CA2293760A1 - Additive for a detergent formulation, detergent formulation comprising such an additive and use of said formation for cleaning bottles - Google Patents
Additive for a detergent formulation, detergent formulation comprising such an additive and use of said formation for cleaning bottles Download PDFInfo
- Publication number
- CA2293760A1 CA2293760A1 CA002293760A CA2293760A CA2293760A1 CA 2293760 A1 CA2293760 A1 CA 2293760A1 CA 002293760 A CA002293760 A CA 002293760A CA 2293760 A CA2293760 A CA 2293760A CA 2293760 A1 CA2293760 A1 CA 2293760A1
- Authority
- CA
- Canada
- Prior art keywords
- bottles
- additive
- formulation
- cleaning
- hydrotrope
- 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.)
- Abandoned
Links
- 238000004140 cleaning Methods 0.000 title claims abstract description 54
- 239000000203 mixture Substances 0.000 title claims abstract description 42
- 238000009472 formulation Methods 0.000 title claims abstract description 39
- 239000000654 additive Substances 0.000 title claims abstract description 30
- 230000000996 additive effect Effects 0.000 title claims abstract description 27
- 239000003599 detergent Substances 0.000 title claims abstract description 22
- 230000015572 biosynthetic process Effects 0.000 title 1
- -1 ethyl glycine diacetic acid Chemical compound 0.000 claims abstract description 27
- 239000002736 nonionic surfactant Substances 0.000 claims abstract description 19
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 15
- 239000003752 hydrotrope Substances 0.000 claims abstract description 15
- QUCDWLYKDRVKMI-UHFFFAOYSA-M sodium;3,4-dimethylbenzenesulfonate Chemical compound [Na+].CC1=CC=C(S([O-])(=O)=O)C=C1C QUCDWLYKDRVKMI-UHFFFAOYSA-M 0.000 claims abstract description 15
- 239000003352 sequestering agent Substances 0.000 claims abstract description 14
- CIEZZGWIJBXOTE-UHFFFAOYSA-N 2-[bis(carboxymethyl)amino]propanoic acid Chemical compound OC(=O)C(C)N(CC(O)=O)CC(O)=O CIEZZGWIJBXOTE-UHFFFAOYSA-N 0.000 claims abstract description 9
- WDJHALXBUFZDSR-UHFFFAOYSA-N acetoacetic acid Chemical compound CC(=O)CC(O)=O WDJHALXBUFZDSR-UHFFFAOYSA-N 0.000 claims abstract description 4
- MGFYIUFZLHCRTH-UHFFFAOYSA-N nitrilotriacetic acid Chemical compound OC(=O)CN(CC(O)=O)CC(O)=O MGFYIUFZLHCRTH-UHFFFAOYSA-N 0.000 claims abstract description 4
- MTCFGRXMJLQNBG-UHFFFAOYSA-N Serine Natural products OCC(N)C(O)=O MTCFGRXMJLQNBG-UHFFFAOYSA-N 0.000 claims abstract description 3
- UWRBFYBQPCJRRL-UHFFFAOYSA-N 3-[bis(carboxymethyl)amino]propanoic acid Chemical compound OC(=O)CCN(CC(O)=O)CC(O)=O UWRBFYBQPCJRRL-UHFFFAOYSA-N 0.000 claims abstract 2
- 238000000034 method Methods 0.000 claims description 18
- 125000004432 carbon atom Chemical group C* 0.000 claims description 14
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 claims description 8
- 229920003171 Poly (ethylene oxide) Polymers 0.000 claims description 8
- 125000001931 aliphatic group Chemical group 0.000 claims description 7
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical group CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 claims description 6
- 239000003795 chemical substances by application Substances 0.000 claims description 6
- 150000001875 compounds Chemical class 0.000 claims description 6
- 229920001451 polypropylene glycol Polymers 0.000 claims description 6
- GPRLSGONYQIRFK-MNYXATJNSA-N triton Chemical group [3H+] GPRLSGONYQIRFK-MNYXATJNSA-N 0.000 claims description 6
- 239000011734 sodium Substances 0.000 claims description 5
- 229910052708 sodium Inorganic materials 0.000 claims description 4
- 238000005406 washing Methods 0.000 claims description 4
- 239000013530 defoamer Substances 0.000 claims description 3
- QMWFSAOKXWLOGH-UHFFFAOYSA-N 1,2-dimethylnaphthalene;sodium Chemical compound [Na].C1=CC=CC2=C(C)C(C)=CC=C21 QMWFSAOKXWLOGH-UHFFFAOYSA-N 0.000 claims 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 claims description 2
- 150000007933 aliphatic carboxylic acids Chemical class 0.000 claims description 2
- 150000004996 alkyl benzenes Chemical class 0.000 claims description 2
- JXLHNMVSKXFWAO-UHFFFAOYSA-N azane;7-fluoro-2,1,3-benzoxadiazole-4-sulfonic acid Chemical compound N.OS(=O)(=O)C1=CC=C(F)C2=NON=C12 JXLHNMVSKXFWAO-UHFFFAOYSA-N 0.000 claims description 2
- 125000002704 decyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 2
- USIUVYZYUHIAEV-UHFFFAOYSA-N diphenyl ether Chemical compound C=1C=CC=CC=1OC1=CC=CC=C1 USIUVYZYUHIAEV-UHFFFAOYSA-N 0.000 claims description 2
- WXMKPNITSTVMEF-UHFFFAOYSA-M sodium benzoate Chemical compound [Na+].[O-]C(=O)C1=CC=CC=C1 WXMKPNITSTVMEF-UHFFFAOYSA-M 0.000 claims description 2
- 239000004299 sodium benzoate Substances 0.000 claims description 2
- 235000010234 sodium benzoate Nutrition 0.000 claims description 2
- 159000000000 sodium salts Chemical class 0.000 claims description 2
- 229910019142 PO4 Inorganic materials 0.000 claims 1
- 229910052783 alkali metal Inorganic materials 0.000 claims 1
- 239000010452 phosphate Substances 0.000 claims 1
- 239000004417 polycarbonate Substances 0.000 abstract description 12
- 229920000515 polycarbonate Polymers 0.000 abstract description 12
- 239000004033 plastic Substances 0.000 abstract description 5
- 229920003023 plastic Polymers 0.000 abstract description 5
- 125000004435 hydrogen atom Chemical group [H]* 0.000 abstract description 4
- 125000000896 monocarboxylic acid group Chemical group 0.000 abstract 2
- 125000000923 (C1-C30) alkyl group Chemical group 0.000 abstract 1
- 125000000739 C2-C30 alkenyl group Chemical group 0.000 abstract 1
- 239000004698 Polyethylene Substances 0.000 abstract 1
- 229920000573 polyethylene Polymers 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 33
- 229920000139 polyethylene terephthalate Polymers 0.000 description 21
- 239000005020 polyethylene terephthalate Substances 0.000 description 21
- 229920001983 poloxamer Polymers 0.000 description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 13
- HEMHJVSKTPXQMS-UHFFFAOYSA-M sodium hydroxide Inorganic materials [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 11
- QFMDFTQOJHFVNR-UHFFFAOYSA-N 1-[2,2-dichloro-1-(4-ethylphenyl)ethyl]-4-ethylbenzene Chemical compound C1=CC(CC)=CC=C1C(C(Cl)Cl)C1=CC=C(CC)C=C1 QFMDFTQOJHFVNR-UHFFFAOYSA-N 0.000 description 8
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Natural products CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 8
- 239000003518 caustics Substances 0.000 description 8
- 241000228245 Aspergillus niger Species 0.000 description 6
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 6
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 description 6
- 235000013336 milk Nutrition 0.000 description 6
- 239000008267 milk Substances 0.000 description 6
- 210000004080 milk Anatomy 0.000 description 6
- 239000002689 soil Substances 0.000 description 6
- 238000005507 spraying Methods 0.000 description 6
- 239000004094 surface-active agent Substances 0.000 description 6
- 235000015193 tomato juice Nutrition 0.000 description 6
- 238000002835 absorbance Methods 0.000 description 5
- 238000002791 soaking Methods 0.000 description 5
- FAPWRFPIFSIZLT-UHFFFAOYSA-M sodium chloride Inorganic materials [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- JGFZNNIVVJXRND-UHFFFAOYSA-N N,N-Diisopropylethylamine (DIPEA) Chemical compound CCN(C(C)C)C(C)C JGFZNNIVVJXRND-UHFFFAOYSA-N 0.000 description 4
- 229920000642 polymer Polymers 0.000 description 4
- 238000002360 preparation method Methods 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 239000008399 tap water Substances 0.000 description 4
- 235000020679 tap water Nutrition 0.000 description 4
- 235000013618 yogurt Nutrition 0.000 description 4
- 229920001817 Agar Polymers 0.000 description 3
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 239000008272 agar Substances 0.000 description 3
- 239000006787 czapek-dox agar Substances 0.000 description 3
- 150000002148 esters Chemical class 0.000 description 3
- 238000011156 evaluation Methods 0.000 description 3
- 239000000194 fatty acid Substances 0.000 description 3
- 239000011521 glass Substances 0.000 description 3
- 229960001031 glucose Drugs 0.000 description 3
- 239000008103 glucose Substances 0.000 description 3
- 230000002209 hydrophobic effect Effects 0.000 description 3
- 239000004310 lactic acid Substances 0.000 description 3
- 235000014655 lactic acid Nutrition 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 229960000907 methylthioninium chloride Drugs 0.000 description 3
- 239000011780 sodium chloride Substances 0.000 description 3
- AEQDJSLRWYMAQI-UHFFFAOYSA-N 2,3,9,10-tetramethoxy-6,8,13,13a-tetrahydro-5H-isoquinolino[2,1-b]isoquinoline Chemical compound C1CN2CC(C(=C(OC)C=C3)OC)=C3CC2C2=C1C=C(OC)C(OC)=C2 AEQDJSLRWYMAQI-UHFFFAOYSA-N 0.000 description 2
- NLMKTBGFQGKQEV-UHFFFAOYSA-N 2-[2-[2-[2-[2-[2-[2-[2-[2-[2-[2-[2-[2-[2-[2-[2-[2-[2-[2-(2-hexadecoxyethoxy)ethoxy]ethoxy]ethoxy]ethoxy]ethoxy]ethoxy]ethoxy]ethoxy]ethoxy]ethoxy]ethoxy]ethoxy]ethoxy]ethoxy]ethoxy]ethoxy]ethoxy]ethoxy]ethanol Chemical compound CCCCCCCCCCCCCCCCOCCOCCOCCOCCOCCOCCOCCOCCOCCOCCOCCOCCOCCOCCOCCOCCOCCOCCOCCOCCO NLMKTBGFQGKQEV-UHFFFAOYSA-N 0.000 description 2
- NECRQCBKTGZNMH-UHFFFAOYSA-N 3,5-dimethylhex-1-yn-3-ol Chemical compound CC(C)CC(C)(O)C#C NECRQCBKTGZNMH-UHFFFAOYSA-N 0.000 description 2
- RZVAJINKPMORJF-UHFFFAOYSA-N Acetaminophen Chemical compound CC(=O)NC1=CC=C(O)C=C1 RZVAJINKPMORJF-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 229920000742 Cotton Polymers 0.000 description 2
- 241000233866 Fungi Species 0.000 description 2
- 229920002257 Plurafac® Polymers 0.000 description 2
- 125000003342 alkenyl group Chemical group 0.000 description 2
- 235000013361 beverage Nutrition 0.000 description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 2
- 230000003750 conditioning effect Effects 0.000 description 2
- NSFKBZXCXCJZDQ-UHFFFAOYSA-N cumene;sodium Chemical compound [Na].CC(C)C1=CC=CC=C1 NSFKBZXCXCJZDQ-UHFFFAOYSA-N 0.000 description 2
- 230000008021 deposition Effects 0.000 description 2
- 235000014113 dietary fatty acids Nutrition 0.000 description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- 229930195729 fatty acid Natural products 0.000 description 2
- 150000004665 fatty acids Chemical class 0.000 description 2
- WQYVRQLZKVEZGA-UHFFFAOYSA-N hypochlorite Chemical compound Cl[O-] WQYVRQLZKVEZGA-UHFFFAOYSA-N 0.000 description 2
- 238000011835 investigation Methods 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- 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 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 239000011049 pearl Substances 0.000 description 2
- 239000011112 polyethylene naphthalate Substances 0.000 description 2
- 229940079842 sodium cumenesulfonate Drugs 0.000 description 2
- 239000000176 sodium gluconate Substances 0.000 description 2
- 235000012207 sodium gluconate Nutrition 0.000 description 2
- 229940005574 sodium gluconate Drugs 0.000 description 2
- QEKATQBVVAZOAY-UHFFFAOYSA-M sodium;4-propan-2-ylbenzenesulfonate Chemical compound [Na+].CC(C)C1=CC=C(S([O-])(=O)=O)C=C1 QEKATQBVVAZOAY-UHFFFAOYSA-M 0.000 description 2
- 235000014214 soft drink Nutrition 0.000 description 2
- 239000008174 sterile solution Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 2
- JNYAEWCLZODPBN-JGWLITMVSA-N (2r,3r,4s)-2-[(1r)-1,2-dihydroxyethyl]oxolane-3,4-diol Chemical class OC[C@@H](O)[C@H]1OC[C@H](O)[C@H]1O JNYAEWCLZODPBN-JGWLITMVSA-N 0.000 description 1
- 125000004178 (C1-C4) alkyl group Chemical group 0.000 description 1
