WO1994013769A1 - Composition nettoyantes acides auto-epaissies - Google Patents
Composition nettoyantes acides auto-epaissies Download PDFInfo
- Publication number
- WO1994013769A1 WO1994013769A1 PCT/US1993/011680 US9311680W WO9413769A1 WO 1994013769 A1 WO1994013769 A1 WO 1994013769A1 US 9311680 W US9311680 W US 9311680W WO 9413769 A1 WO9413769 A1 WO 9413769A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- compositions
- acid
- composition according
- composition
- self
- Prior art date
Links
- 239000000203 mixture Substances 0.000 title claims abstract description 67
- 230000002378 acidificating effect Effects 0.000 title abstract description 9
- 238000004140 cleaning Methods 0.000 title abstract description 6
- 239000002736 nonionic surfactant Substances 0.000 claims abstract description 12
- 230000008719 thickening Effects 0.000 claims abstract description 12
- 239000003093 cationic surfactant Substances 0.000 claims abstract description 11
- 239000002253 acid Substances 0.000 claims description 14
- 125000001183 hydrocarbyl group Chemical group 0.000 claims description 8
- 150000007524 organic acids Chemical class 0.000 claims description 5
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims description 4
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 claims description 4
- 239000011976 maleic acid Substances 0.000 claims description 4
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 claims description 4
- 238000007046 ethoxylation reaction Methods 0.000 claims description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical group [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 2
- 125000004432 carbon atom Chemical group C* 0.000 claims description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 2
- 125000003158 alcohol group Chemical group 0.000 claims 1
- 150000001649 bromium compounds Chemical group 0.000 claims 1
- 150000001875 compounds Chemical class 0.000 description 8
- 239000002562 thickening agent Substances 0.000 description 7
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 description 5
- 239000004615 ingredient Substances 0.000 description 5
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 5
- 230000008901 benefit Effects 0.000 description 4
- 239000004094 surface-active agent Substances 0.000 description 3
- AISMNBXOJRHCIA-UHFFFAOYSA-N trimethylazanium;bromide Chemical compound Br.CN(C)C AISMNBXOJRHCIA-UHFFFAOYSA-N 0.000 description 3
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 2
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical group C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical group CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 2
- 239000003929 acidic solution Substances 0.000 description 2
- 150000007513 acids Chemical class 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- 239000003945 anionic surfactant Substances 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 125000002091 cationic group Chemical group 0.000 description 2
- 229960002798 cetrimide Drugs 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 2
- 230000002209 hydrophobic effect Effects 0.000 description 2
- 150000007522 mineralic acids Chemical class 0.000 description 2
- 235000005985 organic acids Nutrition 0.000 description 2
- 239000012321 sodium triacetoxyborohydride Substances 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 125000003368 amide group Chemical group 0.000 description 1
- 230000000844 anti-bacterial effect Effects 0.000 description 1
- 239000003899 bactericide agent Substances 0.000 description 1
- -1 bleaches Substances 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000003599 detergent Substances 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical group 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 239000002304 perfume Substances 0.000 description 1
- 238000005191 phase separation Methods 0.000 description 1
- 239000002689 soil Substances 0.000 description 1
- 239000002904 solvent 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
- C11D3/16—Organic compounds
- C11D3/20—Organic compounds containing oxygen
- C11D3/2075—Carboxylic acids-salts thereof
- C11D3/2082—Polycarboxylic acids-salts thereof
-
- 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
- C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
- C11D17/0008—Detergent materials or soaps characterised by their shape or physical properties aqueous liquid non soap compositions
- C11D17/003—Colloidal solutions, e.g. gels; Thixotropic solutions or pastes
-
- 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
Definitions
- the present invention relates to cleaning compositions for hard surfaces.
- the compositions of the present invention are designed for optimum performance in removing limescale and are thickened without the use of a thickener compound.
- compositions for cleaning hard surfaces including compositions for removing limescale, are well known in the art.
- Such compositions which are characterized mainly by a strong acidity, are disclosed for instance in EP 496 188.
