CN1250470A - Hard-surface cleaning compositions - Google Patents
Hard-surface cleaning compositions Download PDFInfo
- Publication number
- CN1250470A CN1250470A CN98803209A CN98803209A CN1250470A CN 1250470 A CN1250470 A CN 1250470A CN 98803209 A CN98803209 A CN 98803209A CN 98803209 A CN98803209 A CN 98803209A CN 1250470 A CN1250470 A CN 1250470A
- Authority
- CN
- China
- Prior art keywords
- composition
- weight
- alkyl
- polymkeric substance
- hydroxyalkyl
- 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.)
- Pending
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- 239000000203 mixture Substances 0.000 title claims abstract description 104
- 238000004140 cleaning Methods 0.000 title claims abstract description 60
- 229920006318 anionic polymer Polymers 0.000 claims abstract description 12
- 125000002091 cationic group Chemical group 0.000 claims abstract description 11
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 claims abstract description 7
- 239000000126 substance Substances 0.000 claims description 66
- 241000282326 Felis catus Species 0.000 claims description 38
- 239000013543 active substance Substances 0.000 claims description 21
- 239000003795 chemical substances by application Substances 0.000 claims description 18
- 125000002768 hydroxyalkyl group Chemical group 0.000 claims description 17
- 125000000217 alkyl group Chemical group 0.000 claims description 16
- -1 R3 is C6-C22 alkyl Chemical group 0.000 claims description 14
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- 238000000034 method Methods 0.000 claims description 11
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 10
- 125000002877 alkyl aryl group Chemical group 0.000 claims description 10
- 229910021645 metal ion Inorganic materials 0.000 claims description 9
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 8
- 239000002904 solvent Substances 0.000 claims description 8
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- 239000003945 anionic surfactant Substances 0.000 claims description 7
- 239000004584 polyacrylic acid Substances 0.000 claims description 7
- 125000004178 (C1-C4) alkyl group Chemical group 0.000 claims description 6
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 6
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- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 claims description 6
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- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 claims description 2
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- OCBHHZMJRVXXQK-UHFFFAOYSA-M benzyl-dimethyl-tetradecylazanium;chloride Chemical compound [Cl-].CCCCCCCCCCCCCC[N+](C)(C)CC1=CC=CC=C1 OCBHHZMJRVXXQK-UHFFFAOYSA-M 0.000 description 8
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- 229910021536 Zeolite Inorganic materials 0.000 description 1
- 239000001940 [(1R,4S,6R)-1,7,7-trimethyl-6-bicyclo[2.2.1]heptanyl] acetate Substances 0.000 description 1
- KCDFSJZEDNTQMC-MAZPRZIYSA-N [(1s,4s)-4,7,7-trimethyl-2-bicyclo[2.2.1]heptanyl] acetate Chemical compound C1C[C@@H]2C(OC(=O)C)C[C@@]1(C)C2(C)C KCDFSJZEDNTQMC-MAZPRZIYSA-N 0.000 description 1
- DPDMMXDBJGCCQC-UHFFFAOYSA-N [Na].[Cl] Chemical compound [Na].[Cl] DPDMMXDBJGCCQC-UHFFFAOYSA-N 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 235000012211 aluminium silicate Nutrition 0.000 description 1
- 150000003863 ammonium salts Chemical class 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000010692 aromatic oil Substances 0.000 description 1
- 210000004666 bacterial spore Anatomy 0.000 description 1
- 150000003818 basic metals Chemical class 0.000 description 1
- 230000003115 biocidal effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000012496 blank sample Substances 0.000 description 1
- 229940116229 borneol Drugs 0.000 description 1
- 238000009395 breeding Methods 0.000 description 1
- 230000001488 breeding effect Effects 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- 150000001649 bromium compounds Chemical class 0.000 description 1
- 235000010633 broth Nutrition 0.000 description 1
- 239000007853 buffer solution Substances 0.000 description 1
- 229930008380 camphor Natural products 0.000 description 1
- 229960000846 camphor Drugs 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 150000007942 carboxylates Chemical group 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 239000002738 chelating agent Substances 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- 230000003750 conditioning effect Effects 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 229940071118 cumenesulfonate Drugs 0.000 description 1
- 238000013016 damping Methods 0.000 description 1
- GSVLCKASFMVUSW-UHFFFAOYSA-N decyl(dimethyl)phosphine oxide Chemical compound CCCCCCCCCCP(C)(C)=O GSVLCKASFMVUSW-UHFFFAOYSA-N 0.000 description 1
- ZRKZFNZPJKEWPC-UHFFFAOYSA-N decylamine-N,N-dimethyl-N-oxide Chemical compound CCCCCCCCCC[N+](C)(C)[O-] ZRKZFNZPJKEWPC-UHFFFAOYSA-N 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 239000011928 denatured alcohol Substances 0.000 description 1
- 210000003298 dental enamel Anatomy 0.000 description 1
- 238000009792 diffusion process Methods 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 class [O-]P([O-])(=O)OP([O-])([O-])=O XPPKVPWEQAFLFU-UHFFFAOYSA-J 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 229940009662 edetate Drugs 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- 230000000855 fungicidal effect Effects 0.000 description 1
- 239000000499 gel Substances 0.000 description 1
- 239000003292 glue Substances 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical group 0.000 description 1
- 230000009931 harmful effect Effects 0.000 description 1
- 230000012447 hatching Effects 0.000 description 1
- IPCSVZSSVZVIGE-UHFFFAOYSA-N hexadecanoic acid Chemical compound CCCCCCCCCCCCCCCC(O)=O IPCSVZSSVZVIGE-UHFFFAOYSA-N 0.000 description 1
- 229960002885 histidine Drugs 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 150000001261 hydroxy acids Chemical group 0.000 description 1
- 238000001764 infiltration Methods 0.000 description 1
- 230000008595 infiltration Effects 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- 239000002054 inoculum Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 1
- 239000010501 lemon oil Substances 0.000 description 1
- 231100000225 lethality Toxicity 0.000 description 1
- 239000003550 marker Substances 0.000 description 1
- 239000000693 micelle Substances 0.000 description 1
- 230000000813 microbial effect Effects 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- BAVYZALUXZFZLV-UHFFFAOYSA-N mono-methylamine Natural products NC BAVYZALUXZFZLV-UHFFFAOYSA-N 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
- 235000015097 nutrients Nutrition 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 230000010355 oscillation Effects 0.000 description 1
- 230000001151 other effect Effects 0.000 description 1
- MPQXHAGKBWFSNV-UHFFFAOYSA-N oxidophosphanium Chemical class [PH3]=O MPQXHAGKBWFSNV-UHFFFAOYSA-N 0.000 description 1
- 125000000913 palmityl 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])C([H])([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
- 239000002245 particle Substances 0.000 description 1
- 239000000312 peanut oil Substances 0.000 description 1
- 230000002085 persistent effect Effects 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 150000003016 phosphoric acids Chemical class 0.000 description 1
- 239000011297 pine tar Substances 0.000 description 1
- 229940068124 pine tar Drugs 0.000 description 1
- 235000010482 polyoxyethylene sorbitan monooleate Nutrition 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 229920000053 polysorbate 80 Polymers 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 239000011241 protective layer Substances 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000013207 serial dilution Methods 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 229920002545 silicone oil Polymers 0.000 description 1
- PODWXQQNRWNDGD-UHFFFAOYSA-L sodium thiosulfate pentahydrate Chemical compound O.O.O.O.O.[Na+].[Na+].[O-]S([S-])(=O)=O PODWXQQNRWNDGD-UHFFFAOYSA-L 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 238000010186 staining Methods 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 230000001954 sterilising effect Effects 0.000 description 1
- 238000004659 sterilization and disinfection Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000000516 sunscreening agent Substances 0.000 description 1
- 239000000375 suspending agent Substances 0.000 description 1
- 125000001302 tertiary amino group Chemical group 0.000 description 1
- 238000004448 titration Methods 0.000 description 1
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 1
- PHYFQTYBJUILEZ-IUPFWZBJSA-N triolein Chemical compound CCCCCCCC\C=C/CCCCCCCC(=O)OCC(OC(=O)CCCCCCC\C=C/CCCCCCCC)COC(=O)CCCCCCC\C=C/CCCCCCCC PHYFQTYBJUILEZ-IUPFWZBJSA-N 0.000 description 1
- 229940117972 triolein Drugs 0.000 description 1
- 229960001947 tripalmitin Drugs 0.000 description 1
- 239000006150 trypticase soy agar Substances 0.000 description 1
- 238000009827 uniform distribution Methods 0.000 description 1
- 230000000007 visual effect Effects 0.000 description 1
- 239000003643 water by type Substances 0.000 description 1
- 239000010457 zeolite 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
- C11D3/48—Medical, disinfecting agents, disinfecting, antibacterial, germicidal or antimicrobial compositions
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
- C11D1/66—Non-ionic compounds
- C11D1/835—Mixtures of non-ionic with cationic compounds
-
- 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
- C11D3/37—Polymers
- C11D3/3746—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- C11D3/3757—(Co)polymerised carboxylic acids, -anhydrides, -esters in solid and liquid compositions
- C11D3/3765—(Co)polymerised carboxylic acids, -anhydrides, -esters in solid and liquid compositions in liquid compositions
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
- C11D1/38—Cationic compounds
- C11D1/62—Quaternary ammonium compounds
-
- 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
- C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
- C11D1/66—Non-ionic compounds
- C11D1/72—Ethers of polyoxyalkylene glycols
Landscapes
- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Wood Science & Technology (AREA)
- Organic Chemistry (AREA)
- Detergent Compositions (AREA)
Abstract
The invention provides a hard surface cleaning composition of pH 7-11 comprising: a) 1-30 % by weight of nonionic surfactant, b) 0.005-5 % by weight of a water soluble, anionic polymer having an average molecular weight of less than 1000000, said polymer being free of quaternary nitrogen groups, wherein, the ratio of polymer: nonionic is 0.1: 1 or less, and, c) 0.005-5 % by weight of a cationic surfactant. It is believed that in the presence of the cationic surfactant, negatively charged (i.e. carboxylic dissociated) polymer can interact with the cationic surfactant and the nonionic surfactant to form a three-component complex which deposit the nonionic surfactant upon the soil and/or surface being cleaned. While the mechanism is not entirely clear, this may possibly be due to the interaction of the charged polymer with mixed miscelles of cationic and nonionic surfactant.