- LXOFYPKXCSULTL-UHFFFAOYSA-N 2,4,7,9-tetramethyldec-5-yne-4,7-diol Chemical compound CC(C)CC(C)(O)C#CC(C)(O)CC(C)C LXOFYPKXCSULTL-UHFFFAOYSA-N 0.000 description 1
- 101100135609 Arabidopsis thaliana PAP10 gene Proteins 0.000 description 1
- 125000006539 C12 alkyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- RGHNJXZEOKUKBD-SQOUGZDYSA-M D-gluconate Chemical compound OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C([O-])=O RGHNJXZEOKUKBD-SQOUGZDYSA-M 0.000 description 1
- 239000001888 Peptone Substances 0.000 description 1
- 108010080698 Peptones Proteins 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 125000005024 alkenyl aryl group Chemical group 0.000 description 1
- 125000004453 alkoxycarbonyl group Chemical group 0.000 description 1
- 125000002877 alkyl aryl group Chemical group 0.000 description 1
- 125000002947 alkylene group Chemical group 0.000 description 1
- 239000002518 antifoaming agent Substances 0.000 description 1
- 125000005018 aryl alkenyl group Chemical group 0.000 description 1
- 125000003710 aryl alkyl group Chemical group 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 229920001400 block copolymer Polymers 0.000 description 1
- 150000001720 carbohydrates Chemical class 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 150000002009 diols Chemical class 0.000 description 1
- 230000001804 emulsifying effect Effects 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 150000002191 fatty alcohols Chemical class 0.000 description 1
- 150000002194 fatty esters Chemical class 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 238000005187 foaming Methods 0.000 description 1
- 230000002538 fungal effect Effects 0.000 description 1
- 229940050410 gluconate Drugs 0.000 description 1
- 229930182470 glycoside Natural products 0.000 description 1
- 239000008233 hard water Substances 0.000 description 1
- 125000005842 heteroatom Chemical group 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 125000001165 hydrophobic group Chemical group 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 125000005020 hydroxyalkenyl group Chemical group 0.000 description 1
- 125000002768 hydroxyalkyl group Chemical group 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000002609 medium Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 235000019319 peptone Nutrition 0.000 description 1
- 125000003884 phenylalkyl group Chemical group 0.000 description 1
- 150000003014 phosphoric acid esters Chemical class 0.000 description 1
- 229920003207 poly(ethylene-2,6-naphthalate) Polymers 0.000 description 1
- 229920002503 polyoxyethylene-polyoxypropylene Polymers 0.000 description 1
- 229920001282 polysaccharide Polymers 0.000 description 1
- 239000005017 polysaccharide Substances 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000007127 saponification reaction Methods 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 150000005846 sugar alcohols Polymers 0.000 description 1
- 125000000020 sulfo group Chemical group O=S(=O)([*])O[H] 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 description 1
- UEUXEKPTXMALOB-UHFFFAOYSA-J tetrasodium;2-[2-[bis(carboxylatomethyl)amino]ethyl-(carboxylatomethyl)amino]acetate Chemical class [Na+].[Na+].[Na+].[Na+].[O-]C(=O)CN(CC([O-])=O)CCN(CC([O-])=O)CC([O-])=O UEUXEKPTXMALOB-UHFFFAOYSA-J 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
- 235000015961 tonic Nutrition 0.000 description 1
- 230000001256 tonic effect Effects 0.000 description 1
- 229960000716 tonics Drugs 0.000 description 1
- 229910001428 transition metal ion Inorganic materials 0.000 description 1
- HRXKRNGNAMMEHJ-UHFFFAOYSA-K trisodium citrate Chemical compound [Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O HRXKRNGNAMMEHJ-UHFFFAOYSA-K 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/16—Organic compounds
- C11D3/26—Organic compounds containing nitrogen
- C11D3/33—Amino carboxylic acids
-
- C11D2111/18—
Abstract
An additive for a detergent formulation is described, comprising a sequestrant having formula (I), wherein: X = a COOH group or an alkyl chain comprising a COOH group; Y = an H atom; Z = an H atom, a C1-C30 alkyl group or a C2-C30 alkenyl group; and further comprising a nonionic surfactant and/or a hydrotrope. Preferably, said sequestrant is selected from the group of nitrilo triacetic acid (NTA), .beta.-alanine diacetic acid (.beta.-ADA)), methyl glycine diacetic acid (MGDA), serine diacetic acid (SDA) and ethyl glycine diacetic acid (EGDA). Furthermore, the use of a detergent formulation containing said additive for cleaning bottles, in particular returnable plastic bottles, such as PET (polyethylene teraphthalate) or polycarbonate bottles is described.
Description
~1'O 98/59027 PC7 /EP9b/0369~
ADDITIVE FOR A DETERGENT FORMULATION, DETERGENT FORMULATION
COMPRISING SUCH AN ADDITIVE AND USE
OF SAID FORMULATLON FOR CLEANING BOTTLES
Field of the invention The present invention relates to an additive for a detergent formulation, a detergent formulation comprising said additive, and to the use of said formulation for cleaning bottles, in particular returnable plastic bottles such as PET (polyethylene terephthalate) bottles, polyethylene naphthalate (PEN), copolymers of PET/PEN
and/or returnable polycarbonate bottles.
Background of the invention Many soft drinks are being sold in returnable bottles, these bottles being made of either glass or plastic, in particular PET or polycarbonate. In order to ensure product quality it is very important that such bottles be thoroughly cleaned and disinfected before being refilled with the soft drink for example.
The use of glycine-N-N-diacetic acid (NTA) derivatives as textile detergent builders is known from WO 94/29421.
An existing problem with such beverage bottles after they have been emptied of their contents, is that fungal growth can occur on any residue left behind.
Ari objective of the present invention is to provide an additive suitable for a detergent formulation, for effectively removing mould from beverage bottles.
It was now surprisingly found that a combination of an nonionic and/or a hydrotrope with a specific group of Gl a c~ -~o r /~ o ~ ~- ~c c ~e ~ h ~ it AMENDED S'~EET
,r,cr.W~
WO 9/59027 PCT/EP98,'036~~
ADDITIVE FOR A DETERGENT FORMULATION, DETERGENT FORMULATION
COMPRISING SUCH AN ADDITIVE AND USE
OF SAID FORMULATLON FOR CLEANING BOTTLES
Field of the invention The present invention relates to an additive for a detergent formulation, a detergent formulation comprising said additive, and to the use of said formulation for cleaning bottles, in particular returnable plastic bottles such as PET (polyethylene terephthalate) bottles, polyethylene naphthalate (PEN), copolymers of PET/PEN
and/or returnable polycarbonate bottles.
Background of the invention Many soft drinks are being sold in returnable bottles, these bottles being made of either glass or plastic, in particular PET or polycarbonate. In order to ensure product quality it is very important that such bottles be thoroughly cleaned and disinfected before being refilled with the soft drink for example.
The use of glycine-N-N-diacetic acid (NTA) derivatives as textile detergent builders is known from WO 94/29421.
An existing problem with such beverage bottles after they have been emptied of their contents, is that fungal growth can occur on any residue left behind.
Ari objective of the present invention is to provide an additive suitable for a detergent formulation, for effectively removing mould from beverage bottles.
It was now surprisingly found that a combination of an nonionic and/or a hydrotrope with a specific group of Gl a c~ -~o r /~ o ~ ~- ~c c ~e ~ h ~ it AMENDED S'~EET
,r,cr.W~
WO 9/59027 PCT/EP98,'036~~
sequestrants, as specified below, provides particularly good cleaning performance.
Definition of the invention Consequently, according to a first embodiment of the present invention there is provided an additive for a detergent formulation, said additive ~TT~nri cir,rr n s.~.i~_ _ ~G~ vn fi. Go rte.. ~ o !' n ~ r ~a n h X ' AS a(~1 Lr,'6c~G i"~.
HOOC-CH2 G ~0.rw~ S .
Y
HOOC-CHZ/
Z
wherein:
X - a C96H group or an alkyl chain comprising a COOH
g~P .
Y an H atom Z /= an H atom or C1-C3o, CZ-C3o alkenyl group an,~/ wherein the formulation further comprises one or more In an other aspect of the invention, there is provided a formulation comprising an additive according to the invention wherein the sequestrant is present in a wt$ range of 5-60, preferably 15-35, and the nonionic andj~r hydrotrope in a wt$ range of 0.5-40, preferably 1-25.
The formulation of the invention can ~3dditionally contain other common detergent components, including oxidizing agents, caustic, H202, hypochlorite, anti-foaming agents, alkali sources, threshold agents to prevent deposition of hard water scale, structuring or emulsifying polymers, and bleaches to degrade or decolorise oxidisable stains.
A;wEI~DED SHEET
WO 98/59017 T'C'TJ.h:P9a/0369~
Definition of the invention Consequently, according to a first embodiment of the present invention there is provided an additive for a detergent formulation, said additive ~TT~nri cir,rr n s.~.i~_ _ ~G~ vn fi. Go rte.. ~ o !' n ~ r ~a n h X ' AS a(~1 Lr,'6c~G i"~.
HOOC-CH2 G ~0.rw~ S .
Y
HOOC-CHZ/
Z
wherein:
X - a C96H group or an alkyl chain comprising a COOH
g~P .
Y an H atom Z /= an H atom or C1-C3o, CZ-C3o alkenyl group an,~/ wherein the formulation further comprises one or more In an other aspect of the invention, there is provided a formulation comprising an additive according to the invention wherein the sequestrant is present in a wt$ range of 5-60, preferably 15-35, and the nonionic andj~r hydrotrope in a wt$ range of 0.5-40, preferably 1-25.
The formulation of the invention can ~3dditionally contain other common detergent components, including oxidizing agents, caustic, H202, hypochlorite, anti-foaming agents, alkali sources, threshold agents to prevent deposition of hard water scale, structuring or emulsifying polymers, and bleaches to degrade or decolorise oxidisable stains.
A;wEI~DED SHEET
WO 98/59017 T'C'TJ.h:P9a/0369~
According to a third aspect of the present invention, there is provided the use of the formulation of the invention as a detergent in cleaning bottles, particularly retunable PET bottles, when the formulation comprises no hydrotrope, and particularly returnable polycarbonate bottles when the formulation comprises no nonionic surfactant.
According to a fourth aspect of the invention, there is provided a process for washing bottles, comprising the steps of exposing bottles to a formulation or additive according to the invention, wherein the sequestrant, nonionic surfactant ands hydrotrope and possibly any further standard detergent formulation components, such as TM
a defoamer, for example Dehypon LT109 pare collectively or individually supplied into a bottle washing system Detailed description of the invention the sequestrant according to the present invention preferably comprises one or more of the following:
- hydroxyl groups, preferably not more t five, - formyl groups, - C1- to Cq-alkoxy groups, - phenoxy groups, - C1-C4 alkoxycarbony groups, and/or a phenylalkyl 'th 1-20 C atoms in the alkyl group, and can comprise a or more of the following:
- a fiver or six-membered unsaturated or saturated heterocy is ring preferably with up to 3 hetero-atoms, most referably selected from the group nitrogen, oxygen, AMENDED SHEET
IPEAIEP
WO 98159027 PCT/EP98/9~6°5 ring may comprise one or more of the follo g groups:
- a C1-C4 alkyl group, - a hydroxyl group, - a carboxyl group, - a sulfo group - a phospho group - a sul ate ester - a hosphate ester ~ a C,-C4 alkoxycarbonyl group.