- Limescale is mainly found in such places as sinks, toilet bowls and bathtubs, i.e. vertical surfaces. Therefore, it is desirable to give some viscosity to compositions for removing limescale so as to prevent said compositions from running down said vertical surfaces. Indeed thick compositions cling to vertical surfaces, thus they have more time to act on vertical surfaces before they run down said surfaces. It is however undesirable to use thickener compounds in such compositions for various reasons. For instance, thickener compounds may significantly raise formula costs. Also, thickeners may create issues relating to processing and product stability, especially in extreme acidic conditions. Furthermore, thickeners may affect the limescale removing performance of the composition. Finally, thickeners do not contribute to the cleaning performance of the composition.
- compositions according to the present invention have the advantage that the use of the quaternary ammonium salts cationic surfactants described hereinafter in combination with an acid provides significant disinfectancy benefits. This advantage is particularly useful in a composition which is meant to be used primarily on bathroom and kitchen surfaces.
- GB 2 071 688 teaches that quaternary ammonium salts can be used to thicken an acidic solution, provided they are combined with an amine or amine oxide.
- nonionic surfactants are presented as an alternative to the quaternary ammonium salts.
- EP 188 205 teaches that quaternary ammonium salts can be used to thicken an acidic solution, provided they are combined with a strong mineral acid.
- compositions according to the present invention are aqueous compositions comprising an acid whereby the pH as is of said compositions is of from 0.1 to 4.5, said compositions further comprising a thickening system whereby said compositions are stable and have a viscosity of from
- said thickening system comprises from 0.5% to 15% by weight of the total composition of a mixture of a nonionic surfactant with a cationic surfactant according to the formula R 1 R 2 R 3 R 4 N + X-, wherein X is a counteranion, R 1 is a C 12-20 hydrocarbon chain and R 2 , R 3 and R 4 are independently selected from H or C 1-4 hydrocarbon chains.
- compositions of the present invention are designed for removing limescale or soils comprising limescale as a main component.
- they comprise, as a first essential ingredient, an organic or inorganic acid, or mixtures thereof.
- Appropriate acids for use herein are disclosed for instance in EP 411 708, EP 496 188, GB 2 106 927, EP 200 776, and EP 336 878.
- acids are suitable for use herein from a pure performance viewpoint, it is preferred to avoid the use of strong inorganic acids such as phosphoric acid or HCl, for environmental reasons and for surface safety.
- Preferred for use herein are organic acids or mixtures thereof.
- compositions according to the present invention comprise from 0.1% to 45% by weight of the total composition of an acid or mixtures thereof, preferably from 4% to 25%.
- the compositions according to the present have a pH as is of from 0.1 to 4.5, preferably 0.5 to 2.0, most preferably about 1.0.
- compositions according to the present invention comprise a thickening system which consists of a mixture of certain cationic surfactants with nonionic surfactants.
- compositions according to the present invention are free of a thickener compound, i.e. a compound which has the sole purpose of thickening the composition.
- the suitable cationic surfactants for use herein are according to the formula R 1 R 2 R 3 R 4 N + X-, wherein X is a counteranion, R 1 is a C 12-20 hydrocarbon chain and R 2 , R 3 and R 4 are independently selected from H or C 1-4 hydrocarbon chains.
- R 1 is a C 14-18 hydrocarbon chain, most preferably C 16 or C 18
- R 1 , R 2 and R 3 are all three methyl
- X is halogen, preferably bromide or chloride, most preferably bromide. It is also possible to use mixtures of such cationic surfactants without departing from the spirit of the present invention.
- Suitable nonionic surfactants for use herein include compounds having the general formula RA(CH 2 CH 2 CH 2 O) m (CH 2 CH 2 O) n H, wherein R represents a hydrophobic moiety, A represents a group carrying a reactive hydrogen atom, m represents the average number of propylene oxide moieties and n represents the average number of ethylene oxide moieties. These compounds are typically obtained by condensing ethylene oxide and/or propylene oxide with a hydrocarbon having a reactive hydrogen, e.g. a hydroxyl, carboxyl, or amido group, in the presence of an acidic or basic catalyst.
- the hydrophobic moiety of the nonionic compound can be a primary or secondary, straight or branched alcohol having from about 8 to about 24 carbon atoms, preferably 12 to 18, m is 0 and n varies from 1 to 15.
- suitable surfactants for use herein are commercially available, for instance from Shell under the trade name Dobanol @ , or from BASF under the trade name Lutensol @ . It is of course possible to use mixtures of different nonionic surfactants without departing from the spirit of the present invention.