Description
Technical field
The present invention relates to comprise the general-purpose hard surface liquid cleaning compositions of nonionogenic tenside and polymeric constituent.
Background technology of the present invention
When the composition that is used to clean crust comprises one or more usually from the surface removal dirt as the nonionogenic tenside of clean-out system wherein.The fatty dirt detersive power of nonionogenic tenside is much better than charged tensio-active agent, therefore is generally used for crust, as the general cleaning combination of kitchen bench, bath equipment, floor and analogue.
The very wide various nonionogenic tensides of known range can be used for cleaning combination.For example, these tensio-active agents comprise alcohol alcoxylates usually, and described alcohol alcoxylates can be described as the compound of making by hydrophilic alkylene oxide group and aliphatic series or the reaction of alkane aromatics hydrophobic organic compound condensation.By regulating the length with the hydrophilic or polyalkylene oxide groups of any specific hydrophobic group condensation simply, can obtain a kind of water-soluble cpds that between hydrophilic segment and hydrophobic part, reaches the required balance degree.Its object lesson comprises the straight or branched Fatty Alcohol(C12-C14 and C12-C18) with 8-22 carbon atom and the condensation product of alkylene oxide, has the Oleum Cocois ethylene oxide condenses of 2-15 mole ethylene oxide as every mole of coconut alcohol; Other example comprises that its alkyl comprises the every mole of alkylphenol of 6-12 carbon atom and the condenses of 5-25 mole ethylene oxide.
Known in each component adding nonionic surfactant-based composition, deposit to lip-deep these components like this and can in a step cleaning operation, form anti-soiled protective layer.How we are used in combination some anionic polymer applying for that openly W0 94/26858 discloses with nonionogenic tenside, to improve initial cleaning performance simultaneously and to prevent dirt deposition again on the crust that cleans with the composition that comprises these polymkeric substance.It is believed that polymkeric substance not only can improve the initial detersive power of prescription, but also deposition stays and not only can prevent that dirt from adhering to but also helping the protective membrane of decontamination in cleaning process from the teeth outwards.Except anionic polymer, knownly can reach same effect by deposition silicone material and fluorochemical surfactant.
How W0 94/26858 discloses the cleaning combination that under acid ph value preparation can the deposited polymer protective membrane.As described in WO 94/26858, these polymkeric substance can lose effect owing to the pH value raising of prior art product.In addition, it is believed that the difficulty of acidic products is, they can destroy some surface, on enamel such as bathroom.Preferred in addition cleaning combination should be prepared under high pH value, to obtain good especially fatty dirt detersive power.Therefore, need in whole pH value scope 3-11, to prepare various products, keep the effect of described in these cases decontamination and laborsaving cleaning simultaneously.
Concise and to the point description of the present invention
Now definite, in the presence of cats product, can improve the pH value that contains polymkeric substance and nonionogenic tenside product and the various effects of not losing polymkeric substance.It is believed that to overcome like this and the relevant all difficulties of low pH value preparation, but the adding of cats product also has following described other advantage.
Therefore, the invention provides the hard-surface cleaning composition of a kind of pH value, wherein comprise for 3-12:
A) nonionogenic tenside of 1-30%,
B) molecular-weight average of 0.005-5% is lower than 1000000 water-soluble anionic polymer, and described polymkeric substance does not have the quaternary nitrogen group, wherein the ratio of polymkeric substance and nonionogenic tenside be 0.1: 1 or lower and
C) cats product of 0.005-5%.
Another aspect of the present invention relates to a kind of method of cleaning crust, and it is that the hard-surface cleaning composition of 3-12 is handled this surperficial step that this method comprises with the pH value, and described composition comprises:
A) nonionogenic tenside of 1-30%,
B) molecular-weight average of 0.005-5% is lower than 1000000 water-soluble anionic polymer, and described polymkeric substance does not have the quaternary nitrogen group, wherein the ratio of polymkeric substance and nonionogenic tenside be 0.1: 1 or lower and
C) cats product of 0.005-5%.
Be not subjected in the present invention under the situation of any actual theory limit, it is believed that, because not charged disassociation of nonionogenic tenside and polymkeric substance forms the hydrogen bond title complex between the hydroxy-acid group, therefore in the presence of polymkeric substance, the detersive power of nonionogenic tenside under acid ph value is improved.Along with the rising of pH value, the acidic group of polymkeric substance dissociates, and therefore no longer forms the hydrogen bond title complex.It is believed that, in the presence of cats product required for the present invention, negative electricity (being the carboxylic acid dissociative) polymkeric substance can interact with cats product and nonionogenic tenside, and formation can be deposited on nonionogenic tenside dirt to be cleaned and/or lip-deep three set of dispense compounds.Although and imperfectly understand its mechanism, this may be because the interaction between the mixed micelle of electropolymer and cats product and nonionogenic tenside.
It is believed that this title complex from the teeth outwards deposit two results.At first, can pass through tensio-active agent concentration from the teeth outwards, thereby improve the cleaning performance of initial wash cycle, and reduce the described initial stage and clean required labour.It is believed that in addition, this title complex or at least its some part can after cleaning, keep from the teeth outwards, therefore can prevent that dirt is bonded on this surface again, thereby make this surface be easy to cleaning at secondary with in the cleaning interval subsequently, that is, it has reduced " secondary " and has cleaned required power.
As long as cats product is an antimicrobial, the cats product that is present in so in the present composition also produces antibacterial effect in the cleaning process in the early stage.The composition of the application of the invention can reduce by 5 logarithmic seriess of total plate count.Unexpectedly we are definite, comprise the present composition of antiseptic cationic tensio-active agent, can produce long lasting hygienic condition on the surface of handling through said composition, even and also can keep this antibacterial effect after the rinsing of this surface.It is believed that this part is owing to preparation antibacterial components save power from the teeth outwards, and part is because said preparation can prevent microorganism adhesion more from the teeth outwards.
Therefore, a third aspect of the present invention relates to a kind of molecular-weight average and is lower than 1000000 water-soluble anionic polymer, application in the surface cleaning composition that comprises nonionogenic tenside and antiseptic cationic tensio-active agent, can prolong this antiseptic cationic tensio-active agent like this at described lip-deep antibacterial efficacy, described polymkeric substance does not have the quaternary nitrogen group.
Will be described in more detail as following, the present composition is deposited on lip-deep other useful component in the time of can being included in and carrying out cleaning operation with this composition.
Detailed description of the present invention
Below with the various preferred essential characteristics of more detailed description the present invention.
Polymkeric substance
Water-soluble polymers is a basal component of the present composition.
As mentioned above, polymkeric substance of the present invention is that molecular-weight average is lower than 1000000 and do not have a water-soluble polymers of quaternary nitrogen group.Usually, these polymkeric substance have carboxylate functionality, but do not get rid of the anionic polymer that uses other.In the context of the present invention, anionic polymer is to have the polymkeric substance of negative electricity or the similar polymkeric substance of protonated form, and can adopt polymeric blends.
In embodiments of the invention, preferred polymkeric substance is those that easily bought on market.They be the polymkeric substance of acrylic or methacrylic acid or maleic anhydride one or more these materials combine or with other monomeric multipolymer.
Specially suitable polymkeric substance comprises the multipolymer of polyacrylic acid, polymaleic anhydride and aforementioned substances and ethene, vinylbenzene and methylvinylether.
Most preferred polymkeric substance is a copolymer-maleic anhydride, preferably with the formed multipolymer of vinylbenzene, vinylformic acid, methylvinylether and ethene.The molecular weight of this polymkeric substance preferably at least 5000, more preferably at least 50000, most preferably surpass 100000.Have been found that as polyacrylic VERSICOL E-11[RTM] (from Allied Colloids) be a kind of polymkeric substance that is applicable to the present composition.
Usually, the tensio-active agent based cleaning compositions comprises the polymkeric substance based at least 0.01% weight of product.Even under the low-down situation of the content of polymkeric substance and tensio-active agent, can determine that also polymkeric substance is to improving the positively effect of cleaning performance.This lower concentration threshold value performance in the application of needs very dilute solution, as when the clean floors, particularly advantageous.