The sequestrant is ~~ selected from the group consisting of Nitrilo triacetic acid (NTA), ~i-Alanine diacetic acid (~3-ADA), Methyl glycine diacetic acid (MGDA), Serine diacetic acid (SDA) and Ethyl glycine diacetic acid (EGDA), wherein MGDA and SDA yield particularly good cleaning results.
The non-ionic surfactant preferably comprises one or more of the following:
- polyoxyethylene or polyoxypropylene condensates of aliphatic carboxylic acids having 8 to 18 carbon atoms in an aliphatic chain and incorporating from a.~a~t 2 to a~ae~ 50 ethylene oxide and/or propylene oxide units, polyoxyethylene or polyoxypropylene condensates of aliphatic alcohols having afrom 6 to 24 carbon atoms and incorporating from ahs~ 2 to 50 ethylene oxide and/or propylene oxide units, - a compound of formula:
R-(CHZCHzO)aH
ANfENDED SHEEN' ~pEAIEP
' WO 98/59027 PC7 /EP9b/03695 wherein R is a C6-C24 linear or branched alkyl group and a is an integer from 2 to 50, - a compound of formula:
R'- (CHzCHO) X (CHZCH20) y (CHzCHO) ZH
Rz R3 wherein R' is a linear alkyl group having an average of about 6 to about 18 carbon atoms, Rz and R3 are each linear alkyl groups of 1 to ~be~tt 9 carbon atoms, x is an integer from 1 to 6, y is an integer from 4 to 20 and z is an integer from 4 to 25, - polyoxyethylene or polyoxypropylene condensates of alkyl phenols having about 6 to 12 carbon atoms and incorporating from about 2 to 25 moles of ethylene oxide and/or propylene oxide, - polyoxyethylene derivatives of sorbitan mono-, di-and tri-fatty acid esters wherein the fatty acid component has between 12 and 24 carbon atoms and the polyethylene chains contain between about 9 and 30 ethylene oxide units, - polyoxyethylene-polyoxypropylene block copolymers having the formula:
HO ( CHzCH20 ) a ( CH ( CH3 ) CH20 ) b ( CHZCHZO ) ~H or HO (CH (CH3) CHZO) d (CHZCHZO) a (CH (CH3) CHZO) fH
wherein a, b, c, d, e, and f are integers from 1 to 350 reflecting the respective polyethylene oxide and polypropylene oxide blocks of said polymer, wherein the polyoxyethylene component of the block polymer is at least about 10~ of the block polymer, AMENDED SHEET
IPEAIEP i PC'1'/EP9l~/03h9s - alkyl glycosides having formula:
R90(R50)"(Z1) P
wherein R4 is a monovalent organic radical, for example a monovalent saturated aliphatic, unsaturated aliphatic or aromatic radical such as alkyl, hydroxyalkyl, alkenyl, hydroxyalkenyl, aryl, alkylaryl, hydroxyalkylaryl, arylalkyl, alkenylaryl, arylalkenyl and the like having from aft 6 to 30 carbon atoms, wherein RS is a divalent hydrocarbon radical containing from 2 to a~e~t 4 carbon atoms such as ethylene, propylene or butylene (most preferably the unit (R50)" represents repeating units of ethylene oxide, propylene oxide and/or random or block combinations thereof); n is an integer from 0 to a~e~rt 12;
Z1 represents a moiety derived from a reducing saccharide containing 5 or 6 carbon atoms (most preferably a glucose unit); and p is a number from 0.5 to a~e~ 10, - amine oxides having formula:
R6R'RBN=0 wherein R6, R' and Re are saturated aliphatic groups or substituted saturated aliphatic groups. wherein preferably R6 is an alkyl chain of .a~etrt 10 to 20 carbon atoms and R' and R8 are methyl or ethyl groups or both R6 and R' are alkyl chains of 6 to 14 carbon atoms and R8 is a methyl or ethyl group.
A.n additive with such a non-ionic surfactant in combination with the above sequesr4ant yielded goe:= cleaning results.
The non-ionic surfactant ~r~for~~,~~~ has a hydrophilic-lipophilic balance (HLB) of from abeQt 14-20.
AMENDED Sh~EET
IPE~IEP i WO 98/59027 PCTI~P98/L369~
Non-ionic surfactants can be broadly defined as surface active compounds with one or more uncharged hydrophilic substituents. A major class of non-ionic surfactants are those compounds produced by the condensation of alkylene oxide groups with an organic hydrophobic material which may be aliphatic or alkyl aromatic in nature. The length of the hydrophilic or polyoxyalkylene radical which is condensed with any particular hydrophobic group can be readily adjusted to yield a water-soluble compound having a desired degree of balance between hydrophilic and hydrophobic elements.
The HLB value represents the hydrophilic-lipophilic balance of the molecule. The lower the HLB value the more hydrophobic the material is, and vice versa. For simple alcohol ethoxylates, the HLB value may be calculated from HLH = E/5 (I) where E is the weight percentage of ethylene oxide in the molecule.
The simple straight chain alcohol ethoxylates are usually well defined materials. The inventors have been able to find a relationship between HLB-value (as calculated using equation (I)) and cleaning performance (as measured by mould removal). The straight chain alcohol ethoxylates according to~yhe present invention possess an HLB-value from about .~~to 20.
For fatty esters of polyalcohols and their alkoxylates, the HLB value is given by:
HLB = 20 x (1-S/A) (II) where S = saponification number of the ester, ie. the number of mg of potassium hydroxide needed to neutralise the free and bonded acid in 1 g of the substance;
AMENDED SHEET
tp~~/FP
WO 98159027 PCTiEP98~~364s' A = acid value of the esterified fatty acid, ie. the number of mg of potassium hydroxide to neutralise the free acid in 1 g of the substance.
The inventors have found that an additive with such a non-ionic surfactant, exhibiting the above HLB' values, yields particularly good cleaning results for PET bottles.
The additive most preferably comprise a non-ionic surfactant selected from the group consisting essentially ThJ Tly TM
of Synperonic A7, Synperonic L11, Lutensol A20, Lutensol A030,M Lutensol AT80T~Neodol 45-4ETMDehypon G2084TM Poly-TM ?M TiLJ
Tergent SLF18B45, Surfynol 504 and Plurafac LF231, wherein the non-ionic surfactant preferably has a cleaning score of about 3 or above, preferably about 4 or above and most preferably about 5 or above.
Cleaning score The cleaning results are obtained by measuring the absorbance at ~max between 662.0 en 664.0 nm, which is a measure for the amount of methylene blue in solution. To compare the results of different batches of mould soiled strips, an internal standard was measured for every new batch of strips. This internal standard was a product TM
containing 63.5$ Trilon ES9644 (35$ MGDA, ex. BASF), 7$
TM TM
Dissolvine NG (ex. Akzo Nobel), 1$ Bayhibit AM (ex. Bayer), 4$ Triton H-66T~ex. Union Carbide), 0.8$ Sodium Cumene TM
Sulfonate (40$, ex Huls), 2$ Dehypon LT104 (ex. Henkel).
The difference in cleaning performance between the internal st_:_dard and another observation is significant when the calculated difference is larger than the confidence intervals around the measured averages. This can be transformed into a formula where every significant difference will result in an increase or decrease of the AMENDED SHEET
IPE~EP
W'O 98/59027 PCT/EP98/03695 cleaning score, compared to the internal standard. The cleaning score can be calculated according to equation (III) .
( Xi - XS ) Cleaning score = + Vi Q X Tea-o.~;u~
Where:
Xi - Measured absorbance of the internal standard (corrected for the blanc; i.e. measured absorbance of an unsoiled strip);
XS - Measured absorbance of the sample (corrected for the blanc; i.e. measured absorbance of an unsoiled strip);
Q - Average deviation of the measurement. Following the procedure described above, the average deviation was found to be 0.18;
Tca=o.~;u>= Students value for a two tail test at 80g confidence level with v degrees of freedom;
Vi - Value of internal standard (equals 4 for the internal standard described above).
This definition of the cleaning score leads in this study to a range from 0 to 11 depending on Q, in which the higher the value the better the mould removal performance.
Table 1 shows a selection of preferred non-Tonics.
' WO 98159027 PCTIGP98/u369~
Table 1 Straight chain primary alkanol ethoxylates: H-( CHZ ) "- ( OCHzCHz ) m OH
n 10 12 14 16/18(avg:l7) m 3 aq: not solubleaq: not solubleaq: not solubleaq: not soluble HLB: 9.1 (theoryHLB: 8.3 (theoryHLB: 7.6 (theo~HLB: 6.8 (theory TM
Dehydol D3 Dobanol 23-3 Dobanol 25-3 Atlas G-70140 TM H TM
Dobanol 91-2.5Elfapur LT30SLTMElfapur LP Volpo N3 T'~
rM 25 S~
Ethylan CD Ethylan CD123TMElfapur LP
103 T~ 25 Sirs Ethylan CD Genapol LA-030 Ethylan D253 Genapol Z030XRemcopal 121 Renex 703 TM TM Trr 10 Synperonic Rolfor LA 3 Synperonic 91-2.5 TM A3T~
Synperonic L3 T M
Volpo L3 Special TM
7 d.pnt cl.pnt: cl.pnt:48C cl.pnt:
HLB: 13.2(theor)HLB: 12.5 (theoryHLB: 11.8 HLB: 10.9 (theory (theory Ethylan CD Ethytan CD 127 Dobanol 25-7 Eumulgin WM7 107 rM T~ T~ TH
Ethylan CD Dobanol 23-6.5 Dobanol 45-7 Rolfor CO 7 916 TM rH TM rM
Sy,~,peronic Elfapur LT65SLNT~Renex 711 91-7 T~ Tn Genapol LA-070 Synperonic T~ A7 T~
Genapol LA-079 rH
Synperonic L7 T~
Volpo T7 TH
11 cl.pt approx cl.pnt: cl.pnt > 100Ccl.pnt > 100C
2 0 HLB: 15.1 HLB: 14.4 (theory(5% aq) HLB: 13.1 (theor) (theory r h Sellig LA11 ' HLB: 13.9 Britex CS 11 100M8 (the TO
Synperonic L11TMDobanol 45-11Genapol T-110TM
Etfapur LP110SWTLutensol AT11 TH
Ethylan CD Mariipal 1618111 4511T''~ T'~
Renex 720 Rotfor HT 11 rM T ~
Synperonic Simulsol 56 Synperonic TAE11T
.
20 cl.pnt > 100Ccl.pnt >100C ci.pnt >100C cl.pnt 90C
I
HLe 17.0 (theoryHL3: 16.5 (5% aq) (1 ~ in 5% NaCI) T TM HLB: 16.1 HL3 15.5 (theory Synperonic Seilig LA11 (theory Seltig LA11 Renex 720 Atia~ G-4938 50 ~ T'~ T~' Synperonic Brij 58 (C16) A20 T~ TM
Bnj 78 (C18)TH
Britex S 200tH
Ethylan CS20TM
Genapol T-200TH
Sellig SU 25 100 ~
Volpo CS 20 T~
A~~i~~,'~~D S~~~T
~~'=A/~p , PCT/I:P98/G3695 There are many more primary alkanol ethoxylates e.g. n=10, m=4; n=10, m=5; n=10, m=6; n=10, m=8 ...
n=11, m=3, 9, 5, 6, 7, 8, 9, 10, 11, . . . , 80 n=20, m=3, . . . , 80 The hydrotrope ~~r--Ea~~~~s~--a ~~s~~eiah.~ l is .~ ~ ' U
,Y~ a+-s ~ h«~r~~'r~,~ °-~ is -.off re.~or~~., .. selected from the group consisting l.l-~ of: sodium benzoate, sodium 3-hydroxy-2-naphtoate, sodium xylene sulphonate, phosphate esters, sodium decyl diphenyl oxide, sodium dimethyl naphthalene sulphonate, sodium salts of linear alkyl benzene sulphonate, having from about C8 to C12 in the alkyl portion, as well as mixtures thereof, wherein the h drotro a is most TM
y p preferably Triton H66 also being a solubilizing agent. An additive comprising this hydrotrope yielded particularly good cleaning results.