- compositions according to the present invention comprise from 0.5% to 15% by weight of the total composition of said thickening system, preferably from 1% to 8%.
- the compositions according to the present invention consequently have a viscosity in the range of from 10 cps to 700 cps at 60 RPM at 20°c, preferably from 20 cps to 200 cps, most preferably 30 cps to 60 cps.
- the selection of the most appropriate thickening system depends on such factors as the target viscosity, the acid concentration and the limescale removal performance target. In mere terms of viscosity, it has been found that using straight alkyl chains in both the cationic and the nonionnc surfactants provides the best viscosity build up.
- the combination of the cationic surfactant with the nonionic surfactant allows to build viscosity in an aqueous solution of an acid, even a weak organic acid, whereby this system is stable and the limescale removal performance of said viscosified solution is substantially preserved.
- An appropriate way to proceed in determining a suitable thickening system for a given composition is to start by defining the desired limescale removing performance for said composition, i.e. the type and concentration of acid, and to prepare a corresponding aqueous solution of said acid. Then various combinations of cationic and nonionic surfactants can be tried in order to obtain the target viscosity as a stable composition.
- stable it is meant herein that the composition undergoes no phase separation during a substantial period of time in a temperature range of from 0°c to 50°c. The most appropriate system can thus be selected by trial and error.
- compositions according to the present invention may further comprise such optional ingredients as solvents, bleaches, bactericides, perfumes, dyes and the like, provided they are compatible in the acidic medium of the compositions according to the present invention.
- compositions according to the present invention are further illustrated by the following examples. Examples
- compositions are prepared by mixing the listed ingredients in the listed proportions.
- Viscosity (cps at 60rpm) 30 54 200 41
- CTAB stands for a C16 trimethyl ammonium bromide
- Cetrimide stands for C14 trimethyl ammonium bromide
- STAB stands for C18 trimethyl ammonium bromide
- Dobanol @ 23-3 is a C12-C13 ethoxylated alcohol with an average degree of ethoxylation of 3, available from Shell
- Lutensol @ ON 30 is a C8-C12 ethoxylated alcohol with an average degree of ethoxylation of 3.
- compositions according to the examples above were stable during 10 days at 50°c.
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)
- Health & Medical Sciences (AREA)
- Emergency Medicine (AREA)
- Dispersion Chemistry (AREA)
- Detergent Compositions (AREA)
Abstract
L'invention concerne des compositions nettoyantes acides qui s'auto-épaississent. Le système d'épaississement comprend un mélange d'un tensioactif cationique et d'un tensioactif non ionique. Les compositions sont particulièrement appropriés pour éliminer le tartre.
Priority Applications (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US08/446,758 US5656580A (en) | 1992-12-04 | 1993-12-02 | Acidic cleaning compositions self-thickened by a mixture of cationic and nonionic surfactants |
CA002150914A CA2150914C (fr) | 1992-12-04 | 1993-12-02 | Composition nettoyante acide autoepaississante |
Applications Claiming Priority (4)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
EP92870195 | 1992-12-04 | ||
EP92870195.2 | 1992-12-04 | ||
EP93870120A EP0601990B1 (fr) | 1992-12-04 | 1993-06-25 | Composition acide de nettoyage auto-épaissie |
EP93870120.8 | 1993-06-25 |
Publications (1)
Publication Number | Publication Date |
---|---|
WO1994013769A1 true WO1994013769A1 (fr) | 1994-06-23 |
Family
ID=26132648
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/US1993/011680 WO1994013769A1 (fr) | 1992-12-04 | 1993-12-02 | Composition nettoyantes acides auto-epaissies |
Country Status (3)
Country | Link |
---|---|
CA (1) | CA2150914C (fr) |
MX (1) | MX9307695A (fr) |
WO (1) | WO1994013769A1 (fr) |