The content of polymkeric substance is preferably 0.05-5.0% weight, at this moment can produce significant especially anti-resoiling effect.The polymkeric substance that more preferably has 0.2-2.0% weight.We are definite, and under common extension rate, the polymkeric substance of high level can not produce significantly other cleaning advantage, has just increased the cost of composition.It is believed that the polymkeric substance of high level can improve the viscosity of product, therefore hindered this product the wetting of dirt and infiltration.But for the concentrated product of wanting before use Macrodilution, the initial content of polymkeric substance can be up to 5% weight.
As mentioned above, the molecular weight of polymkeric substance preferably is lower than 1000000 dalton.The cleaning performance that it is believed that polymkeric substance reduces along with the increase of molecular weight.
Tensio-active agent
Must comprise at least a nonionogenic tenside according to composition of the present invention.Composition of the present invention comprises the detergent active thing that can be selected from commercially available nonionic detergent active thing.Suitable nonionic detergent-active compounds can briefly be described as, the compound of making by hydrophilic alkylene oxide group and aliphatic series or the reaction of alkane aromatics hydrophobic organic compound condensation.Preferred especially alkoxylated alkanols.
By regulating the length with the hydrophilic or polyalkylene oxide groups of specific hydrophobic group condensation simply, can obtain a kind of water-soluble cpds that between hydrophilic segment and hydrophobic part, reaches the required balance degree.In general, these compounds can be the 1-20 molar equivalent ethylene oxide on having the C8-C22 alkyl chain and being connected it and/or the alcohol alcoxylates of propylene oxide residue.
Its object lesson comprises the straight or branched Fatty Alcohol(C12-C14 and C12-C18) with 8-18 carbon atom and the condensation product of 2-15 mole ethylene oxide, and this examples of substances comprises that every mole of coconut alcohol has the Oleum Cocois ethylene oxide condenses of 2-15 mole ethylene oxide; Every mole of alkyl comprises the alkylphenol of 6-12 carbon atom and the condenses of 5-25 mole ethylene oxide.
Preferred nonionic is the condensation product of C9-15 alcohol and ethylene oxide.In embodiments of the invention, having been found that DOBANOL[RTM] serial ethoxylated alcohol nonionic surfactant (from Shell) is suitable.Preferred material comprises DOBANOL 91-5[TM] (C9-C11 alkyl, the 5EO alkylethoxylate is from Shell) and DOBANOL91-8[TM] (C9-C11 alkyl, the 8EO alkylethoxylate is from Shell).
Can use the mixture of nonionogenic tenside.As in greater detail following, these mixed systems have some advantage on the anti-foam performance of product.
Operable other nonionogenic tenside material comprise the reaction product of quadrol and propylene oxide and ethylene oxide condenses, comprise the polyoxyethylene group of 40-80% weight, and molecular weight is the condenses of 5000-11000; Structure R
3NO (one of them R group is the alkyl with 8-18 carbon atom, and other be respectively methyl, ethyl or hydroxyethyl) tertiary amino oxides, as dimethyldecylamine oxide; Structure R
3PO (one of them R group is the alkyl with 10-18 carbon atom, and other be respectively alkyl or hydroxyalkyl with 1-3 carbon atom) phosphine oxides, as the dimethyl decyl phosphine oxide; With structure R
2The dialkyl sulphoxide of SO (one of them R group is the alkyl with 10-18 carbon atom, and other is methyl or ethyl) is as methyl four decyl sulfoxides; Fatty acid alkyl amide; The alkylene oxide condensate of fatty acid alkyl amide and alkyl sulfhydryl.In addition, alkyl polyglycoside it is believed that and can be used as nonionogenic tenside.
The consumption of nonionic detergent active thing in the present composition is generally 1-30% weight, preferred 3-15% weight.Active matter content above 15% improves seldom on the performance when being used to clean purely, but for the product that will carry out Macrodilution before using, can adopt higher content.These compositions comprise the nonionic actives based on the 5-10% weight of product usually.The ratio of anion surfactant can be lower, but preferably do not have anion surfactant in the composition.As in greater detail following, the form that a spot of anion surfactant can soap becomes the part of anti-foam system.The present composition preferably comprises and is lower than 2% weight, preferably is lower than the anion surfactant of 1% weight.
Usually, cats product is to have general formula R
1R
2R
3R
4N
+X
-Material, wherein all groups are the alkyl that has or do not have hydroxyl substituent, at least one group among the R1-R4 is C6-C22 alkyl, alkaryl or hydroxyalkyl, and at least one group among the R1-R4 is C1-C4 alkyl or hydroxyalkyl, and X is the monovalence counter anion.
Cats product is preferably has general formula R
1R
2R
3R
4N
+X
-The season hydrogen compound, wherein R1 and R2 are identical or different C1-C4 alkyl or hydroxyalkyl, R3 is C6-C22 alkyl, alkaryl or hydroxyalkyl, R4 is C1-C22 alkyl, alkaryl or hydroxyalkyl, and X is the monovalence counter anion.
X is preferably halogen, most preferably chlorine or bromine.
R1 and R2 are preferably methyl.In embodiments of the invention, R3 is preferably the C8-C18 alkyl, more preferably the C10-C16 alkyl.In embodiment of the present invention, R4 preferable methyl, C8-C18 alkyl or benzyl.Therefore, used cats product can have three " short chain " groups, as methyl and fat-soluble " long-chain " group; Or two " short chain " and two fat-soluble " long-chain ", wherein said " long-chain " can be the straight or branched hydrocarbon or comprise aromatic ring.
Another advantage that the present composition comprises cats product is that preferred cationic surfactants can be given the preparation anti-microbial property.We determine that astoundingly the present composition that comprises the antiseptic cationic tensio-active agent can produce long lasting hygienic condition on the surface of handling through said composition.
Specially suitable cationic detersive active compound comprises hexadecyl trimethylammonium bromide (CTAB), sclerosis two butter alkyl dimethyl ammonium chlorides (can buy from the market, BARDAC 2250), Zephiran chloride and composition thereof.
The cats product that comprises an aryl substituent is particularly preferred, can produce good especially antibacterial effect because it is believed that them.
The consumption of cats product is generally the 0.05-3% weight based on product.The preferable amount of cats product is about 1-3% weight.
The total amount that is used for the detergent-active compounds of detergent composition of the present invention is generally 1.5-30% weight, preferred 2-20% weight, most preferably 5-20% weight.
Solvent
Solvent can be present in the present composition.
The present composition preferably comprises the solvent with following general formula that is no more than 2% weight:
R
1-O-(EO)
m-(PO)
n-R
2
R wherein
1And R
2Be C2-6 alkyl or H independently, but can not be hydrogen atom simultaneously that m and n are 0-5 independently.It is believed that the use of polymkeric substance in the present composition can offset harmful effect that any solvent was produced when product was used for some plastic material.
More preferably wherein there is the solvent that is selected from diglycol monotertiary n-butyl ether, monoethylene glycol mono-n-butyl ether, propylene glycol n-butyl ether and composition thereof that is no more than 2% weight.Favourable and effectively, there is not other solvent beyond dewatering.
The metal ion wedding agent
Said composition preferably comprises washing assistant or the non-genus ion chelating agent of abacusing that helps, and they are generically and collectively referred to as the metal ion wedding agent.
Suitable metal ion wedding agent comprises mixture, zeolite of nitrilotriacetic acid(NTA) salt, multi-carboxylate, Citrate trianion, dicarboxylic acid, water-soluble phosphate (especially poly-phosphate), orthophosphoric acid salt and pyrophosphate salt and composition thereof.As described below, these wedding agents also can be used as abrasive when consumption surpasses its water solubility.In general, if the metal ion wedding agent is used as washing assistant, its amount preferably accounts for the 0.05-25% weight of composition.
In addition, can optionally use following metal ion wedding agent, as edetate (as, EDTA), amino poly-phosphate (as, series product of (TM) buying with " DEQUEST ") and phosphoric acid salt and various other multiple functionalized organic acid and salt (comprising glycine oxalic acid methyl esters (MGDA)).
More particularly comprise the metal ion wedding agent, preferred organic acetate, more preferably MGDA or EDTA other advantage is, can improve cats product, the anti-microbial property under the hard water condition especially is especially at Gram-negative bacteria.
The consumption of metal ion wedding agent is preferably 0.05-5% weight, preferred 0.1-3.0% weight, most preferably 1.5-3% weight.In the preferred composition that comprises about 2% cats product, organic acetate sequestrant of 1.5-3% can reduce by 5 logarithmic seriess of survival bacterium, even ticklish bacterial isolates, as Pseudomonas aeruginosa.
The MGDA or the EDTA that comprise 1.5-3% weight according to preferred composition of the present invention.
Except cleaning performance, we determine that the preparation that comprises polymkeric substance, alcohol, ethoxylate, cats product and sequestrant also has other effect, that is, it can reduce the adhesivity on fungi and/or bacterial spores and surface.Below will be described in more detail according to embodiment.
A small amount of thing
Composition of the present invention can include and helps its cleanup action and other general composition.
Usually, other optional component that is used for the present composition is can produce a large amount of foamy foams in use to regulate material, and the example that foam is regulated material is a soap.Soap is a soap, comprising alkali metal soap, as comprises about 8-24 carbon atom, the sodium of the higher fatty acid of preferably about 10-20 carbon atom, potassium, ammonium and alkanol ammonium salt.Useful especially be derived from the sodium of the fatty acid mixt of Oleum Cocois and peanut oil and potassium and single-, two-and triethanolamine salt.If use, the consumption of soap can account at least 0.005% of said composition weight, preferred 0.5-2%.