An hydrotrope is preferable to a non-ionic surfactant when cleaning polycarbonate bottles, since non-ionic surfactants are thought to damage these.
The invention will now be described by way of the following examples and results, referring to figures 1-2 and the tables.
Experimental Standard soiling The standard soiling was made by mixing Tomato juice and a solution of Aspergillus niger.
AMENDED SHEET
IPEA/EP
Preparation of standard soiling Mntcri~lc - Aspergillus niger ATC 6275 - Czapek Dox agar (code CM97 ex Oxoid) - D-Glucose monohydrate - l0o Lactic acid solution SR 021 K
- Bacto Pepton L37 (ex Oxoid) - Sodium chloride Procedures Aspergillus niger was grown on 2 plates containing Czapek Dox agar with 2~ glucose and 10 ml lactic acid (10$) per litre agar. The mould was grown for 5 days at 25°C. Subsequently, the moulds were taken from the plate with two times 9 ml of a sterile solution containing 1 g/1 Pepton and 8.5 g/1 NaCl per plate. The mould solution was added (=18 ml) to 300 gr of tomato juice (Zontomaatje ex Riedel) and homogenised.
Preparation of ref-PET strips M ~ t c r ; W c - New ref-PET bottles - Sodium hydroxide Procedure The bottom and the neck were cut from a 1.5 ltr ref-PET bottle. The middle ,of thA bottle was used to cut pieces of 70 x 25 mm from the length direction of the bottle. The strips were then treated with 1.5~ caustic of 59°C for 15 minutes. The strips were rinsed with water to remove the caustic and the strips were dried.
Applying the soiling to the strips Strips were taken and submerged for 75~
vertically in the standard soiling (tomato juice with Aspergillus niger). The strips were then taken out of the solution and held 5-10 sec. vertically. In this way the excess soiling can drip off the strips. The strips were placed with the bold side up in a petri dish and put together with other strips in a plastic bag in an incubator at 25°C. After 5 days the plastic bag was removed and the strips, in closed petri-dishes, were restored in the incubator for 2 more days. After this the strips were ready for a quality check before use.
Quality check and cleaning procedure The standard soiled strips were taken and washed for 10 minutes in 1.5o caustic to check the quality of the soiling.
~r~+-o,-; ~ ~
- Beaker broad model 2000 ml - Magnetic stirrer (25 mm X 5 mm triangle shaped) - Temperature and rotation controlled stirrer - Stripholder - Chronograph r-1, o,., ; ~- ~ i - Methylene blue solution (0.10$), TNO procedure COP for ref-PET, V18 method A
- Acetic acid (1.00$) - Caustic solution (1.500 + additive (0.2~) Conditioning procedure - Take the petri dishes with the standard soiled strips out of the incubator.
- Take 4 soiled strips from the petri dishes and 2 unsoiled and place them in the stripholder.
- Heat a 1000 ml 1.50$ caustic solution up to 59°Ct 1°C
and set the stirring speed to 600 rpm. Place the stripholder with the 9 soiled ref-PET strips and 2 clean ref-PET strips for exactly 10.0 minutes in the caustic solution.
- Rinse the strips (3 times 5 sec) in 1000 ml of demineralised water.
- Wait 1 minute.
- After this the strips are dyed for 20 seconds in a 0.10$ methylene blue solution.
- Wait 1 minute.
- The strips are again rinsed for 3 times 5 sec. in 1000 ml of fresh demineralised water.
- Wait 1 minute.
- Put the 4 dyed strips in a closable can with 25 g of 1.00 acetic acid. Repeat this for the two blanc strips. Shake the dye from the strips.
- Filtrate 10 ml of the solution ( within 24 hrs) over a 0.45 /.cm filter and discard the first 5 ml. Put the other 5 ml in a 1 cm cuvet.
- Measure the absorption at JlmaX (between 662.0 and 664.0 nm) against 1.00 ~ acetic acid.
- Carry out the above steps with another 3 x 6 strips in the same cleaning solution.
WO 98/59027 1'CT/EP98/~365'S
Investigation of additives and formulations according to the present invention To assess the mould removal performance of various bottlewashing additives, PET strips standardly 5 soiled with a tomato juice contaminated with a common mould species (Aspergillus niger) were used. After conditioning, as above, these strips were soaked in an alkaline medium (1.5$ caustic in 8.5 DH water) for 10 minutes. The method to quantify the soil residue, as detailed above was used to 10 determining the cleaning score for the various additives and formulations, results of which are shown in the following tables.
Table 2 Sequestrant Supplier Level in Cleaning (Trade or development formulation Score name) (w~) EDTA, tetra sodium salt B~F 80.0 3 TM
lTrilon E39, 39% solution) Potassium tripolyphosphategudenhelm 27.2 1 (50% solution) m salt B~F 5 4 u 63 MGDA, tri sod T .
H
lTrilon ES9964, 35%
solution) SDA, tri sodium salt g~cF 24.2 4 The results shown in table 2 were obtained using formulations that, in addition to the sequestrant listed, AMENDED SHEET
lPEA/EP
' WO 98/59027 PC ~ /EP9~/03G9~
TM
contained sodium gluconate (70), Bayhibit AM (1~ of a 500 TM
solution), Triton H66 (4$ of a 50o solution), sodium cumene TM
sulfonate (0.80 of a 40~ solution), and Dehypon LT104 (20).
These formulations were dosed at a 0.2$ level in water of 8.5DH hardness, containing 1.5$ NaOH. The mould soiled strips were soaked in these solutions for 10 min at 59°C.
The results shown in tables 3-8 were obtained using formulations that, in addition to the surfactant, TM
contained Trilon ES9644 (63.5$ of a 35$ solution), sodium gluconate (7$), Bayhibit AM M1~ of a 50$ solution), Triton H66TM4$ of a 50$ solution), and sodium cumene sulfonate (0.8~ of a 40$ solution). These formulations were dosed at a 0.2$ level in water of 8.5DH hardness, containing 1.5~
NaOH. The mould soiled strips were soaked in these solutions for 10 min at 59°C (see above).
The formulations in table 3 exhibited good cleaning scores.
Table 3 Trade name Supplier Alkyl EO HLB Cleaning (Nonionic chain calculated Score surfactant) using (I) TM
synperonic ICI C10 7 11.8 4 T
synperonic ICI C12-14 11 19 5 Lil ZOTM
Lutensol .~ BASF C13-15 20 16.2 5 Lutenso11~o30 BASF C13-15 30 17 5 TM
Lutensol AT80 BASF C13-15 80 18.5 6 ~~'~~~~,n'_v Sr"~'~w ". ~1 ;~, WO 98759027 f~CT~~P98/J3693 On the other hand, straight chain alcohol ethoxylates with lower HLB-values exhibited a lesser cleaning score, as shown by table 4:
Table 4 Trade name Supplie Alkyl EO 8LB Cleaning (Nonionic r chain calculated Score surfactant) using (I) TM
Neodol 45-4E Shell C14-C15 4 8.9 1 Also some capped non-ionic surfactants showed good cleaning scores, as shown by table 5:
Table 5 Trade name Supplie Alkyl EO PO Cap Cleanin (Nonionic r chain g Score surfactant) (s / b) TM
Dehypon 62084 Henkel C16-20 8 - Butyl 4 (b) Dehypon LT104 Henkel C12-C18 10 - Butyl 9 T M
(s) Poly-Tergent Olin C20-C30 20 1 Octyl 5 ShF18B45 TM (s) Additional nonionics that showed good performance are shown in table 6:
AMENDED SHEET
IPEA/EP
WO 98/59027 PCT,'EPSB/33655 Table 6 Trade name Supplier Technical information Cleaning by (Nonionic supplier Score surf actant) TM per Ethoxylated 9 Surfynol 509 Products tetramethyldecynediol TM
AG 6202 Akzo-NobelLow-foaming 9 alkylpolyglucoside with C12 alkyl chain ~
Plurafac LF231 BASF Alkali-stable, low-foaming9 fatty alcohol alkoxylate Many nonionic surfactants however did not exhibit good cleaning scores in combination with sequestrant types, as shown by table 7:
Table 7 Trade name Supplier Alkyl EO PO Cleaning (Nonionic chain Score surfactant) TM
Dehypon LS24 Henkel C12-14 2 4 2 TM
Dehypon LS36 Henkel C12-14 3 6 1 TM
Dehypon LS45 Henkel C12-14 4 5 2 Dehypon LS54T~ Henkel C12-14 5 4 2 TM
Dynol 604 Air ethoxylated 2 Products acetylenic n , diols AMENDED SHEE'~
IPEA/EP
WO 98/59027 YL f ~EP98~U3~-'>
The following formulations were investigated according to the cleaning procedure and yielded the following results, Table 8:
H
f r r1 1' N V tf1 NI O H
m a rv yn ~o r .r r o H
N m V
H
r .. ~ N v ~~
a n o 11 ,0 1I1 m r ., ~ N H
p i n o H
m a r wn f N a 1!1 V
,D
N ~ V
O a V
~n m a w . r .n r . , ., ~o a N m H
r .a a N a 1 a N
a H
Y r .~ r . N a H
a O
v w C a D a a " T
' ' o m a ~
- r. m w - 'r .
a N H h ~ ' Tm -n H ., ~ a ~
i ~' c ' t ' ., t~ c ~ . o I a a -o ~ ~ ~ ~ o ~ ~ ~ a H v. c w a ~ a o~ 1- C r .~ w 4 4 o V
c t0 ~ ~ a .Z a JC w 2 o . . ..
4. Z a O -~ c c N ~ . . .~
r .. C a o o o > .~
47a ~ m > . ~ V ~
o ~ ~
0 L ~ ~ = i ~~ P um u v ~ ~ ~
... < , a. ..~ t . . a a ..~ a a x x , w w ~ ..r ~ ~ v i a o a x x ~ a ~ W
a -. a x r-1 H H o m t~ H ~ ~ ~ . e r. - a a a a a a ~
a .L7 E
~t,r9EI~DED SHEE t IPFA/EP
WO S3/59027 PCT/EP9FIU3E9~
The cleaning score (as given in the last row of this table) is a measure for the cleaning performance of these formulations. The higher the score the better the performance.
Functionality of components:
T
Dissolvine NG (Na gluconate) - transition metal ion sequestrant T1~1 Bayhibit AM - threshold agent, prevents 10 deposition of inorganic scales Triton H-66 T~ - hydrotrope or solubilising agent Sodium Cumene Sulfonate - hydrotrope or 15 solubilising agent Keltrol F T~ - structurant that (Xanthon polysaccharide...) stabilises nonionic in water emulsions (suspends-non-ionic) For reference purposes, the mould removal performance of a few current commercial formulations were tested under the same conditions. The results are shown in table 9.
Table 9 Detergent trade name Supplier Cleaning score M
Stabilon Flussig Henkel-Ecolab 1 SU860 - DiverseyLever 2 AMENDED SHEET
IPEA/EP
Investigation of mould removal from PET bottles Procedure for pre-washing PET bottles New 1.5 litre PET bottles were washed/rinsed according to the following procedure:
- 30 min soaking in 1.5o NaOH at 58-60°C; empty the bottles - 5 min delay - 15 min rinsing / soaking in fresh tapwater (rinse 1) - 5 min delay - 15 min rinsing / soaking in fresh tapwater (rinse 2) - 5 min delay - 15 min rinsing / soaking in fresh tapwater (rinse 3) - store bottles bottom-up in crates for 1 - 2 hours - post - rinse with 0.5 litre demineralised water per bottle - storage of the bottles bottom-up in crates for 30 - 60 min - wipe outside of the bottles until dry with absorbing paper - store the bottles, in upright position and allow the remaining bit of water to evaporate (at least 24 hours) before further use of the bottle.
Procedure for mould-soiling of pre-washed PET bottles The pre-washed PET bottles were "mould-soiled" as follows:
- grow Aspergillns niger on 2 plates containing Czapek Dox Agar with 2$ glucose and 10 ml lactic acid (10~) per litre agar.
