of providing growth sites for said reaction product.
- a further class of detergency builder materials useful in the present invention are insoluble sodium aluminosilicates, particularly those described in U.S. Patent 4,605,509, issued August 12, 1986, incorporated herein by reference.
- the detergent compositions of this invention can contain all of the usual components of detergent compositions including the ingredients set forth in U.S. Patent 3,936,537, Baskerville et al, incorporated herein by reference.
- Such components include color speckles, suds boosters, suds suppressors, antitarnish and/or anticorrosion agents, soil-suspending agents, soil-release agents, dyes, fillers, optical brighteners, germicides, alkalinity sources, hydrotropes, antioxidants, enzymes, enzyme stabilizing agents, etc.
- suitable enzymes can be found in U.S. Patent 4,101,457, Place et al, issued July 18, 1978, incorporated herein by reference.
- a freshly-prepared sample of NAPAA wet cake which typically consists of about 60% water, about 2% peroxyacid available oxygen (AvO) (corresponding to about 36% NAPAA), and the rest (about 4%) unreacted starting material, is obtained.
- This wet cake is the crude reaction product of NAAA (monononyl amide of adipic acid), sulfuric acid, and hydrogen peroxide which is subsequently quenched by addition to water followed by filtration, washing with distilled water, phosphate buffer washing and final suction filtration to recover the wet cake.
- a portion of the wet cake is air-dried at room temperature to obtain a dry sample which typically consists of about 5% AvO (corresponding about to 90% NAPAA) and about 10% unreacted starting material.
- the sample pH is about 4.5.
- the average amide peroxyacid particle (agglomerate) size is about 90-100 ⁇ m and the median particle size is about 40-50 ⁇ m, as determined by Malvern particle size analysis.
- NAPAA granules are prepared by mixing about 51.7 parts of the dried NAPAA wet cake (containing about 10% unreacted), about 11.1 parts of sodium C 12.3 linear alkyl benzene sulfonate (LAS) paste (45% active), about 43.3 parts of sodium sulfate, and about 30 parts of water in a Cuisinart mixer. After drying, the granules (which contain about 47% NAPAA) are sized by passing through a No. 14 Tyler mesh sieve and retaining all particles not passing through a No. 65 Tyler mesh.
- LAS linear alkyl benzene sulfonate
- the bleach granules are then admixed with a granular detergent to provide a finished bleach-containing detergent composition having the following Composition A.
- Similar bleach granules made containing about 50% NAPAA and 40% sulfate are admixed with a granular detergent to provide the following Composition B.
- Perfume ingredients are evaluated for stability when in direct contact with the above unperfumed detergent compositions (ingredients tested with Composition B are noted by *, the other ingredients are tested with Composition A), using the following method.
- a pefume composition of the present invention is as follows: Ingredient Wt.% amyl salicylate 3.00 benzyl salicylate 15.00 cyclohexyl salicylate (Henkel) 5.00 Galaxolide 50% 15.00 LRG 201 (Roure) 0.50 Mayol (Firmenich) 10.00 methyl cedrylone 15.00 methyl cyclogeraniate (Firmenich) 0.50 Nardorosol (Quest) 10.00 paramethoxy acetophenone 0.50 phenyl ethyl alcohol 10.00 Tonalid (PFW) 10.00 Trepanol (Takasago) 0.50 Ylang Oliffac 765 (IFF) 5.00 Total 100.00
- the above perfume composition which contains 100% by weight of perfume ingredients having a stability grade of 7B or higher after three months and 75% by weight of ingredients having a stability grade of 8B or higher after three months, is sprayed directly onto the following granular detergent and bleaching composition of the present invention.
- Example II The perfume composition of Example II is sprayed directly onto the following granular detergent and bleaching composition of the present invention.