Other example that foam is regulated material is organic solvent, hydrophobic silicon dioxide, silicone oil and hydrocarbon.
Other foam is regulated material and is comprised mixing EO/PO nonionogenic tenside.Suitable ethoxylated/propoxylated ionic surfactant pack is drawn together the straight or branched Fatty Alcohol(C12-C14 and C12-C18) with 8-22 carbon atom and the condensation product of ethylene oxide and propylene oxide, as having the Oleum Cocois ethylene oxide/propylene oxide condenses of 2-15 mole ethylene oxide and propylene oxide altogether in every mole of coconut alcohol.The mol ratio of ethylene oxide and propylene oxide is preferably 1: 5-5: 1.
Particularly preferred ethoxylated/propoxylated ionic surfactant pack is drawn together the molecule with following structural formula:
R(EO)
n(PO)
mH
Wherein R is C8-C14 for the average carbon chain length degree, the alkyl residue of preferred C9-C11, and EO is the ethylene oxide residue, and n is 1-10, and PO is that propylene oxide residue and m are 1-5.Particularly preferred material is C9-11 5-8EO 1-3PO, most preferably C9-11 6EO 2PO.
The consumption of ethoxylated/propoxylated nonionic detergent active thing in the present composition is generally 2-10% weight, most preferably 3-6% weight.
The ratio of ethoxylated surfactant and ethoxylated/propoxylated tensio-active agent is preferably 4: 1-2: 1, and wherein ethoxylated surfactant is outweighing the ethoxylated/propoxylated tensio-active agent.
Except these compositions of having mentioned, composition of the present invention also can comprise other optional component, as pH value conditioning agent, sun-screening agent, tinting material, white dyes, soil-suspending agent, enzyme, compatible SYNTHETIC OPTICAL WHITNER, gel control agent, freeze-thaw stabilizer, other antiseptic-germicide, sanitas, washing hydrotropic agent, spices and opacifying agent.
Hydrotropic agent is useful selectable components.It is believed that hydrotropic use can improve the cloud point of composition, and need not to add anion surfactant.
Suitable hydrotropic agent comprises basic metal tosylate, urea, basic metal dimethylbenzene and cumene sulfonate, short chain, preferred C
2-C
5Pure and mild dibasic alcohol.In these hydrotropic agents, preferred sulfonate, especially cumene and tosylate.
The hydrotropic typical amounts of sulfonate type is 0-5%.Institute's expense of urea and alcohol is corresponding higher.Diluted product does not generally need hydrotropic agent.
If the present composition comprises and a kind ofly can effectively tensio-active agent/polymer complexes be deposited on lip-deep reagent to be cleaned, the present composition also can comprise and wishes to be deposited on lip-deep various component so.Three kinds of preferred other components are spices, non-cationic surfactant antibacterial components and wormer and/or sterilant.
If the present composition has comprised a kind of cats product and has been alkalescence, just there has been certain anti-microbial activity in said composition so.Other suitable non-cationic surfactant antibacterial components is known in the art.The exemplary of this material comprises antibiotic aromatic oil and oil ingredient.
The typical amounts of non-cationic antimicrobial agent in prescription is 0.01-8%, 0.05-4% weight wherein, especially about 2% is that conventional composition institute is preferred, in so-called concentrated product then the concentration height to 2-4 doubly.For spray product, the concentration of antiseptic-germicide is 0.05-0.5% weight.
Specially suitable wormer comprises essential oil, as pennyroyal, and especially arvensis peppermint, piperita peppermint, spicata peppermint and cardica peppermint; Lemongrass East India oil, lemon oil, lemongrass, China fir and pine tar; Terpenoid, especially limonene, Karvon, Terpane, coriandrol, camphor glue, lemongrass, α and β-terpenol, fencholic acid, borneol, iso-borneol, dl-Bornyl Acetate and isobornyl acetate.Most preferred wormer is a terpenoid, especially limonene.Known above-mentioned many oil have antibacterial effect, and can be used as wormer and/or spices.
Institute's expense of wormer changes along with used Substance Properties.For essential oil and terpenoid, preferable amount is the 0.1-5% of product.
The present composition particle that preferably do not rub basically.
The preferred pH value of net products is 7-12, the more preferably pH value scope of 7-11 wherein, and especially preferably the pH value scope of about 10-11 makes cleaning effect and hygiene efficacy reach balance like this.
The particularly preferred present composition is the mobile liquid, aqueous of pH value=7-12 (preferred 7-11), wherein comprises:
A) the ethoxylation 2-15EO C8-C18 of 5-20% weight alcohol nonionogenic tenside,
B) be lower than the anion surfactant of 1% weight,
C) molecular-weight average of 0.2-2% weight is lower than 1000000 water-soluble anionic polymer, described polymkeric substance be vinylformic acid, methacrylic acid or maleic anhydride are at least a and vinylformic acid, methacrylic acid, maleic anhydride, ethene, vinylbenzene and methylvinylether are at least a polymkeric substance and
D) cats product of 0.05-5% weight (preferred 0.05-2% weight) is a general formula R
1R
2R
3R
4N
+X
-The quaternary nitrogen compound, wherein R1 and R2 are identical or different C1-C4 alkyl or hydroxyalkyl, R3 is C6-C22 alkyl, alkaryl or hydroxyalkyl, R4 is C1-C22 alkyl, alkaryl or hydroxyalkyl, and X be the monovalence counter anion and
E) be no more than 2% the solvent that is selected from diglycol monotertiary n-butyl ether, monoethylene glycol mono-n-butyl ether, propylene glycol n-butyl ether and composition thereof.
The more particularly preferred present composition is described above, but wherein comprises cats product (Zephiran chloride) and the organic acetate metal ion wedding agent with anti-microbial property.These compositions have improved first and secondary cleaning effect under high pH value, but also various microorganism is had permanently effective anti-microbial property.
These compositions can be made into anhydrous basically powder, add water then and form the present composition.
In order further to understand the present invention, below be described by indefiniteness embodiment.
Embodiment
Embodiment 1-6: first and secondary cleaning
Described below all clean among embodiment, by spraying dirt deposition with specified quantitative on " DECAMEL " (RTM is from Formica) test surfaces of " A4 " size.This dirt is to comprise 1% tripalmitin, 0.5% triolein, 0.5% kaolin, 0.2% whiteruss, 0.1% palmitinic acid, 0.02% carbon black in the methylated spirit.Before cleaning, with the at room temperature aging one section specified time of this dirt.Being called the initial stage below the required initiation power of clean surface cleans required power.
If detect the secondary cleaning effect,, before staining, carry out abundant rinsing then with this DECAMEL sheet material of test composition pre-treatment to determine anti-resoiling performance.Clean the required reactive force in resoiling surface and be called the required power of secondary cleaning.
In first and secondary cleaning process, the rig that use is furnished with device for measuring force is measured with cellulose sponge cloth from the test surfaces required total force of dirt that gets on.Because the experiment condition difference, therefore following data should be in the serial experiment of different table comparative result.
These prescriptions comprise nonionogenic tenside and water, wherein are with or without polymkeric substance, and are with or without cats product.Used nonionogenic tenside is DOBANOL 91-5[TM] (C9-C11 alkyl, the 5EO alkylethoxylate is from Shell) and DOBANOL91-8[TM] (C9-C11 alkyl, the 8EO alkylethoxylate is from Shell).The example of polymkeric substance of the present invention is polyacrylic acid (VERSICOL E11[TM], from AlliedColloids), and its molecular-weight average is 250000 dalton.Used cats product is C
n-alkyl trimethyl amine bromide (C
nTAB: wherein n is 12,14 and 16), two hexadecyl dimethyl and three hexadecyl methyl amine bromides (being respectively DTAB and TTAB).The pH value of regulating composition with sodium hydroxide or following carbonate buffer system.
Embodiment 1a-1d in the following table 1 has provided with 0.5mg/cm
2The covering amount is coated with after the dirt, uses the required first cleanup action power of composition that comprises given prescription after aging 2 days on above-mentioned dirt.
Table 1
| ?1a | ?1b | ?1c | ?1d | |
| Dobanol?91-5 | ?7％ | ?7％ | ?7％ | ?7％ |
| Hexadecyl TAB | ?- | ?- | ?1％ | ?1％ |
| Versicol?E11 | ?- | ?0.5％ | ?- | ?0.5％ |
| Carbonate | ?pH9 | ?pH9 | ?pH9 | ?pH9 |
| Clean required reactive force (N/s) | ?1036 | ?769 | ?689 | ?412 |
As can be seen from Table 1, exist at the same time under the situation of cats product and polymkeric substance (embodiment 1d), the required reactive force of first cleaning reduces under the alkaline pH value, and if there is no or not have these components simultaneously, then need higher reactive force (comparing) with Comparative Examples 1a, 1b and 1c.It is believed that this is can improve the tensio-active agent polymkeric substance of concentration/tensio-active agent title complex from the teeth outwards owing to having formed.
Following table 2 has provided cationic influence to the required reactive force of first cleaning.With 0.25mg/cm
2The covering amount is coated with after the dirt, tests on above-mentioned dirt after aging 1 day.