- grow the mould for at least 7 days at 25°C.
- take the moulds from the plate with 9 ml of a sterile solution containing 1 g/L Peptone and 8.5 g/L NaCl per plate.
- add twice 9 ml of the mould suspension to 300 g of tomato juice (Zontomaatje ex Riedel, the Netherlands) and homogenate with glass pearls.
Application of this soil onto the inside surface of the (1.5 litre, transparent colourless) pre-washed ref-PET bottle was carried out within 6 hours after preparation of the soil. 5 g of soil was used to cover the inner wall/bottom up to 1/3 of the height of each bottle.
The soiled bottles stoppered by a wad of cotton wool were stored for 6 weeks at room temperature in order to allow the fungi to grow/sporulate and to allow the tomato juice to dry.
Test procedure for cleaning PET bottles The performance of a series of (n) cleaning solutions, 70 litres, was compared by taking n sets of m standard mould-soiled bottles.
A method, mimicking the conditions and mechanical action in an industrial bottlewasher was used. Each detergent solution was used to clean several sets of (maximum 4) bottles:
t = 0 min: immerse (soak) 4 bottles in (70 1) detergent solution (58-60°C).
t = 3 min: take bottles out of s~'_ution and empty them t = 4 min: immerse bottles a fi + (fresh) water bath t = 6 min: take bottles out of first water bath and empty them t = 7 min: immerse bottles in second (fresh) water bath t = 9 min: take bottles out of second water bath and empty them After this cleaning procedure, the bottles were stored, overnight, bottom-up in crates for further evaluation.
Per cleaning solution, the n (e. g. 12) cleaned bottles were coded according to their ranking (1 =
cleanest, n = dirtiest. The result is m (e. g. 4) crates containing n (e. g. 12) ranked bottles each.
Table 10 1-1 1-2 1-3 - - etc = - 4-1 4-2 4-3 >
1-10 1-11 1-12 - - etc = - 4-10 4-11 4-12 >
Procedure for evaluation of the cleaning result After cleaning (procedure see: ), the (nxm) bottles (coded 1-1, 1-2, ..1-m, 2-1, .., n-m) were ranked 1, 2, .., nxm-1, nxm (1: best cleaning result; nxm (e.g.48): worst cleaning result).
The sum of all rankings is: S (= e.g.
1+2+,..,.+47+48 = 1176).
Per cleaning solution: T = sum (total) of rankings The best possible result for T is: B (e. g.
1+2+...+11+12 = 78) The worst possible result for T is: W(e.g.
37+38+...+47+48 = 510) In some cases, the average ranking was taken such that "S" remained constant (e.g. 2x13.5 instead of 13 and 14, or 3x46 instead of 45, 46, and 47), The relative cleaning performance, P, is given as:
P = 10 x (W - T) / (W - B) (10 = best relative performance, 0 = worst relative performance) Table 11 below shows the formulation tested, whilst figure 1 shows the relative performance of a number of formulations according to the present invention.
W
a r m m o .-i rv m m H wn ~o r 3 o d ~ N N N N N r N N N
N
N
W
N
'i d p o N o , .1 r1 p U1 ~D ~
0W ~i rl N c0 x N
p a H
N .o r u~ r ... b r., n N r .-1 r-1 ,..p, N .-1 N N
a -n N
r1 O O ~D m N
amn ~o r r x m r1 .H e1 N N -n N N N ..i .
W
m C
H
N
N
E" .r N ~ a mo amn r m av W
N
.i \ O O O O O O
O O O m O u1 N n1 N rl O A
W
Q
0 0 o a o 0 y n o 0 o ao 0 N
rv n n7 r .~ v~ c N
H O A
a a G
a Y, ~a ro x ~ A
E
E
x C
O
.a a x "~
o o~
x N
an a u, a a ~o a a m a ~~ x a a O
x x o ~
c a f ~
au ~
C x ~a cap '_ y C
~
L
a .a p 9 .
p c p p, H ~ ~ ~
u ' a 4 F t n Z
x w p, WO 98/59027 PCT/EP98l03695 Procedure for mould-soiling of pre-washed PC bottles Grow Aspergillus niger (ATCC 16404) on 2 plates containing Malt Extract Agar. Grow the mould for 5 days at 25°C . Take the moulds form the plate with 10 ml of milk per plate. Add the 2x10 ml mould contaminated milk to 200 g yoghurt/milk mixture (150 g yoghurt Campina "halfvol" and 50 g milk Campina "halfvol") and homogenate with glass pearls.
Application of this soil onto the inside surface of the (1.0 litre, transparent colourless) pre-washed PC
bottle should occur within 6 hours after preparation of the soil. An amount of 10 g mould contaminated milk/yoghurt is used to cover the inner wall/bottom up to 1/2 of the height of the bottle. The bottles are, loosely, closed by means of a wad of cotton wool.
The soiled bottles are incubated for at least 6 weeks at 30°C in order to allow the fungi to grow/sporulate and to allow the milk/yoghurt to dry.
Cleaning procedure for mould-soiled PC bottles The performance of a series of (n) cleaning solutions, 70 litres, is compared by taking n sets of m standard mould-soiled bottles. Soiling of the bottles must have taken place at least 6 weeks before, according to the procedure for mould-soiling of pre-washed PC bottles.
The cleaning procedure for polycarbonate (PC) be ..les comprises a combination of soaking in a 70 litre ba~:h filled with detergent solution during 10 min at 79-81°C, and spraying with the same cleaning solution into the bottle according to the spraying program given below.
1. 15 sec spraying, followed by 10 sec delay 2. 15 sec spraying, followed 10 sec delay by 3. 15 sec spraying, followed 10 sec delay by 4. 15 sec spraying, followed 10 sec delay by 5. 15 sec spraying For this detergent rinse, the bottles (one by one) are placed, bottom-up, vertically over a nozzle.
Through this nozzle, a jet of cleaning liquid is directed exactly to the middle of the bottom of the bottle. The flow IO is adjusted to 1750-2000 ml per five pulses of 15 seconds each. Nozzle: NF2000 (BSP BETE), supplied by Spraybest, angle=)°, max flow = 20 1/min Total contact time = 5 x 15 s = 75 s = 1 min 15 s Flow rate = 1.4-1.6 1/min After the cleaning procedure, the bottles are rinsed by immersing them in cold tapwater directly followed by emptying. The bottles are stored, bottom-up in crates for further evaluation.
Per cleaning solution, the n (e. g. 12) cleaned bottles are coded according to their ranking in the same way as described in the procedure for PET bottles.
Table, l2 below shows the formulation tested, whilst figure 2 shows the results thereof.
w a Ei H
h.' M cr tn 00 l0 ~ lD l0 3 '~ ~ .~ mn M
~ ,- M
M
~f1 In N
d' rl N M
M ~
ri '-I
ri ~O
H N M tl1 M
1:1 ~ H
ll'1 lD 0p lD
N N
U
I~
I~ N d~ 01 lD
rl ri d~ ri r-I
(~
H
U E-' C~
W ri N M In ll1 O d~
~ ~
Tf 01 O O
r1 O O
, 3 . .
O ~r 04 ~ ~r b ~n o00 r-.i ~ ~n o 0 3 '"'i ~r M G ~
x ~-i N O O
e-( lD L(1 O
M v-i W N p4 l0 O
tr1 00 O
O
rt~ p0 N
_ U
w o .., - u~ x x - o N
ri v ~o ~~x zoa .
m H
According to a fourth aspect of the invention, there is provided a process for washing bottles, comprising the steps of exposing bottles to a formulation or additive according to the invention, wherein the sequestrant, nonionic surfactant ands hydrotrope and possibly any further standard detergent formulation components, such as TM
a defoamer, for example Dehypon LT109 pare collectively or individually supplied into a bottle washing system Detailed description of the invention the sequestrant according to the present invention preferably comprises one or more of the following:
- hydroxyl groups, preferably not more t five, - formyl groups, - C1- to Cq-alkoxy groups, - phenoxy groups, - C1-C4 alkoxycarbony groups, and/or a phenylalkyl 'th 1-20 C atoms in the alkyl group, and can comprise a or more of the following:
- a fiver or six-membered unsaturated or saturated heterocy is ring preferably with up to 3 hetero-atoms, most referably selected from the group nitrogen, oxygen, AMENDED SHEET
IPEAIEP
WO 98159027 PCT/EP98/9~6°5 ring may comprise one or more of the follo g groups:
- a C1-C4 alkyl group, - a hydroxyl group, - a carboxyl group, - a sulfo group - a phospho group - a sul ate ester - a hosphate ester ~ a C,-C4 alkoxycarbonyl group.
The sequestrant is ~~ selected from the group consisting of Nitrilo triacetic acid (NTA), ~i-Alanine diacetic acid (~3-ADA), Methyl glycine diacetic acid (MGDA), Serine diacetic acid (SDA) and Ethyl glycine diacetic acid (EGDA), wherein MGDA and SDA yield particularly good cleaning results.
The non-ionic surfactant preferably comprises one or more of the following:
- polyoxyethylene or polyoxypropylene condensates of aliphatic carboxylic acids having 8 to 18 carbon atoms in an aliphatic chain and incorporating from a.~a~t 2 to a~ae~ 50 ethylene oxide and/or propylene oxide units, polyoxyethylene or polyoxypropylene condensates of aliphatic alcohols having afrom 6 to 24 carbon atoms and incorporating from ahs~ 2 to 50 ethylene oxide and/or propylene oxide units, - a compound of formula:
R-(CHZCHzO)aH
ANfENDED SHEEN' ~pEAIEP
' WO 98/59027 PC7 /EP9b/03695 wherein R is a C6-C24 linear or branched alkyl group and a is an integer from 2 to 50, - a compound of formula:
R'- (CHzCHO) X (CHZCH20) y (CHzCHO) ZH
Rz R3 wherein R' is a linear alkyl group having an average of about 6 to about 18 carbon atoms, Rz and R3 are each linear alkyl groups of 1 to ~be~tt 9 carbon atoms, x is an integer from 1 to 6, y is an integer from 4 to 20 and z is an integer from 4 to 25, - polyoxyethylene or polyoxypropylene condensates of alkyl phenols having about 6 to 12 carbon atoms and incorporating from about 2 to 25 moles of ethylene oxide and/or propylene oxide, - polyoxyethylene derivatives of sorbitan mono-, di-and tri-fatty acid esters wherein the fatty acid component has between 12 and 24 carbon atoms and the polyethylene chains contain between about 9 and 30 ethylene oxide units, - polyoxyethylene-polyoxypropylene block copolymers having the formula:
HO ( CHzCH20 ) a ( CH ( CH3 ) CH20 ) b ( CHZCHZO ) ~H or HO (CH (CH3) CHZO) d (CHZCHZO) a (CH (CH3) CHZO) fH
wherein a, b, c, d, e, and f are integers from 1 to 350 reflecting the respective polyethylene oxide and polypropylene oxide blocks of said polymer, wherein the polyoxyethylene component of the block polymer is at least about 10~ of the block polymer, AMENDED SHEET
IPEAIEP i PC'1'/EP9l~/03h9s - alkyl glycosides having formula:
R90(R50)"(Z1) P
wherein R4 is a monovalent organic radical, for example a monovalent saturated aliphatic, unsaturated aliphatic or aromatic radical such as alkyl, hydroxyalkyl, alkenyl, hydroxyalkenyl, aryl, alkylaryl, hydroxyalkylaryl, arylalkyl, alkenylaryl, arylalkenyl and the like having from aft 6 to 30 carbon atoms, wherein RS is a divalent hydrocarbon radical containing from 2 to a~e~t 4 carbon atoms such as ethylene, propylene or butylene (most preferably the unit (R50)" represents repeating units of ethylene oxide, propylene oxide and/or random or block combinations thereof); n is an integer from 0 to a~e~rt 12;
Z1 represents a moiety derived from a reducing saccharide containing 5 or 6 carbon atoms (most preferably a glucose unit); and p is a number from 0.5 to a~e~ 10, - amine oxides having formula:
R6R'RBN=0 wherein R6, R' and Re are saturated aliphatic groups or substituted saturated aliphatic groups. wherein preferably R6 is an alkyl chain of .a~etrt 10 to 20 carbon atoms and R' and R8 are methyl or ethyl groups or both R6 and R' are alkyl chains of 6 to 14 carbon atoms and R8 is a methyl or ethyl group.