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Claims (7)
- Granulatförmige Wasch- oder Bleichmittelzusammensetzung, dadurch gekennzeichnet, daß sie, bezogen auf Gewicht, folgendes umfaßt:
(a) 1 bis 75 % eines Amidoperoxysäure-Bleichmittels der Formel:(b) 0,1 bis 2% eines Duftstoffs, der mindestens 60 Gew.-%, vorzugsweise mindestens etwa 70 Gew.-% Duftstoffbestandteile umfaßt, die aus der Amylsalicylat, Anisaldehyd, Benzylsalicylat, Butylzimtaldehyd. Citronellol, Cyclohexylsalicylat, Eugenol, Exaltex, Tricyclodecenylacetat, Geraniol, Herbavert, Ionon-Beta, Ionon-Gammamethyl, Keon, Methylcedrylon, Methylcyclogeraniat, Rosenoxid DL, Patschuli, Phenylethylalkohol, Terpineol, Tonalid, Undecavertol, Vanillin, Ylang Oliffac 765, Ambreton, Linacsol, Methanylacetat T. Methylsandeflor, Trepanol, Dihydroterpineol T, Grisalva, Mayol, Ambrox coeur, Parmantheme, Coumarin, LRG 201, Paramethoxyacetophenon, Moschusketon, Galaxolide 50, Tricyclodecenylproprionat, Traseolide 70, Sinocitryl, Dimethyloctanol, Moschusxylol, Cashmeran, Clonal, Camekol DH, Sandalore, Rhubafuran V-9042, Ceromel 3, Marenil (N), Corps rhubarb, Nelkenöl, Phenylethylacetat, Tonkalacton, Exaltolide, Isojasmon, Ambrettolid, Dihydrofloralol, Cedar English, Nardorosol, Fenchylalkohol, B Naphthylmethylether und Tridecen-2-nitril umfassenden Gruppe gewählt sind;wobei der Duftstoff in direktem Kontakt mit dem Amidoperoxysäure-Bleichmittel ist. - Zusammensetzung nach Anspruch 1, wobei das Amidoperoxysäure-Bleichmittel das Nonylamid von Peroxyadipinsäure ("NAPAA") ist.
- Zusammensetzung nach Anspruch 2, wobei das NAPAA in einem Bleichmittelgranulat vorliegt, umfassend:(a) 5 bis 70 Gew.-% NAPAA mit einer durchschnittlichen Teilchengröße vom 0,1 bis 260 µm;(b) 1 bis 40 Gew. -% bleichmittelstabiles Tensid, gewählt aus der anionische, nichtionische, ampholytische, zwitterionische Bleichmittel und Kombinationen davon umfassenden Gruppe; und(c) 10 bis 95 Gew.-% eines hydratisierbaren, NAPAA-verträglichen Materials.
- Zusammensetzung nach Anspruch 3, wobei das Bleichmittelgranulat im wesentlichen aus:(a) 20 bis 60 Gew.-% NAPAA mit einer durchschnittlichen Teilchengröße von 5 bis 40 µm;(b) 2 bis 7 Gew-% lineares Natrium-C₁₂₋₁₃-alkylbenzolsulfonat; und(c) 30 bis 50 Gew.-% Natriumsulfatbesteht.
- Granulatförmige Waschmittelzusammensetzung, umfassend 2 bis 50 Gew.-% Bleichmittelgranulate nach Anspruch 4, 5 bis 50 Gew. -% Waschmitteltensid und 10 bis 60 Gew.-% Waschmittelbuilder.
- Zusammensetzung nach mindestens einem der vorangehenden Ansprüche, wobei die Duftstoffbestandteile aus der Amylsalicylat, Anisaldehyd. Benzylsalicylat, Cyclohexylsalicylat, Eugenol, Exaltex, Herbavert, Ionon-Beta, Keon. Methylcyclogeraniat, Tonalid, Vanillin, Ylang Oliffac 765, Linacsol, Trepanol, Dihydroterpineol T, Mayol, Ambrox coeur, Parmantheme, LRG 201, Paramethoxyacetophenon, Moschusketon, Galaxolide 50, Sinocitryl, Dimethyloctanol, Moschusxylol, Cashmeran, Clonal, Camekol DH, Rhubafuran V-9042, Marenil (N), Tonkalacton, Isojasmon, Dihydrofloralol, Nardorosol, Fenchylalkohol, B Naphthylmethylether und Tridecen-2-nitril umfassenden Gruppe gewählt sind.