Table 2
| ?2a | ?2b | ?2c | ?2d | ?2e | ?2f | ?2g | ?2h | |
| Dobanol?91-8 | ?7％ | ?7％ | ?7％ | ?7％ | ?7％ | ?7％ | ?7％ | ?7％ |
| TTAB | ?- | ?- | ?1％ | ?1％ | ?- | ?- | ?- | ?- |
| DTAB | ?- | ?- | ?- | ?- | ?1％ | ?1％ | ?- | ?- |
| CTAB | ?- | ?- | ?- | ?- | ?- | ?- | ?1％ | ?1％ |
| Versicol?E11 | ?- | ?0.5％ | ?- | ?0.5％ | ?- | ?0.5％ | ?- | ?0.5％ |
| Add oxyhydroxide | ?pH9 | ?pH9 | ?pH9 | ?pH9 | ?pH9 | ?pH9 | ?pH9 | ?pH9 |
| Clean required reactive force (N/s) | ?1754 | ?1408 | ?1520 | ?399 | ?1728 | ?617 | ?1324 | ?442 |
As can be seen from Table 2, (Comparative Examples 2a) compares with comparison, the required power of first cleaning under all situations all can obviously reduce (embodiment 2d, 2f and 2h) by tensio-active agent, polymkeric substance and being used in combination of cats product, and this can compare with the system that only adds cats product (Comparative Examples 2c, 2e and 2 grams).Under the situation that does not have cats product, only add polymkeric substance (Comparative Examples 2b) and can obviously not reduce the required power of first cleaning under this pH value.As can be seen, in employed different cats products, TTAB and CTAB can provide the product that needs minimum cleaning force.
Following table 3 also illustrated under given pH value, and in the presence of different content CTAB, the pH value is to the influence of the composition that comprises 7%Dobanol 91-5 and 0.5%Versicol E11.Regulate pH value with oxyhydroxide, be coated with after the dirt with 0.25mg/cm2 covering amount then, after wearing out 1 day, on above-mentioned dirt, test.These results clean required first total force, represent with N/s.
Table 3
| ??3a | ??3b | ??3c | |
| pH | ??pH6 | ??pH8 | ??pH10 |
| 0％???CTAB | ??213 | ??262 | ??- |
| 25％??CTAB | ??163 | ??195 | ??193 |
| 0.5％?CTAB | ??142 | ??180 | ??175 |
| 1％??CTAB | ??151 | ??131 | ??190 |
As can be seen from Table 3, in this pH value scope, first cleanup action power generally reduces along with the increase of cationic surfactant concentration.
Following table 4 provided shown under the pH value, when different content CTAB (C) and DTAB (D), the pH value is to comprising the influence of the composition of 8% actives and 0.5% Versicol E11 altogether.The non-cationic actives is Dobanol 91-5.Regulate the pH value with oxyhydroxide, then with 0.25mg/cm
2The covering amount is coated with after the dirt, tests on above-mentioned dirt after aging 1 day.These results are total required reactive forces of first cleaning, represent with N/s.
Table 4
| 4a | 4b | 4c | 4d | |
| pH | pH4 | pH7 | pH4 | pH7 |
| The type of cation activity thing | C | C | D | D |
| 0.00% cation activity thing | 162 | 749 | 162 | 749 |
| 0.13% cation activity thing | 171 | 399 | 171 | 308 |
| 0.25% cation activity thing | 188 | 288 | 173 | 227 |
| 0.50% cation activity thing | 190 | 403 | 162 | 269 |
As can be seen from Table 4, these compositions have bad cleanup action under higher pH value, unless there is cats product.In lower pH value scope (embodiment 4a and 4c), WO 94/26858 disclosed effect it is believed that and can reduce initial stage cleanup action power demand, and the adding cats product does not have obvious effects (if any yet, just said composition becomes poor slightly), although still can maintain the cleaning performance of usefulness.
Under higher pH (embodiment 4b and 4d), as can be seen, add cats product and obviously reduced the required reactive force of cleaning, make this nonionogenic tenside/polymeric system to reach simultaneously and be similar to the more resulting result of acidic products.
Following table 5 has provided, and has the modification nonionogenic tenside, to the influence of first cleanup action power demand and cloud point.These compositions comprise 7% Dobanol 91-5 and mixture, 1%CTAB and the 0.5%Versicol E11 of Dobanol91-8.This tabular has gone out the percentage ratio of Dobanol91-8 in the nonionic part of surfactant mixture, and the remainder of mixture is Dobanol 91-5.
Table 5
| ?％Dobanol?91-8 | Required reactive force (N/s) | Cloud point | |
| ?5a | ??????0 | ?????331 | ???30 |
| ?5b | ??????25 | ?????401 | ???42.5 |
| ?5c | ??????50 | ?????479 | ???53 |
| ?5d | ??????75 | ?????809 | ???64 |
| ?5e | ??????100 | ?????876 | ???75 |
As can be seen from Table 5, the composition that is rich in Dobanol 91-5 tensio-active agent (for example, 5a) descend on the required reactive force at most first the cleaning, and the composition that is rich in Dobanol 91-8 tensio-active agent (for example, 5e) also can effectively descend, but the situation of other tensio-active agent changes more not remarkable relatively first the cleaning on the required reactive force.Can clearly be seen that from this table, by selecting suitable combinations-of surfactants, the cloud point of may command composition.
Following table 6 has provided uses the influence of two kinds of different cats products to the secondary cleaning reactive force demand of the present composition in the cleaning interval subsequently." VARI " material is Varisoft 442-100P (TM: from Sherex-Witco), a kind of sclerosis two butter alkyl dimethyl ammonium chlorides.
Table 6
| ???6a | ???6b | ???6c | ???6d | |
| ???CTAB | ???CTAB | ???VARI | ???VARI | |
| For the first time | Recontaminate | For the first time | Recontaminate | |
| ?pH6 | ???886 | ???203 | ???846 | ???364 |
| ?pH8 | ???679 | ???257 | ???745 | ???460 |
| ?pH10 | ???969 | ???426 | ???958 | ???602 |
| ?pH12 | ???637 | ???211 | ???501 | ???408 |
As can be seen from Table 6, in all cases, prove that these surfaces are in secondary cleaning easy cleaning (with 6a and 6b relatively, with 6c and 6d comparison) more in the cycle.This explanation, one or more components of said composition deposit from the teeth outwards, and stay a kind of residual film that blocks the dirt bonding or assist in removing dirt, and the required reactive force of secondary cleaning after the promptly surperficial recontaminate is reduced.
Above embodiment illustrates how the present composition reduces first and the required reactive force of secondary cleaning simultaneously in wide ph range.
Embodiment 7-9: sterilization effect
Following table 7 has provided uses following bacterium (from National Collection of TypeCulture or American Type Culture Collection) to carry out the result of fungicidal effectiveness test.Culture remains on the bead in-80 ℃ of cold sanitass.
Staphylococcus aerogenes NCTC 10788
False green pus Zymomonas mobilis ATCC 15442
Yeast saccharomyces cerevisiae ATCC 9763
In order to prepare inoculum, bead is taken out from storage bottle, aseptic then transferring in 100 milliliters of nutrient broths, and under 37 ℃, in shaking bath, hatch 24 hours (bacterium).After hatching, transfer in two 50 milliliters of centrifuge tubes culture suspension is aseptic, then under 2180 grams centrifugal treating (Mistral 1000, MSE) to obtain cell in 10 minutes.Supernatant liquid is poured out, then precipitation is resuspended in the peptone diluent (0.1% peptone and 0.85% sodium-chlor, pH value are 7.0).This suspension, is used for before the test suspension at room temperature being placed on the worktable 30 minutes at least until the need time spent in 4 ℃ of placements.
Testing is a kind of titer plate analysis, and this is similar with " the anti-microbial activity testing method of food sanitation sterilant ", often is called European suspension test (EST).The bovine albumin that in some tests, adds low levels (0.03%) or high-content (0.3%).In " water of standard hardness " that above method is mentioned, make 1/15 dilution preparation.
B row by 270 milliliters of quenching solutions being added each plate and 270 milliliters of peptone thinners are added C-G row be ready to titer plate (Bibby Sterilin, aseptic 96-well, flat).This quenching solution is by Tween 80 (3.0%), Yelkin TTS (0.3%), L-Histidine (0.1%), Sulfothiorine (0.5%) and 0.25N KH
2PO
4Damping fluid (1%) is made in sterile distilled water (1 liter).With sterile distilled water or if appropriate with among bovine albumin (120ml) the adding testing well A row.Then preparation (150 milliliters 1/15 solution) is added in the suitable testing well.With these preparations stochastic distribution onboard.This plate is placed on stainless steel " plate brooder " dish that is connected to circulator bath (remaining on 20 ℃).