A.n additive with such a non-ionic surfactant in combination with the above sequesr4ant yielded goe:= cleaning results.
The non-ionic surfactant ~r~for~~,~~~ has a hydrophilic-lipophilic balance (HLB) of from abeQt 14-20.
AMENDED Sh~EET
IPE~IEP i WO 98/59027 PCTI~P98/L369~
Non-ionic surfactants can be broadly defined as surface active compounds with one or more uncharged hydrophilic substituents. A major class of non-ionic surfactants are those compounds produced by the condensation of alkylene oxide groups with an organic hydrophobic material which may be aliphatic or alkyl aromatic in nature. The length of the hydrophilic or polyoxyalkylene radical which is condensed with any particular hydrophobic group can be readily adjusted to yield a water-soluble compound having a desired degree of balance between hydrophilic and hydrophobic elements.
The HLB value represents the hydrophilic-lipophilic balance of the molecule. The lower the HLB value the more hydrophobic the material is, and vice versa. For simple alcohol ethoxylates, the HLB value may be calculated from HLH = E/5 (I) where E is the weight percentage of ethylene oxide in the molecule.
The simple straight chain alcohol ethoxylates are usually well defined materials. The inventors have been able to find a relationship between HLB-value (as calculated using equation (I)) and cleaning performance (as measured by mould removal). The straight chain alcohol ethoxylates according to~yhe present invention possess an HLB-value from about .~~to 20.
For fatty esters of polyalcohols and their alkoxylates, the HLB value is given by:
HLB = 20 x (1-S/A) (II) where S = saponification number of the ester, ie. the number of mg of potassium hydroxide needed to neutralise the free and bonded acid in 1 g of the substance;
AMENDED SHEET
tp~~/FP
WO 98159027 PCTiEP98~~364s' A = acid value of the esterified fatty acid, ie. the number of mg of potassium hydroxide to neutralise the free acid in 1 g of the substance.
The inventors have found that an additive with such a non-ionic surfactant, exhibiting the above HLB' values, yields particularly good cleaning results for PET bottles.
The additive most preferably comprise a non-ionic surfactant selected from the group consisting essentially ThJ Tly TM
of Synperonic A7, Synperonic L11, Lutensol A20, Lutensol A030,M Lutensol AT80T~Neodol 45-4ETMDehypon G2084TM Poly-TM ?M TiLJ
Tergent SLF18B45, Surfynol 504 and Plurafac LF231, wherein the non-ionic surfactant preferably has a cleaning score of about 3 or above, preferably about 4 or above and most preferably about 5 or above.
Cleaning score The cleaning results are obtained by measuring the absorbance at ~max between 662.0 en 664.0 nm, which is a measure for the amount of methylene blue in solution. To compare the results of different batches of mould soiled strips, an internal standard was measured for every new batch of strips. This internal standard was a product TM
containing 63.5$ Trilon ES9644 (35$ MGDA, ex. BASF), 7$
TM TM
Dissolvine NG (ex. Akzo Nobel), 1$ Bayhibit AM (ex. Bayer), 4$ Triton H-66T~ex. Union Carbide), 0.8$ Sodium Cumene TM
Sulfonate (40$, ex Huls), 2$ Dehypon LT104 (ex. Henkel).
The difference in cleaning performance between the internal st_:_dard and another observation is significant when the calculated difference is larger than the confidence intervals around the measured averages. This can be transformed into a formula where every significant difference will result in an increase or decrease of the AMENDED SHEET
IPE~EP
W'O 98/59027 PCT/EP98/03695 cleaning score, compared to the internal standard. The cleaning score can be calculated according to equation (III) .
( Xi - XS ) Cleaning score = + Vi Q X Tea-o.~;u~
Where:
Xi - Measured absorbance of the internal standard (corrected for the blanc; i.e. measured absorbance of an unsoiled strip);
XS - Measured absorbance of the sample (corrected for the blanc; i.e. measured absorbance of an unsoiled strip);
Q - Average deviation of the measurement. Following the procedure described above, the average deviation was found to be 0.18;
Tca=o.~;u>= Students value for a two tail test at 80g confidence level with v degrees of freedom;
Vi - Value of internal standard (equals 4 for the internal standard described above).
This definition of the cleaning score leads in this study to a range from 0 to 11 depending on Q, in which the higher the value the better the mould removal performance.
Table 1 shows a selection of preferred non-Tonics.
' WO 98159027 PCTIGP98/u369~
Table 1 Straight chain primary alkanol ethoxylates: H-( CHZ ) "- ( OCHzCHz ) m OH
n 10 12 14 16/18(avg:l7) m 3 aq: not solubleaq: not solubleaq: not solubleaq: not soluble HLB: 9.1 (theoryHLB: 8.3 (theoryHLB: 7.6 (theo~HLB: 6.8 (theory TM
Dehydol D3 Dobanol 23-3 Dobanol 25-3 Atlas G-70140 TM H TM
Dobanol 91-2.5Elfapur LT30SLTMElfapur LP Volpo N3 T'~
rM 25 S~
Ethylan CD Ethylan CD123TMElfapur LP
103 T~ 25 Sirs Ethylan CD Genapol LA-030 Ethylan D253 Genapol Z030XRemcopal 121 Renex 703 TM TM Trr 10 Synperonic Rolfor LA 3 Synperonic 91-2.5 TM A3T~
Synperonic L3 T M
Volpo L3 Special TM
7 d.pnt cl.pnt: cl.pnt:48C cl.pnt:
HLB: 13.2(theor)HLB: 12.5 (theoryHLB: 11.8 HLB: 10.9 (theory (theory Ethylan CD Ethytan CD 127 Dobanol 25-7 Eumulgin WM7 107 rM T~ T~ TH
Ethylan CD Dobanol 23-6.5 Dobanol 45-7 Rolfor CO 7 916 TM rH TM rM
Sy,~,peronic Elfapur LT65SLNT~Renex 711 91-7 T~ Tn Genapol LA-070 Synperonic T~ A7 T~
Genapol LA-079 rH
Synperonic L7 T~
Volpo T7 TH
11 cl.pt approx cl.pnt: cl.pnt > 100Ccl.pnt > 100C
2 0 HLB: 15.1 HLB: 14.4 (theory(5% aq) HLB: 13.1 (theor) (theory r h Sellig LA11 ' HLB: 13.9 Britex CS 11 100M8 (the TO
Synperonic L11TMDobanol 45-11Genapol T-110TM
Etfapur LP110SWTLutensol AT11 TH
Ethylan CD Mariipal 1618111 4511T''~ T'~
Renex 720 Rotfor HT 11 rM T ~
Synperonic Simulsol 56 Synperonic TAE11T
.
20 cl.pnt > 100Ccl.pnt >100C ci.pnt >100C cl.pnt 90C
I
HLe 17.0 (theoryHL3: 16.5 (5% aq) (1 ~ in 5% NaCI) T TM HLB: 16.1 HL3 15.5 (theory Synperonic Seilig LA11 (theory Seltig LA11 Renex 720 Atia~ G-4938 50 ~ T'~ T~' Synperonic Brij 58 (C16) A20 T~ TM
Bnj 78 (C18)TH
Britex S 200tH
Ethylan CS20TM
Genapol T-200TH
Sellig SU 25 100 ~
Volpo CS 20 T~
A~~i~~,'~~D S~~~T
~~'=A/~p , PCT/I:P98/G3695 There are many more primary alkanol ethoxylates e.g. n=10, m=4; n=10, m=5; n=10, m=6; n=10, m=8 ...
n=11, m=3, 9, 5, 6, 7, 8, 9, 10, 11, . . . , 80 n=20, m=3, . . . , 80 The hydrotrope ~~r--Ea~~~~s~--a ~~s~~eiah.~ l is .~ ~ ' U
,Y~ a+-s ~ h«~r~~'r~,~ °-~ is -.off re.~or~~., .. selected from the group consisting l.l-~ of: sodium benzoate, sodium 3-hydroxy-2-naphtoate, sodium xylene sulphonate, phosphate esters, sodium decyl diphenyl oxide, sodium dimethyl naphthalene sulphonate, sodium salts of linear alkyl benzene sulphonate, having from about C8 to C12 in the alkyl portion, as well as mixtures thereof, wherein the h drotro a is most TM
y p preferably Triton H66 also being a solubilizing agent. An additive comprising this hydrotrope yielded particularly good cleaning results.
An hydrotrope is preferable to a non-ionic surfactant when cleaning polycarbonate bottles, since non-ionic surfactants are thought to damage these.
The invention will now be described by way of the following examples and results, referring to figures 1-2 and the tables.
Experimental Standard soiling The standard soiling was made by mixing Tomato juice and a solution of Aspergillus niger.
AMENDED SHEET
IPEA/EP
Preparation of standard soiling Mntcri~lc - Aspergillus niger ATC 6275 - Czapek Dox agar (code CM97 ex Oxoid) - D-Glucose monohydrate - l0o Lactic acid solution SR 021 K
- Bacto Pepton L37 (ex Oxoid) - Sodium chloride Procedures Aspergillus niger was grown on 2 plates containing Czapek Dox agar with 2~ glucose and 10 ml lactic acid (10$) per litre agar. The mould was grown for 5 days at 25°C. Subsequently, the moulds were taken from the plate with two times 9 ml of a sterile solution containing 1 g/1 Pepton and 8.5 g/1 NaCl per plate. The mould solution was added (=18 ml) to 300 gr of tomato juice (Zontomaatje ex Riedel) and homogenised.
Preparation of ref-PET strips M ~ t c r ; W c - New ref-PET bottles - Sodium hydroxide Procedure The bottom and the neck were cut from a 1.5 ltr ref-PET bottle. The middle ,of thA bottle was used to cut pieces of 70 x 25 mm from the length direction of the bottle. The strips were then treated with 1.5~ caustic of 59°C for 15 minutes. The strips were rinsed with water to remove the caustic and the strips were dried.
Applying the soiling to the strips Strips were taken and submerged for 75~
vertically in the standard soiling (tomato juice with Aspergillus niger). The strips were then taken out of the solution and held 5-10 sec. vertically. In this way the excess soiling can drip off the strips. The strips were placed with the bold side up in a petri dish and put together with other strips in a plastic bag in an incubator at 25°C. After 5 days the plastic bag was removed and the strips, in closed petri-dishes, were restored in the incubator for 2 more days. After this the strips were ready for a quality check before use.
Quality check and cleaning procedure The standard soiled strips were taken and washed for 10 minutes in 1.5o caustic to check the quality of the soiling.
~r~+-o,-; ~ ~
- Beaker broad model 2000 ml - Magnetic stirrer (25 mm X 5 mm triangle shaped) - Temperature and rotation controlled stirrer - Stripholder - Chronograph r-1, o,., ; ~- ~ i - Methylene blue solution (0.10$), TNO procedure COP for ref-PET, V18 method A
- Acetic acid (1.00$) - Caustic solution (1.500 + additive (0.2~) Conditioning procedure - Take the petri dishes with the standard soiled strips out of the incubator.
- Take 4 soiled strips from the petri dishes and 2 unsoiled and place them in the stripholder.
- Heat a 1000 ml 1.50$ caustic solution up to 59°Ct 1°C
and set the stirring speed to 600 rpm. Place the stripholder with the 9 soiled ref-PET strips and 2 clean ref-PET strips for exactly 10.0 minutes in the caustic solution.
- Rinse the strips (3 times 5 sec) in 1000 ml of demineralised water.
- Wait 1 minute.
- After this the strips are dyed for 20 seconds in a 0.10$ methylene blue solution.
- Wait 1 minute.
- The strips are again rinsed for 3 times 5 sec. in 1000 ml of fresh demineralised water.
- Wait 1 minute.
- Put the 4 dyed strips in a closable can with 25 g of 1.00 acetic acid. Repeat this for the two blanc strips. Shake the dye from the strips.
- Filtrate 10 ml of the solution ( within 24 hrs) over a 0.45 /.cm filter and discard the first 5 ml. Put the other 5 ml in a 1 cm cuvet.
- Measure the absorption at JlmaX (between 662.0 and 664.0 nm) against 1.00 ~ acetic acid.