- Zusammensetzung nach mindestens einem der vorangehenden Ansprüche, wobei die Duftstoffbestandteile aus der Exaltex, Methylcyclogeraniat, Vanillin, Ylang Oliffac 765, Trepanol, Ambrox coeur, Paramethoxyacetophenon, Sinocitryl, Clonal, Camekol DH, Isojasmon, Dihydrofloralol, Nardorosol, Fenchylalkohol und Tridecen-2-nitril umfassenden Gruppe gewählt sind.
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US613427 | 1984-05-24 | ||
US61342790A | 1990-11-14 | 1990-11-14 | |
PCT/US1991/008206 WO1992008780A1 (en) | 1990-11-14 | 1991-11-06 | Granular detergent or bleaching compositions containing amidoperoxyacid bleach and perfume |
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EP0557419A1 EP0557419A1 (de) | 1993-09-01 |
EP0557419B1 true EP0557419B1 (de) | 1996-01-17 |
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EP (1) | EP0557419B1 (de) |
JP (1) | JPH06502669A (de) |
CN (1) | CN1062375A (de) |
AR (1) | AR244802A1 (de) |
AT (1) | ATE133195T1 (de) |
AU (1) | AU9053891A (de) |
BR (1) | BR9106962A (de) |
CA (1) | CA2096254C (de) |
DE (1) | DE69116572T2 (de) |
ES (1) | ES2082445T3 (de) |
IE (1) | IE913949A1 (de) |
MA (1) | MA22338A1 (de) |
MX (1) | MX9102021A (de) |
NZ (1) | NZ240572A (de) |
PT (1) | PT99511A (de) |
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CA2160900A1 (en) * | 1993-04-19 | 1994-10-27 | Cornelis Marinus Van't Land | Fluidized bed coated amidoperozyacid bleach composition |
US5500154A (en) * | 1994-10-20 | 1996-03-19 | The Procter & Gamble Company | Detergent compositions containing enduring perfume |
EP0821723A1 (de) * | 1995-04-03 | 1998-02-04 | The Procter & Gamble Company | Bleichmittelzusammensetzungen enthaltend ausgewählte parfüme für die maskierung des bleichmittelgeruchs |
EP0778342A1 (de) * | 1995-12-06 | 1997-06-11 | The Procter & Gamble Company | Waschmittelzusammensetzungen |
US5780404A (en) * | 1996-02-26 | 1998-07-14 | The Procter & Gamble Company | Detergent compositions containing enduring perfume |
WO1998056337A1 (en) * | 1997-06-09 | 1998-12-17 | The Procter & Gamble Company | Malodor reducing composition containing amber and musk materials |
GB9809772D0 (en) * | 1998-05-07 | 1998-07-08 | Quest Int | Perfume composition |
EP1072673A3 (de) * | 1999-07-20 | 2001-03-21 | The Procter & Gamble Company | Riechstoffkompositionen |
DE102005054565A1 (de) * | 2005-11-14 | 2007-05-16 | Henkel Kgaa | Oxidationsmittel enthaltende,wohlriechende Verbrauchsprodukte |
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---|---|---|---|---|
FI780439A (fi) * | 1978-01-12 | 1979-07-13 | Unilever Nv | Tvaettmedel |
FR2537732A1 (fr) * | 1982-12-10 | 1984-06-15 | Thomson Csf | Dispositif d'echauffement d'une zone annulaire superficielle d'un objet filiforme |
GB8334159D0 (en) * | 1983-12-22 | 1984-02-01 | Unilever Plc | Perfume |