Use the hyperchannel transfer pipet, the aliquots containig of microbial suspension (30 milliliters) is added in titer plate A row's the well simultaneously.The test mixing thing after 20 ℃ contact 5 minutes ± 5 seconds down, is transferred to B row (hardening liquid) with aliquots containig (30 milliliters), form 10
-1Diluent.After 5 ± 1 minutes, aliquots containig (30 milliliters) is transferred to C row (peptone thinner).According to identical mode, carry out other serial dilution, up to G row (10
-6Dilution) till.Use the Miles-Misra technology to survey bacterial count.Three aliquots containigs (10 milliliters) of each diluent are formed stain being divided on the predrying Tryptone Soya Agar plate of 6 parts.With these stain dryings, then plate was hatched 24 hours down at 37 ℃.Each stain selects to have the 3-50cfu diluent partly with this plate counting, calculates the mean value of 3 stains then.Calculating this value denary logarithm, is to deduct the logarithmic value at the end from 10 of raw value then, obtains the drop-out value of logarithmic series.
All prescriptions all comprise Dobanol 91-8 (8%) and polymkeric substance (polyacrylic acid, 0.5% weight), then the pH value are adjusted to 9.In the presence of WSH (water of standard hardness) and dirt (bovine albumin), in test with preparation dilution 1/30.Given example is the preparation that comprises CTAB and Zephiran chloride.
Table 7
| Organism | ??CTAB ??(％) | ??BAAC(％) | Average logarithmic series drop-out value (2 revision tests) | |
| Low dirt | High dirt | |||
| Staphylococcus aerogenes | ??1.0 ??2.0 ??- ??- | ??- ??- ??1.0 ??2.0 | ??4.5 ??7.4 ??7.2 ??7.2 | ??4.7 ??7.6 ??7.2 ??7.2 |
| False green pus Zymomonas mobilis | ??1.0 ??2.0 ??- ??- | ??- ??- ??1.0 ??2.0 | ??0.1 ??0.04 ??2.3 ??3.5 | ??0.03 ??0.01 ??2.6 ??3.1 |
| Yeast saccharomyces cerevisiae | ??1.0 ??2.0 ??- ??- | ??- ??- ??1.0 ??2.0 | ??4.4 ??7.0 ??6.0 ??6.0 | ??3.5 ??2.7 ??6.0 ??6.0 |
From the result of table 7 as can be seen, the content that is used for the cats product of the present composition is enough to produce antibacterial effect.Also can find out, even Zephiran chloride also has improved antibacterial effect to common ticklish false green pus Zymomonas mobilis.
In order to provide the effect that sequestrant improves bacterium lethality, prepare the preparation that comprises Dobanol 91-8 (7% weight) and polymkeric substance (VERSICOL E11 polyacrylic acid, 0.5% weight), then the pH value is adjusted to 11.In the presence of WSH (water of standard hardness) and 0.03% dirt (bovine albumin), with final suspension preparation dilution 1/20.Given example is the preparation of the Zephiran chloride (BAC) that comprises 1.0 and 2.0% weight respectively.According to shown in the table 8, use EDTA or MGDA sequestrant.Bacteria tested is false green pus Zymomonas mobilis ATCC 15442, analyzes as mentioned above.The logarithmic series drop-out value provides with boldface letter above 5 example.
Table 8
| BAC％ | ??EDTA％ | ??MGDA％ | The logarithmic series drop-out value |
| ??1 | ???0.5 | ???0 | ???1.22 |
| ??1 | ???1 | ???0 | ???1.1 |
| ??1 | ???1.5 | ???0 | ???5.54 |
| ??1 | ???2 | ???0 | ???5.66 |
| ??1 | ???2.5 | ???0 | ???5.66 |
| ??2 | ???0.5 | ???0 | ???1.86 |
| ??2 | ???1 | ???0 | ???2.17 |
| ??2 | ???1.5 | ???0 | ???5.66 |
| ??2 | ???2 | ???0 | ???5.3 |
| ??2 | ???2.5 | ???0 | ???5.66 |
| ??1 | ???0 | ???0.5 | ???0.89 |
| ??1 | ???0 | ???1 | ???1.23 |
| ??1 | ???0 | ???1.5 | ???1.44 |
| ??1 | ???0 | ???2 | ???4.57 |
| ??1 | ???0 | ???2.5 | ???5.42 |
| ??2 | ???0 | ???0.5 | ???1.7 |
| ??2 | ???0 | ???1 | ???2.95 |
| ??2 | ???0 | ???1.5 | ???3.46 |
| ??2 | ???0 | ???2 | ???5.48 |
| ??2 | ???0 | ???2.5 | ???5.74 |
The result of table 8 shows, by using the sequestrant of appropriate amount, the survival number can be reduced by 5 logarithmic seriess.
Use the long lasting hygienic advantages that the present composition brought in order to illustrate, prepare the preparation that comprises Dobanol 91-8 (7% weight), wherein be with or without polymkeric substance (VERSICOLE11 polyacrylic acid, 0.5% weight), then the pH value be adjusted to 11.In the presence of WSH (water of standard hardness) and 0.03% dirt (bovine albumin), with final suspension preparation dilution 1/20.Given example is the preparation of the Zephiran chloride (BAC) that comprises 1.5 and 2.0% weight respectively.According to shown in the table 9, use EDTA or MGDA sequestrant.
By following method, measure effectiveness to staphylococcus aerogenes NCTC 6538.
Deceive glazing Cristal (TM) watt (from H﹠amp with no decorative pattern; R Johnson), is cut into glazing ceramic tile square block (being of a size of 2.5 * 2.5 centimetres), removes all hypotenuses.Before using test soln or product, fully clean these watts, can on water-wetted surface, evenly coat like this.Cleaning is to carry out in that day of products applied, is no more than then in time of 24 hours to carry out rinsing before carrying out antibacterial test.These watts are to clean like this, that is, the calcite powder is administered to watt, use the clean violent wiping of moist sponge cloth then.With these watts of rinsed with deionized water, flow through on it with less water then, determine whether total hydrophilic of this watt.Water should flow through watt gently, forms uniform films then on whole surface.Be still hydrophobicly if leave any zone, then use calcite and repeated washing again.After the cleaning, with clean paper handkerchief (Kimsoft (TM) medicated napkin) wiping drying.
50 μ l cleaning products (no matter being according to prescription of the present invention, comparison or Comparative Examples) are placed on clean watt, use flat droplet tip that it carefully is diffused on the whole watt of surface then.Will be dry watt in 30 ℃ of brooders, carry out rinsing then, be about to each watt and be placed among 100 milliliters of aseptic WSH 30 seconds, take out, be placed in 30 ℃ of brooders dry then.
After handling with product of the present invention, Comparative Examples product or blank thing, will watt be stored in the microbiology safety box and pollute to reduce.
For significant antibacterial effect is described, use the blank preparation of 50 μ l sterile distilled waters as blank test, each product is tested in duplicate.0 o'clock time, use 20 μ l cultures, will watt inoculate (as mentioned above) according to what the present invention handled with blank test, in 0.03% bovine albumin dirt, have about 2 * 10 like this
7Bacterium/watt.Use aseptic dispenser that bacterium is diffused on the whole watt of surface.Bacterium with watt contact 30 minutes after, with quenching solution that aseptic microbiology cotton swab is wetting, fully clean this watt along orthogonal both direction.After the end, the end of this cotton swab fractureed to be put in 10 milliliters of quenching solutions, repeats this step to remove remaining liquid and bacterium with dry cotton swab then.The bottle that will quench is placed the cell of being injured (60 minutes, for E.Coli) is recovered.After recovery, each bottle that quenches is rotated 15 seconds at a high speed down so that cell is resuspended in the quenching solution equably.
For each to be measured watt, use 270 μ l peptone waters to inoculate delegation's well in the aseptic titer plate, vacate first well in each case.Sign solution with 300 μ l quenching and charge into first well.The label solution that in addition 500 μ l quenched is placed directly on the agar plate, uses aseptic dispenser diffusion then.This plate is used to count low survival number.Prepare 10 times of diluents of series of solution, be about to 30 μ l solution and transfer to 1-2 row; Mix, repeat this step then till the 6th row, can obtain the diluent (the titration tip is changed) of 10-6 like this between transfer process.
For each watt sample of being got, (drying plate faces down, and removes lid, is placed on before use in 60 ℃ of stoves 15 minutes to agar plate with the liquid dropping of 10 μ l volumes, and being divided into 6 moieties at its bottom mark with marker pen) suitable part forms stain, 3 stains of each part.All plates are faced up carry out drying, placed face down is in 37 ℃ of brooders 24 hours then.Obtain the counting of these plates, from state log10 counting [blank sample], deduct log10 counting [test sample] then, obtain the log10 drop-out value.
The result of this test provides in following table 9: all compositions all comprise dirt and above-mentioned nonionogenic tenside, and other component that defecates in the cleaning composition provides in table.As mentioned above, the blank thing with respect to handling with sterilized water but not " cleaning combination " calculates the logarithmic series drop-out value.
Table 9
| Embodiment | BAAC％ | Polymkeric substance % | EDTA％ | MGDA％ | The logarithmic series drop-out value, rinsing | Logarithmic series drop-out value, not rinsing |
| 9a | 1.5 | 0.5 | - | 2.5 | 1.41 | 3.49 |
| 9b | 1.5 | - | - | 2.5 | 1.01 | 4.02 |
| 9c | 1.5 | 0.5 | 1.5 | - | 1.80 | 3.87 |
| 9d | 1.5 | - | 1.5 | - | 0.35 | 4.02 |
| 9e | 2.0 | 0.5 | - | 2.5 | 2.18 | 4.02 |
| 9f | 2.0 | - | - | 2.5 | 0.38 | 4.02 |
| 9g | 2.0 | 0.5 | 1.5 | - | 2.67 | 4.02 |
| 9h | 2.0 | - | 1.5 | - | 0.01 | 2.48 |
From the result of table 9 as can be seen, if not rinsing surface, the bacteria living rate that reclaims from the surface of handling with the present composition in advance obviously descend (a decline 2-4 logarithmic series).Exsiccant contains antimicrobial on this surface as long as the surface has been exposed to subsequently, the decline of this survival rate just can occur.