- Carry out the above steps with another 3 x 6 strips in the same cleaning solution.
WO 98/59027 1'CT/EP98/~365'S
Investigation of additives and formulations according to the present invention To assess the mould removal performance of various bottlewashing additives, PET strips standardly 5 soiled with a tomato juice contaminated with a common mould species (Aspergillus niger) were used. After conditioning, as above, these strips were soaked in an alkaline medium (1.5$ caustic in 8.5 DH water) for 10 minutes. The method to quantify the soil residue, as detailed above was used to 10 determining the cleaning score for the various additives and formulations, results of which are shown in the following tables.
Table 2 Sequestrant Supplier Level in Cleaning (Trade or development formulation Score name) (w~) EDTA, tetra sodium salt B~F 80.0 3 TM
lTrilon E39, 39% solution) Potassium tripolyphosphategudenhelm 27.2 1 (50% solution) m salt B~F 5 4 u 63 MGDA, tri sod T .
H
lTrilon ES9964, 35%
solution) SDA, tri sodium salt g~cF 24.2 4 The results shown in table 2 were obtained using formulations that, in addition to the sequestrant listed, AMENDED SHEET
lPEA/EP
' WO 98/59027 PC ~ /EP9~/03G9~
TM
contained sodium gluconate (70), Bayhibit AM (1~ of a 500 TM
solution), Triton H66 (4$ of a 50o solution), sodium cumene TM
sulfonate (0.80 of a 40~ solution), and Dehypon LT104 (20).
These formulations were dosed at a 0.2$ level in water of 8.5DH hardness, containing 1.5$ NaOH. The mould soiled strips were soaked in these solutions for 10 min at 59°C.
The results shown in tables 3-8 were obtained using formulations that, in addition to the surfactant, TM
contained Trilon ES9644 (63.5$ of a 35$ solution), sodium gluconate (7$), Bayhibit AM M1~ of a 50$ solution), Triton H66TM4$ of a 50$ solution), and sodium cumene sulfonate (0.8~ of a 40$ solution). These formulations were dosed at a 0.2$ level in water of 8.5DH hardness, containing 1.5~
NaOH. The mould soiled strips were soaked in these solutions for 10 min at 59°C (see above).
The formulations in table 3 exhibited good cleaning scores.
Table 3 Trade name Supplier Alkyl EO HLB Cleaning (Nonionic chain calculated Score surfactant) using (I) TM
synperonic ICI C10 7 11.8 4 T
synperonic ICI C12-14 11 19 5 Lil ZOTM
Lutensol .~ BASF C13-15 20 16.2 5 Lutenso11~o30 BASF C13-15 30 17 5 TM
Lutensol AT80 BASF C13-15 80 18.5 6 ~~'~~~~,n'_v Sr"~'~w ". ~1 ;~, WO 98759027 f~CT~~P98/J3693 On the other hand, straight chain alcohol ethoxylates with lower HLB-values exhibited a lesser cleaning score, as shown by table 4:
Table 4 Trade name Supplie Alkyl EO 8LB Cleaning (Nonionic r chain calculated Score surfactant) using (I) TM
Neodol 45-4E Shell C14-C15 4 8.9 1 Also some capped non-ionic surfactants showed good cleaning scores, as shown by table 5:
Table 5 Trade name Supplie Alkyl EO PO Cap Cleanin (Nonionic r chain g Score surfactant) (s / b) TM
Dehypon 62084 Henkel C16-20 8 - Butyl 4 (b) Dehypon LT104 Henkel C12-C18 10 - Butyl 9 T M
(s) Poly-Tergent Olin C20-C30 20 1 Octyl 5 ShF18B45 TM (s) Additional nonionics that showed good performance are shown in table 6:
AMENDED SHEET
IPEA/EP
WO 98/59027 PCT,'EPSB/33655 Table 6 Trade name Supplier Technical information Cleaning by (Nonionic supplier Score surf actant) TM per Ethoxylated 9 Surfynol 509 Products tetramethyldecynediol TM
AG 6202 Akzo-NobelLow-foaming 9 alkylpolyglucoside with C12 alkyl chain ~
Plurafac LF231 BASF Alkali-stable, low-foaming9 fatty alcohol alkoxylate Many nonionic surfactants however did not exhibit good cleaning scores in combination with sequestrant types, as shown by table 7:
Table 7 Trade name Supplier Alkyl EO PO Cleaning (Nonionic chain Score surfactant) TM
Dehypon LS24 Henkel C12-14 2 4 2 TM
Dehypon LS36 Henkel C12-14 3 6 1 TM
Dehypon LS45 Henkel C12-14 4 5 2 Dehypon LS54T~ Henkel C12-14 5 4 2 TM
Dynol 604 Air ethoxylated 2 Products acetylenic n , diols AMENDED SHEE'~
IPEA/EP
WO 98/59027 YL f ~EP98~U3~-'>
The following formulations were investigated according to the cleaning procedure and yielded the following results, Table 8:
H
f r r1 1' N V tf1 NI O H
m a rv yn ~o r .r r o H
N m V
H
r .. ~ N v ~~
a n o 11 ,0 1I1 m r ., ~ N H
p i n o H
m a r wn f N a 1!1 V
,D
N ~ V
O a V
~n m a w . r .n r . , ., ~o a N m H
r .a a N a 1 a N
a H
Y r .~ r . N a H
a O
v w C a D a a " T
' ' o m a ~
- r. m w - 'r .
a N H h ~ ' Tm -n H ., ~ a ~
i ~' c ' t ' ., t~ c ~ . o I a a -o ~ ~ ~ ~ o ~ ~ ~ a H v. c w a ~ a o~ 1- C r .~ w 4 4 o V
c t0 ~ ~ a .Z a JC w 2 o . . ..
4. Z a O -~ c c N ~ . . .~
r .. C a o o o > .~
47a ~ m > . ~ V ~
o ~ ~
0 L ~ ~ = i ~~ P um u v ~ ~ ~
... < , a. ..~ t . . a a ..~ a a x x , w w ~ ..r ~ ~ v i a o a x x ~ a ~ W
a -. a x r-1 H H o m t~ H ~ ~ ~ . e r. - a a a a a a ~
a .L7 E
~t,r9EI~DED SHEE t IPFA/EP
WO S3/59027 PCT/EP9FIU3E9~
The cleaning score (as given in the last row of this table) is a measure for the cleaning performance of these formulations. The higher the score the better the performance.
Functionality of components:
T
Dissolvine NG (Na gluconate) - transition metal ion sequestrant T1~1 Bayhibit AM - threshold agent, prevents 10 deposition of inorganic scales Triton H-66 T~ - hydrotrope or solubilising agent Sodium Cumene Sulfonate - hydrotrope or 15 solubilising agent Keltrol F T~ - structurant that (Xanthon polysaccharide...) stabilises nonionic in water emulsions (suspends-non-ionic) For reference purposes, the mould removal performance of a few current commercial formulations were tested under the same conditions. The results are shown in table 9.
Table 9 Detergent trade name Supplier Cleaning score M
Stabilon Flussig Henkel-Ecolab 1 SU860 - DiverseyLever 2 AMENDED SHEET
IPEA/EP
Investigation of mould removal from PET bottles Procedure for pre-washing PET bottles New 1.5 litre PET bottles were washed/rinsed according to the following procedure:
- 30 min soaking in 1.5o NaOH at 58-60°C; empty the bottles - 5 min delay - 15 min rinsing / soaking in fresh tapwater (rinse 1) - 5 min delay - 15 min rinsing / soaking in fresh tapwater (rinse 2) - 5 min delay - 15 min rinsing / soaking in fresh tapwater (rinse 3) - store bottles bottom-up in crates for 1 - 2 hours - post - rinse with 0.5 litre demineralised water per bottle - storage of the bottles bottom-up in crates for 30 - 60 min - wipe outside of the bottles until dry with absorbing paper - store the bottles, in upright position and allow the remaining bit of water to evaporate (at least 24 hours) before further use of the bottle.
Procedure for mould-soiling of pre-washed PET bottles The pre-washed PET bottles were "mould-soiled" as follows:
- grow Aspergillns niger on 2 plates containing Czapek Dox Agar with 2$ glucose and 10 ml lactic acid (10~) per litre agar.
- grow the mould for at least 7 days at 25°C.
- take the moulds from the plate with 9 ml of a sterile solution containing 1 g/L Peptone and 8.5 g/L NaCl per plate.
- add twice 9 ml of the mould suspension to 300 g of tomato juice (Zontomaatje ex Riedel, the Netherlands) and homogenate with glass pearls.
Application of this soil onto the inside surface of the (1.5 litre, transparent colourless) pre-washed ref-PET bottle was carried out within 6 hours after preparation of the soil. 5 g of soil was used to cover the inner wall/bottom up to 1/3 of the height of each bottle.
The soiled bottles stoppered by a wad of cotton wool were stored for 6 weeks at room temperature in order to allow the fungi to grow/sporulate and to allow the tomato juice to dry.
Test procedure for cleaning PET bottles The performance of a series of (n) cleaning solutions, 70 litres, was compared by taking n sets of m standard mould-soiled bottles.
A method, mimicking the conditions and mechanical action in an industrial bottlewasher was used. Each detergent solution was used to clean several sets of (maximum 4) bottles:
t = 0 min: immerse (soak) 4 bottles in (70 1) detergent solution (58-60°C).
t = 3 min: take bottles out of s~'_ution and empty them t = 4 min: immerse bottles a fi + (fresh) water bath t = 6 min: take bottles out of first water bath and empty them t = 7 min: immerse bottles in second (fresh) water bath t = 9 min: take bottles out of second water bath and empty them After this cleaning procedure, the bottles were stored, overnight, bottom-up in crates for further evaluation.
Per cleaning solution, the n (e. g. 12) cleaned bottles were coded according to their ranking (1 =
cleanest, n = dirtiest. The result is m (e. g. 4) crates containing n (e. g. 12) ranked bottles each.
Table 10 1-1 1-2 1-3 - - etc = - 4-1 4-2 4-3 >
1-10 1-11 1-12 - - etc = - 4-10 4-11 4-12 >
Procedure for evaluation of the cleaning result After cleaning (procedure see: ), the (nxm) bottles (coded 1-1, 1-2, ..1-m, 2-1, .., n-m) were ranked 1, 2, .., nxm-1, nxm (1: best cleaning result; nxm (e.g.48): worst cleaning result).
The sum of all rankings is: S (= e.g.
1+2+,..,.+47+48 = 1176).
Per cleaning solution: T = sum (total) of rankings The best possible result for T is: B (e. g.
1+2+...+11+12 = 78) The worst possible result for T is: W(e.g.
37+38+...+47+48 = 510) In some cases, the average ranking was taken such that "S" remained constant (e.g. 2x13.5 instead of 13 and 14, or 3x46 instead of 45, 46, and 47), The relative cleaning performance, P, is given as:
P = 10 x (W - T) / (W - B) (10 = best relative performance, 0 = worst relative performance) Table 11 below shows the formulation tested, whilst figure 1 shows the relative performance of a number of formulations according to the present invention.
W
a r m m o .-i rv m m H wn ~o r 3 o d ~ N N N N N r N N N
N
N
W
N
'i d p o N o , .1 r1 p U1 ~D ~
0W ~i rl N c0 x N
p a H
N .o r u~ r ... b r., n N r .-1 r-1 ,..p, N .-1 N N
a -n N
r1 O O ~D m N
amn ~o r r x m r1 .H e1 N N -n N N N ..i .
W
m C
H
N
N
E" .r N ~ a mo amn r m av W
N
.i \ O O O O O O
O O O m O u1 N n1 N rl O A
W
Q
0 0 o a o 0 y n o 0 o ao 0 N
rv n n7 r .~ v~ c N
H O A
a a G
a Y, ~a ro x ~ A
E
E
x C
O
.a a x "~
o o~
x N
an a u, a a ~o a a m a ~~ x a a O
x x o ~
c a f ~
au ~
C x ~a cap '_ y C
~
L
a .a p 9 .
p c p p, H ~ ~ ~
u ' a 4 F t n Z
x w p, WO 98/59027 PCT/EP98l03695 Procedure for mould-soiling of pre-washed PC bottles Grow Aspergillus niger (ATCC 16404) on 2 plates containing Malt Extract Agar. Grow the mould for 5 days at 25°C . Take the moulds form the plate with 10 ml of milk per plate. Add the 2x10 ml mould contaminated milk to 200 g yoghurt/milk mixture (150 g yoghurt Campina "halfvol" and 50 g milk Campina "halfvol") and homogenate with glass pearls.