US4634551A (en) * | 1985-06-03 | 1987-01-06 | Procter & Gamble Company | Bleaching compounds and compositions comprising fatty peroxyacids salts thereof and precursors therefor having amide moieties in the fatty chain |
DE3623619C1 (de) * | 1986-07-12 | 1987-09-10 | Ant Nachrichtentech | Verfahren zum Ausrichten zweier Lichtleitfaserenden auf stirnseitigen Kontakt |
US4686063A (en) * | 1986-09-12 | 1987-08-11 | The Procter & Gamble Company | Fatty peroxyacids or salts thereof having amide moieties in the fatty chain and low levels of exotherm control agents |
US4727237A (en) * | 1987-05-04 | 1988-02-23 | Hewlett-Packard Company | Pyrolysis coated optical fiber splices: apparatus and method |
US4909953A (en) * | 1988-06-30 | 1990-03-20 | The Procter & Gamble Company | Phosphate buffer wash for improved amidoperoxyacid storage stability |
US4932989A (en) * | 1989-04-05 | 1990-06-12 | At&T Bell Laboratories | Method and apparatus for fabricating microlenses on optical fibers |
GB8914055D0 (en) * | 1989-06-19 | 1989-08-09 | Unilever Plc | Low-odour deodorant perfume compositions |
-
1991
- 1991-11-06 AU AU90538/91A patent/AU9053891A/en not_active Abandoned
- 1991-11-06 DE DE69116572T patent/DE69116572T2/de not_active Expired - Fee Related
- 1991-11-06 ES ES92900440T patent/ES2082445T3/es not_active Expired - Lifetime
- 1991-11-06 CA CA002096254A patent/CA2096254C/en not_active Expired - Fee Related
- 1991-11-06 WO PCT/US1991/008206 patent/WO1992008780A1/en active IP Right Grant
- 1991-11-06 JP JP4501056A patent/JPH06502669A/ja active Pending
- 1991-11-06 EP EP92900440A patent/EP0557419B1/de not_active Expired - Lifetime
- 1991-11-06 AT AT92900440T patent/ATE133195T1/de not_active IP Right Cessation
- 1991-11-06 BR BR919106962A patent/BR9106962A/pt unknown
- 1991-11-12 MX MX9102021A patent/MX9102021A/es unknown
- 1991-11-13 IE IE394991A patent/IE913949A1/en not_active Application Discontinuation
- 1991-11-13 MA MA22621A patent/MA22338A1/fr unknown
- 1991-11-13 NZ NZ240572A patent/NZ240572A/en unknown
- 1991-11-13 TR TR91/1071A patent/TR26092A/xx unknown
- 1991-11-13 AR AR91321142A patent/AR244802A1/es active
- 1991-11-14 CN CN91111518.8A patent/CN1062375A/zh not_active Withdrawn
- 1991-11-14 PT PT99511A patent/PT99511A/pt not_active Application Discontinuation
Also Published As
Publication number | Publication date |
---|---|
CA2096254C (en) | 1998-01-06 |
MA22338A1 (fr) | 1992-07-01 |
BR9106962A (pt) | 1993-08-31 |
CA2096254A1 (en) | 1992-05-15 |
ES2082445T3 (es) | 1996-03-16 |
MX9102021A (es) | 1994-04-29 |
DE69116572T2 (de) | 1996-09-19 |
WO1992008780A1 (en) | 1992-05-29 |
DE69116572D1 (de) | 1996-02-29 |
AU9053891A (en) | 1992-06-11 |
EP0557419A1 (de) | 1993-09-01 |
NZ240572A (en) | 1994-12-22 |
ATE133195T1 (de) | 1996-02-15 |
PT99511A (pt) | 1992-09-30 |
AR244802A1 (es) | 1993-11-30 |
JPH06502669A (ja) | 1994-03-24 |
IE913949A1 (en) | 1992-05-20 |
TR26092A (tr) | 1994-12-15 |
CN1062375A (zh) | 1992-07-01 |
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