For rinsing watt, have only with what the preparation that contains polymkeric substance (9a, 9c, 9e and 9g) was handled just obviously to be better than 1 logarithmic series (decline 90%) the bacterium recovery situation under.Use the preparation of BAAC, polymkeric substance and the sequestrant (9e and 9g) of 2% weight to have best effect in an embodiment, on the survival number, descend 99%.It is believed that these results show, the present composition does not have the Comparative composition of polymkeric substance to have persistent antibacterial effect relatively.
Embodiment 10: fungi brood cell adhesivity
Recommending under the extent of dilution (1: 20,30 minutes, room temperature), with 20 milliliters of test products processing plastics Petri dishs (9 cm diameters, 2 centimetres dark), inclining then solution and with the plate drying.Blank plate then is untreated.Before dilution, embodiment preparation (10a) comprises Dobanol 91-8 (7% weight) and polymkeric substance (VERSICOL E11 polyacrylic acid, 0.5% weight), cats product (2% weight BAAC) and sequestrant (2.5% weight MGDA), with sodium hydroxide the pH value is adjusted to 11 then.The comparative example also can carry out at Lysoform (TM) (a kind of commercially available sterilant product).
The aspergillus niger brood cell's that will in sterile distilled water, make (ATCC 6275) suspension add entering plate (20 milliliters/plate, 3 * 10
5Brood cell/milliliter) in.In the orbital oscillation device, stir this plate, make brood cell's uniform distribution (1 minute, 100rpm), room temperature was placed 30 minutes then, stir again (1 minute, 100rpm).Abandon supernatant liquid, and with the plate drying.These plates carry out drying after pre-treatment He before being exposed to the brood cell, so the brood cell is not exposed to the pretreatment compositions of high level.Brood cell and initial cohesiveness treated and that be untreated between the plate can be measured by following given method.
In order to show rinsing effect, will as above handle the duplicate culture dish of (comprise and be exposed to mould brood cell) and carry out rinsing, be about to standard hard water (10 milliliters) and add in each culture dish, mix then (1 minute, 100rpm).Abandon supernatant liquid, then that plate is at room temperature dry.
For wiping effect is described, use all rotatable wiping arrangements, the duplicate culture dish of inoculating with the brood cell is as mentioned above carried out wiping.The prewashing sponge cloth of use standard (getting wet with standard hard water) is with 80 gram/cm
2Fixation pressure come wipe surfaces (10 circle, speed 4).Then that culture dish is at room temperature dry as mentioned above.
Under light microscope (* 40 magnification), observe each above-mentioned culture dish, each from 5 predetermined visuals field determined the mean number that adheres to the brood cell then.Again count the plate in rinsing and the wipe test, and record brood cell number.Adhesion percentage ratio after each the processing uses following equation to calculate:
Brood cell's mean number * 100 of counting
Brood cell's mean number of the blank example that is untreated
The result provides in following table 10, with the adhesion brood cell percentage ratio contrast of untreatment surface.
Table 10
| Initial adhesion | Adhesion after the rinsing | Adhesion after the wiping | |
| 10a | 45.05 | 32.67 | 5.41 |
| Lysoform(TM) | 64.26 | 53.07 | 14.74 |
| Contrast | 100.00 | 77.53 | 38.83 |
These results as expection show and can remove some mould brood cell to untreatment surface rinsing and wiping, but stay almost 40% brood cell from the teeth outwards, even after wiping.These results show, the brood cell is difficult for adhering on the surface of handling with the present composition, even and adhere to, these brood cells are not bonded on the surface securely yet.
The statistical results show of these data is compared with reference product Lysoform (RTM), and is compared with untreatment surface, is containing in the presence of the preparation of polymkeric substance, adheres to lip-deep brood cell's percentage ratio obviously descend (at least 95%).As mentioned above, this species diversity all can be found out in each stage for the treatment of processes.
It is believed that these results show, the present composition to small part prevents that the brood cell from adhering on the surface, therefore it is believed that the application of the invention composition, can reduce the regrowth speed of microorganism (comprising the mould or bacterium by brood cell's breeding) on the clean surface.
Claims (10)
1. hard-surface cleaning composition that the pH value is 3-12 wherein comprises:
A) nonionogenic tenside of 1-30% weight,
B) molecular-weight average of 0.005-5% weight is lower than 1000000 water-soluble anionic polymer, and described polymkeric substance does not have the quaternary nitrogen group, wherein the ratio of polymkeric substance and nonionogenic tenside be 0.1: 1 or lower and
C) cats product of 0.005-5% weight.
2. according to the composition of claim 1, wherein said polymkeric substance is that the polymkeric substance of acrylic or methacrylic acid or maleic anhydride or in them one or more form multipolymer together or with other monomer.
3. according to the composition of claim 2, wherein said polymkeric substance is selected from the no matter the sort of multipolymer that forms with ethene, vinylbenzene and methylvinylether of polyacrylic acid, polymaleic anhydride and aforementioned substances.
4. according to the composition of claim 1, wherein said cats product has general formula R
1R
2R
3R
4N
+X
-, wherein all groups all are the alkyl that is with or without hydroxyl substituent, and at least one among the R1-R4 is C6-C22 alkyl, alkaryl or hydroxyalkyl, and at least one among the R1-R4 is C1-C4 alkyl or hydroxyalkyl, and X is the monovalence counter anion.
5. according to the composition of claim 4, wherein R1 and R2 are identical or different C1-C4 alkyl or hydroxyalkyl, and R3 is C6-C22 alkyl, alkaryl or hydroxyalkyl, and R4 is C1-C22 alkyl, alkaryl or hydroxyalkyl, and X is the monovalence counter anion.
6. according to the composition of claim 5, wherein R1 and R2 are methyl, and R3 is that C8-C18 alkyl and R4 are methyl, C8-C18 alkyl or benzyl.
7. according to the composition of claim 1, it also comprises the metal ion wedding agent.
8. hard-surface cleaning composition that the pH value is 7-11 wherein comprises:
A) the ethoxylation 2-15E0 C8-C18 of 5-20% weight alcohol nonionogenic tenside,
B) be lower than the anion surfactant of 1% weight,
C) molecular-weight average of 0.2-2% weight is lower than 1000000 water-soluble anionic polymer, described polymkeric substance be vinylformic acid, methacrylic acid or maleic anhydride are at least a and vinylformic acid, methacrylic acid, maleic anhydride, ethene, vinylbenzene and methylvinylether are at least a polymkeric substance and
D) cats product of 0.05-2% weight, it is a kind of general formula R that has
1R
2R
3R
4N
+X
-The quaternary nitrogen compound, wherein R1 and R2 are identical or different C1-C4 alkyl or hydroxyalkyl, R3 is C6-C22 alkyl, alkaryl or hydroxyalkyl, R4 is C1-C22 alkyl, alkaryl or hydroxyalkyl, and X be the monovalence counter anion and
E) be no more than 2% the solvent that is selected from diglycol monotertiary n-butyl ether, monoethylene glycol mono-n-butyl ether, propylene glycol n-butyl ether and composition thereof.
9. method of cleaning crust is comprising the step with the cleaning combination treat surface of any one among the claim 1-8.