Application of this soil onto the inside surface of the (1.0 litre, transparent colourless) pre-washed PC
bottle should occur within 6 hours after preparation of the soil. An amount of 10 g mould contaminated milk/yoghurt is used to cover the inner wall/bottom up to 1/2 of the height of the bottle. The bottles are, loosely, closed by means of a wad of cotton wool.
The soiled bottles are incubated for at least 6 weeks at 30°C in order to allow the fungi to grow/sporulate and to allow the milk/yoghurt to dry.
Cleaning procedure for mould-soiled PC bottles The performance of a series of (n) cleaning solutions, 70 litres, is compared by taking n sets of m standard mould-soiled bottles. Soiling of the bottles must have taken place at least 6 weeks before, according to the procedure for mould-soiling of pre-washed PC bottles.
The cleaning procedure for polycarbonate (PC) be ..les comprises a combination of soaking in a 70 litre ba~:h filled with detergent solution during 10 min at 79-81°C, and spraying with the same cleaning solution into the bottle according to the spraying program given below.
1. 15 sec spraying, followed by 10 sec delay 2. 15 sec spraying, followed 10 sec delay by 3. 15 sec spraying, followed 10 sec delay by 4. 15 sec spraying, followed 10 sec delay by 5. 15 sec spraying For this detergent rinse, the bottles (one by one) are placed, bottom-up, vertically over a nozzle.
Through this nozzle, a jet of cleaning liquid is directed exactly to the middle of the bottom of the bottle. The flow IO is adjusted to 1750-2000 ml per five pulses of 15 seconds each. Nozzle: NF2000 (BSP BETE), supplied by Spraybest, angle=)°, max flow = 20 1/min Total contact time = 5 x 15 s = 75 s = 1 min 15 s Flow rate = 1.4-1.6 1/min After the cleaning procedure, the bottles are rinsed by immersing them in cold tapwater directly followed by emptying. The bottles are stored, bottom-up in crates for further evaluation.
Per cleaning solution, the n (e. g. 12) cleaned bottles are coded according to their ranking in the same way as described in the procedure for PET bottles.
Table, l2 below shows the formulation tested, whilst figure 2 shows the results thereof.
w a Ei H
h.' M cr tn 00 l0 ~ lD l0 3 '~ ~ .~ mn M
~ ,- M
M
~f1 In N
d' rl N M
M ~
ri '-I
ri ~O
H N M tl1 M
1:1 ~ H
ll'1 lD 0p lD
N N
U
I~
I~ N d~ 01 lD
rl ri d~ ri r-I
(~
H
U E-' C~
W ri N M In ll1 O d~
~ ~
Tf 01 O O
r1 O O
, 3 . .
O ~r 04 ~ ~r b ~n o00 r-.i ~ ~n o 0 3 '"'i ~r M G ~
x ~-i N O O
e-( lD L(1 O
M v-i W N p4 l0 O
tr1 00 O
O
rt~ p0 N
_ U
w o .., - u~ x x - o N
ri v ~o ~~x zoa .
m H
Claims (9)
1. Additive for a detergent formulation, said additive comprising a sequestrant selected from the group consisting of nitrilo triacetic acid (NTA), .beta.-alanine diacetic acid (.beta.-ADA) methyl glycine diacetic acid (MGDA), serine diacetic acid (SDA) and ethyl glycine diacetic acid (EGDA), and wherein the formulation further comprises a non-ionic surfactant having a hydrophilic - lipophylic balance of between 14 - 20 and a hydrotrope selected from the group consisting of sodium benzoate, sodium 3-hydroxy-2-naphtoate, sodium xylene sulphonate, sodium decyl diphenyl oxide, sodium dimethyl naphthalene sulphonate, sodium salts of linear alkyl benzene sulphonate having from C8 to C12 in the alkyl portion, as well as mixtures thereof.
2. Additive according to claim 1, wherein the non-ionic surfactant comprises one or more of the following:
- polyoxyethylene or polyoxypropylene condensates of aliphatic carboxylic acids having 8 to 18 carbon atoms in an aliphatic chain and incorporating from 2 to 50 ethylene oxide and/or propylene oxide units, - polyoxyethylene or polyoxypropylene condensates of aliphatic alcohols having from 6 to 24 carbon atoms and incorporating from 2 to 50 ethylene oxide and/or propylene oxide units, - a compound of formula:
R- (CH2CH2O) aH
- polyoxyethylene or polyoxypropylene condensates of aliphatic carboxylic acids having 8 to 18 carbon atoms in an aliphatic chain and incorporating from 2 to 50 ethylene oxide and/or propylene oxide units, - polyoxyethylene or polyoxypropylene condensates of aliphatic alcohols having from 6 to 24 carbon atoms and incorporating from 2 to 50 ethylene oxide and/or propylene oxide units, - a compound of formula:
R- (CH2CH2O) aH
3. Additive according to claim 1, wherein the hydrotrope is also a solubilising agent.
4. Additive according to claim 3, wherein the hydrotrope is Triton H66 (an alkali metal salt of a phosphate ester).
5. Additive according to claim 1, further comprising a structurant to aid in solubilising the non-ionic surfactant.
6. Additive according to claim 1, further comprising a defoamer.
7. Formulation comprising an additive according to claim 1 wherein the sequestrant is present in a wt% range of 5-60, preferably 15-35, and the non-ionic and hydrotrope in a wt% range of 0.5-40, preferably 1-25.
8. Use of the formulation according to claim 8 as a detergent in cleaning bottles.
9. Process for washing bottles comprising the steps of exposing bottles to a formulation of claim 7 or additive according to claim 1, wherein the sequestrant, non-ionic surfactant and the hydrotrope and possibly any further standard detergent formulation components, such as a defoamer, are
Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
EP97201939 | 1997-06-24 | ||
EP97201939.2 | 1997-06-24 | ||
PCT/EP1998/003695 WO1998059027A1 (en) | 1997-06-24 | 1998-06-10 | Additive for a detergent formulation, detergent formulation comprising such an additive and use of said formation for cleaning bottles |
Publications (1)
Publication Number | Publication Date |
---|---|
CA2293760A1 true CA2293760A1 (en) | 1998-12-30 |
Family
ID=8228479
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CA002293760A Abandoned CA2293760A1 (en) | 1997-06-24 | 1998-06-10 | Additive for a detergent formulation, detergent formulation comprising such an additive and use of said formation for cleaning bottles |
Country Status (7)
Country | Link |
---|---|
EP (1) | EP0991745A1 (en) |
AU (1) | AU8216498A (en) |
BR (1) | BR9810315A (en) |
CA (1) | CA2293760A1 (en) |
TR (1) | TR199903221T2 (en) |
WO (1) | WO1998059027A1 (en) |
ZA (1) | ZA985422B (en) |
Families Citing this family (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
AU2005305095B2 (en) * | 2004-11-03 | 2011-07-14 | Diversey, Inc. | Method of cleaning containers for recycling |
US20130261197A1 (en) * | 2012-04-03 | 2013-10-03 | Luigi Bacchiocchi | Additive for Use in Wash Step of PET Recycling Process |
CN109952366B (en) | 2016-08-16 | 2022-09-20 | 戴弗西公司 | Compositions and methods for aesthetic improvement of food and beverage containers |
US10800996B2 (en) | 2019-02-11 | 2020-10-13 | American Sterilizer Company | High foaming liquid alkaline cleaner concentrate composition |
Family Cites Families (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE3504451A1 (en) * | 1985-02-09 | 1986-08-14 | Degussa Ag, 6000 Frankfurt | DETERGENT PICTURES |
DE3712329A1 (en) * | 1987-04-11 | 1988-10-20 | Basf Ag | METHOD FOR THE PRODUCTION OF SERINE-N, N-DIACETIC ACID AND DERIVATIVES, THEIR USE, IN PARTICULAR AS COMPLEXING AGENTS, AND DETERGENT AND CLEANING AGENT THEREOF |
DE3833047C2 (en) * | 1988-09-29 | 1993-12-16 | Henkel Kgaa | Acid, machine dishwashing detergent |
DE4240697A1 (en) * | 1992-12-03 | 1994-06-09 | Basf Ag | Iminodiacetic acid derivs. from use as complexing agents or builders - in technical hard surface cleaners, have high calcium binding capacity and can be formulated without organic solvent |
DE4240695A1 (en) * | 1992-12-03 | 1994-06-09 | Basf Ag | Iminodiacetic acid derivs. for use as complexing agents or builders - in aq. cleaning compsns. for the food and beverage industries, have high calcium binding capacity and can be formulated without organic solvent |
DE4319935A1 (en) * | 1993-06-16 | 1994-12-22 | Basf Ag | Use of glycine-N, N-diacetic acid derivatives as complexing agents for alkaline earth and heavy metal ions |
-
1998
- 1998-06-10 TR TR1999/03221T patent/TR199903221T2/en unknown
- 1998-06-10 EP EP98932170A patent/EP0991745A1/en not_active Withdrawn
- 1998-06-10 CA CA002293760A patent/CA2293760A1/en not_active Abandoned
- 1998-06-10 BR BR9810315-6A patent/BR9810315A/en not_active Application Discontinuation
- 1998-06-10 AU AU82164/98A patent/AU8216498A/en not_active Abandoned
- 1998-06-10 WO PCT/EP1998/003695 patent/WO1998059027A1/en not_active Application Discontinuation
- 1998-06-22 ZA ZA9805422A patent/ZA985422B/en unknown
Also Published As
Publication number | Publication date |
---|---|
BR9810315A (en) | 2000-09-05 |
EP0991745A1 (en) | 2000-04-12 |
AU8216498A (en) | 1999-01-04 |
TR199903221T2 (en) | 2000-08-21 |
ZA985422B (en) | 1999-12-22 |
WO1998059027A1 (en) | 1998-12-30 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
US20240052271A1 (en) | Alkyl amides for enhanced food soil removal and asphalt dissolution | |
CN102292428B (en) | Development of an aluminum hydroxycarboxylate builder | |
US8071520B2 (en) | Sulfonated alkyl polyglucoside use for enhanced food soil removal | |
CA2265407C (en) | Aqueous cleaning and disinfecting compositions which include quaternary ammonium compounds, block copolymer surfactants and further mitigating compounds which compositions featurereduced irritation | |
JP2022089915A (en) | Use of eo/po block copolymer surfactant for controlling viscoelasticity in highly concentrated liquid compound | |
AU673072B2 (en) | Novel low foaming rinse agents comprising alkylene oxide modified sorbitol fatty acid ester and defoamin agent | |
CN102414090A (en) | Wetting agents for aseptic filling | |
US20120322710A1 (en) | Poly phosphate functionalized alkyl polyglucosides for enhanced food soil removal | |
US8262805B2 (en) | Poly sulfonate functionalized alkyl polyglucosides for enhanced food soil removal | |
CN114874860B (en) | Solid enzyme detergent compositions and methods of use and manufacture thereof | |
WO2011055318A2 (en) | Alkyl polyglucosides and a propoxylated-ethoxylated extended chain surfactant | |
CA2265363C (en) | Aqueous cleaning and disinfecting compositions having reduced irritation characteristics based on quaternary ammonium compounds including block copolymer surfactants and further surfactants | |
WO2012025872A2 (en) | Ethoxylated alcohol and monoethoxylated quaternary amines for enhanced food soil removal | |
US8969285B2 (en) | Phosphate functionalized alkyl polyglucosides used for enhanced food soil removal | |
JP6188199B2 (en) | Dishwasher cleaner | |
CA2293760A1 (en) | Additive for a detergent formulation, detergent formulation comprising such an additive and use of said formation for cleaning bottles | |
JPH1017900A (en) | Composition for enhancing deterging and drying effects for dish washer | |
CN110373287A (en) | A kind of automatic dish-washing machine cleansing tablet with heterogeneous structure | |
CN110343578A (en) | A kind of automatic dish-washing machine detergent composition | |
JP2004263013A (en) | Detergent composition for tableware dish washing device |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
FZDE | Discontinued |