10. a molecular-weight average is lower than 1000000 the application of water-soluble anionic polymer in the hard-surface cleaning composition that comprises nonionogenic tenside and antiseptic cationic tensio-active agent, it can prolong the antibacterial efficacy of antiseptic cationic tensio-active agent on described crust, and described polymkeric substance does not have the quaternary nitrogen group.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| GB9704989.4 | 1997-03-11 | ||
| GBGB9704989.4A GB9704989D0 (en) | 1997-03-11 | 1997-03-11 | Improvements relating to hard-surface cleaning compositions |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN1250470A true CN1250470A (en) | 2000-04-12 |
Family
ID=10809027
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN98803209A Pending CN1250470A (en) | 1997-03-11 | 1998-02-24 | Hard-surface cleaning compositions |
Country Status (18)
| Country | Link |
|---|---|
| EP (1) | EP0971997B1 (en) |
| JP (1) | JP2001514693A (en) |
| KR (1) | KR20000076119A (en) |
| CN (1) | CN1250470A (en) |
| AU (1) | AU734919B2 (en) |
| BR (1) | BR9808003A (en) |
| CA (1) | CA2280877A1 (en) |
| DE (1) | DE69816603T2 (en) |
| ES (1) | ES2202825T3 (en) |
| GB (1) | GB9704989D0 (en) |
| HU (1) | HUP0001503A3 (en) |
| ID (1) | ID22433A (en) |
| IN (1) | IN190010B (en) |
| MY (1) | MY120141A (en) |
| PL (1) | PL187303B1 (en) |
| TR (1) | TR199902201T2 (en) |
| WO (1) | WO1998040452A1 (en) |
| ZA (1) | ZA981574B (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102703247A (en) * | 2012-06-01 | 2012-10-03 | 句容市恒祥金属再生利用有限公司 | Dephosphorized cleaning agent for cleaning grinding wheel dust |
| CN103890160A (en) * | 2011-11-03 | 2014-06-25 | 荷兰联合利华有限公司 | A liquid hard surface antimicrobial cleaning composition |
| CN103946356A (en) * | 2011-11-03 | 2014-07-23 | 荷兰联合利华有限公司 | A liquid hard surface antimicrobial cleaning composition |
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|---|---|---|---|---|
| US6080387A (en) * | 1998-07-15 | 2000-06-27 | The Clorox Company | Aerosol antimicrobial compositions |
| AU1557200A (en) * | 1998-12-10 | 2000-06-26 | Unilever Plc | Detergent compositions |
| DE19910788A1 (en) * | 1999-03-11 | 2000-09-14 | Cognis Deutschland Gmbh | Gel-shaped detergent for flush toilets |
| WO2001081519A1 (en) * | 2000-04-20 | 2001-11-01 | Colgate-Palmolive Company | Toilet bowl cleaning compositions |
| JP2002121593A (en) * | 2000-09-26 | 2002-04-26 | Spartan Chemical Co Inc | Sterilizing water-based composition for washing rigid surface and using method thereof |
| GB0023898D0 (en) * | 2000-09-29 | 2000-11-15 | Reckitt Benckiser Inc | Improvements in or relating to organic compositions |
| KR20040039615A (en) * | 2002-11-04 | 2004-05-12 | 애경산업(주) | Liquid cleasing composition having improved capacity for forming foam and low temperature stability |
| KR20040051869A (en) * | 2002-12-13 | 2004-06-19 | 주식회사 엘지생활건강 | Composition of Liquid Cleaner having Excellent Viscosity and Detergency |
| US7442679B2 (en) | 2004-04-15 | 2008-10-28 | Ecolab Inc. | Binding agent for solidification matrix comprising MGDA |
| KR20050119490A (en) * | 2004-06-16 | 2005-12-21 | 애경산업(주) | Liquid detergent composition in the form of o/w microemulsion containing fabric softening agent |
| JP5281420B2 (en) * | 2009-01-20 | 2013-09-04 | 花王株式会社 | Liquid detergent composition for hard surfaces |
| WO2011142424A1 (en) * | 2010-05-14 | 2011-11-17 | ユケン工業株式会社 | Aqueous cleaning agent composition |
| JP5536563B2 (en) * | 2010-06-28 | 2014-07-02 | 株式会社Ａｄｅｋａ | Cleaning composition for dishwasher and cleaning method using the composition |
| FR2980955B1 (en) * | 2011-10-05 | 2014-12-12 | Anios Lab Sarl | DISINFECTANT AND DETERGENT COMPOSITIONS. |
| FR2990364B1 (en) * | 2012-05-11 | 2014-06-13 | Commissariat Energie Atomique | METHOD FOR RADIOACTIVE DECONTAMINATION OF EARTH BY DISPERSE AIR FLOTATION FOAM AND FOAM |
| WO2014040869A1 (en) * | 2012-09-12 | 2014-03-20 | Unilever N.V. | Hard surface treatment composition |
| RU2678838C2 (en) | 2013-07-03 | 2019-02-04 | Басф Се | Use of gel-like polymer composition obtained by polymerization of acid group containing monomer in presence of polyester compound in formulations for automatic dishwashing |
| WO2016196020A1 (en) * | 2015-05-29 | 2016-12-08 | 3M Innovative Properties Company | Enzyme cleaner for textiles with styrene maleic anhydride copolymers |
| CN107735072B (en) | 2015-07-01 | 2023-09-15 | 3M创新有限公司 | Composition for removing spores |
| CN106701351A (en) * | 2015-11-12 | 2017-05-24 | 艺康美国股份有限公司 | Low-foaming vessel cleaning agent and mixed cationic/nonionic surfactant system for enhancing removal of oil-containing dirt |
| US11634666B2 (en) | 2015-12-22 | 2023-04-25 | 3M Innovative Properties Company | Methods for spore removal comprising a polysorbate surfactant and cationic antimicrobial mixture |
| WO2018128965A1 (en) | 2017-01-04 | 2018-07-12 | 3M Innovative Properties Company | Methods of removing spores |
| MX2020002635A (en) | 2017-09-06 | 2020-07-13 | Basf Se | Washing- and cleaning-active polymer films, process for their production and their use. |
| JP7170300B2 (en) * | 2017-12-11 | 2022-11-14 | 株式会社ニイタカ | liquid detergent composition |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| LU84753A1 (en) * | 1983-04-15 | 1984-11-28 | Oreal | CLEANSING AND FOAMING COMPOSITION BASED ON NON-IONIC SURFACTANTS AND ANIONIC POLYMERS |
| PH25826A (en) * | 1986-03-14 | 1991-11-05 | Johnson & Son Inc S C | Prespotter laundry detergent |
| JPH01250473A (en) * | 1988-03-31 | 1989-10-05 | Lion Corp | Liquid softening agent composition |
| WO1989012673A1 (en) * | 1988-06-21 | 1989-12-28 | Vax Appliances Limited | Fabric cleaning and sanitizing compositions |
| GB9310365D0 (en) * | 1993-05-18 | 1993-06-30 | Unilever Plc | Hard surface cleaning compositions comprising polymers |
| CZ174497A3 (en) * | 1994-12-09 | 1998-06-17 | Unilever N. V. | Cleansing agent |
-
1997
- 1997-03-11 GB GBGB9704989.4A patent/GB9704989D0/en active Pending
-
1998
- 1998-02-24 PL PL98335609A patent/PL187303B1/en not_active IP Right Cessation
- 1998-02-24 JP JP53918698A patent/JP2001514693A/en not_active Ceased
- 1998-02-24 CA CA002280877A patent/CA2280877A1/en not_active Abandoned
- 1998-02-24 ES ES98912446T patent/ES2202825T3/en not_active Expired - Lifetime
- 1998-02-24 CN CN98803209A patent/CN1250470A/en active Pending
- 1998-02-24 KR KR1019997008208A patent/KR20000076119A/en not_active Application Discontinuation
- 1998-02-24 WO PCT/EP1998/001273 patent/WO1998040452A1/en active IP Right Grant
- 1998-02-24 DE DE69816603T patent/DE69816603T2/en not_active Expired - Fee Related
- 1998-02-24 BR BR9808003-2A patent/BR9808003A/en not_active Application Discontinuation
- 1998-02-24 EP EP98912446A patent/EP0971997B1/en not_active Expired - Lifetime
- 1998-02-24 TR TR1999/02201T patent/TR199902201T2/en unknown
- 1998-02-24 AU AU67280/98A patent/AU734919B2/en not_active Ceased
- 1998-02-24 HU HU0001503A patent/HUP0001503A3/en unknown
- 1998-02-24 ID IDW991001A patent/ID22433A/en unknown
- 1998-02-25 ZA ZA9801574A patent/ZA981574B/en unknown
- 1998-02-26 IN IN101BO1998 patent/IN190010B/en unknown
- 1998-03-09 MY MYPI98001010A patent/MY120141A/en unknown
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103890160A (en) * | 2011-11-03 | 2014-06-25 | 荷兰联合利华有限公司 | A liquid hard surface antimicrobial cleaning composition |
| CN103946356A (en) * | 2011-11-03 | 2014-07-23 | 荷兰联合利华有限公司 | A liquid hard surface antimicrobial cleaning composition |
| CN103946356B (en) * | 2011-11-03 | 2017-02-15 | 荷兰联合利华有限公司 | A liquid hard surface antimicrobial cleaning composition |
| CN102703247A (en) * | 2012-06-01 | 2012-10-03 | 句容市恒祥金属再生利用有限公司 | Dephosphorized cleaning agent for cleaning grinding wheel dust |
| CN102703247B (en) * | 2012-06-01 | 2014-06-18 | 句容市恒祥金属再生利用有限公司 | Dephosphorized cleaning agent for cleaning grinding wheel dust |
Also Published As
| Publication number | Publication date |
|---|---|
| PL187303B1 (en) | 2004-06-30 |
| DE69816603T2 (en) | 2004-06-09 |
| EP0971997B1 (en) | 2003-07-23 |
| PL335609A1 (en) | 2000-05-08 |
| EP0971997A1 (en) | 2000-01-19 |
| JP2001514693A (en) | 2001-09-11 |
| HUP0001503A3 (en) | 2003-02-28 |
| BR9808003A (en) | 2000-03-08 |
| ID22433A (en) | 1999-10-14 |
| MY120141A (en) | 2005-09-30 |
| ZA981574B (en) | 1999-08-25 |
| DE69816603D1 (en) | 2003-08-28 |
| ES2202825T3 (en) | 2004-04-01 |
| TR199902201T2 (en) | 2000-05-22 |
| WO1998040452A1 (en) | 1998-09-17 |
| IN190010B (en) | 2003-05-31 |
| CA2280877A1 (en) | 1998-09-17 |
| AU734919B2 (en) | 2001-06-28 |
| AU6728098A (en) | 1998-09-29 |
| GB9704989D0 (en) | 1997-04-30 |
| HUP0001503A2 (en) | 2000-09-28 |
| KR20000076119A (en) | 2000-12-26 |
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