Cited By (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO1995021232A1 (fr) * | 1994-02-03 | 1995-08-10 | The Procter & Gamble Company | Compositions d'elimination des depots de calcaire |
WO1995021231A1 (fr) * | 1994-02-03 | 1995-08-10 | The Procter & Gamble Company | Preparations detergentes acides |
US5672578A (en) * | 1994-02-03 | 1997-09-30 | The Procter & Gamble Company | Limescale removing compositions |
EP0839898A1 (fr) | 1996-11-04 | 1998-05-06 | The Procter & Gamble Company | Compositions de nettoyage à épaississement propre |
WO1999016854A1 (fr) * | 1997-09-30 | 1999-04-08 | Reckitt Benckiser Inc. | Compositions acides epaissies pour le nettoyage et la desinfection |
WO2000063337A1 (fr) * | 1999-04-16 | 2000-10-26 | Reckitt Benckiser Inc. | Compositions nettoyantes et desinfectantes acides pour surfaces dures |
EP1894989A1 (fr) * | 2006-09-01 | 2008-03-05 | The Procter and Gamble Company | Composition pâteuse pour articles sanitaires |
Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4666622A (en) * | 1985-01-03 | 1987-05-19 | Lever Brothers Company | Stable thickened low pH liquid bleaching compositions containing inorganic peroxy compounds |
US4891150A (en) * | 1985-12-05 | 1990-01-02 | Joh. A. Benckiser Gmbh | Liquid sanitary cleansing and descaling agents and process for their production |
US5008030A (en) * | 1989-01-17 | 1991-04-16 | Colgate-Palmolive Co. | Acidic disinfectant all-purpose liquid cleaning composition |
US5100660A (en) * | 1989-04-21 | 1992-03-31 | Allied Colloids Limited | Thickened acidic aqueous compositions using cross-linked dialkylaminoacrylic microparticles |
EP0518401B1 (fr) * | 1991-06-14 | 1995-11-02 | The Procter & Gamble Company | Compositions de nettoyage à épaississement propre |
-
1993
- 1993-12-02 WO PCT/US1993/011680 patent/WO1994013769A1/fr active Application Filing
- 1993-12-02 CA CA002150914A patent/CA2150914C/fr not_active Expired - Fee Related
- 1993-12-06 MX MX9307695A patent/MX9307695A/es not_active IP Right Cessation
Patent Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4666622A (en) * | 1985-01-03 | 1987-05-19 | Lever Brothers Company | Stable thickened low pH liquid bleaching compositions containing inorganic peroxy compounds |
US4891150A (en) * | 1985-12-05 | 1990-01-02 | Joh. A. Benckiser Gmbh | Liquid sanitary cleansing and descaling agents and process for their production |
US5008030A (en) * | 1989-01-17 | 1991-04-16 | Colgate-Palmolive Co. | Acidic disinfectant all-purpose liquid cleaning composition |
US5100660A (en) * | 1989-04-21 | 1992-03-31 | Allied Colloids Limited | Thickened acidic aqueous compositions using cross-linked dialkylaminoacrylic microparticles |
EP0518401B1 (fr) * | 1991-06-14 | 1995-11-02 | The Procter & Gamble Company | Compositions de nettoyage à épaississement propre |
Cited By (10)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO1995021232A1 (fr) * | 1994-02-03 | 1995-08-10 | The Procter & Gamble Company | Compositions d'elimination des depots de calcaire |
WO1995021231A1 (fr) * | 1994-02-03 | 1995-08-10 | The Procter & Gamble Company | Preparations detergentes acides |
US5672578A (en) * | 1994-02-03 | 1997-09-30 | The Procter & Gamble Company | Limescale removing compositions |
AU701869B2 (en) * | 1994-02-03 | 1999-02-04 | Procter & Gamble Company, The | Limescale removing compositions |
EP0839898A1 (fr) | 1996-11-04 | 1998-05-06 | The Procter & Gamble Company | Compositions de nettoyage à épaississement propre |
WO1999016854A1 (fr) * | 1997-09-30 | 1999-04-08 | Reckitt Benckiser Inc. | Compositions acides epaissies pour le nettoyage et la desinfection |
US6239092B1 (en) | 1997-09-30 | 2001-05-29 | Reckitt Benckiser Inc. | Thickened acidic, hard surface cleaning and disinfecting compositions particularly useful for ceramic surfaces |
WO2000063337A1 (fr) * | 1999-04-16 | 2000-10-26 | Reckitt Benckiser Inc. | Compositions nettoyantes et desinfectantes acides pour surfaces dures |
EP1894989A1 (fr) * | 2006-09-01 | 2008-03-05 | The Procter and Gamble Company | Composition pâteuse pour articles sanitaires |
WO2008026192A1 (fr) * | 2006-09-01 | 2008-03-06 | The Procter & Gamble Company | Composition pâteuse destinée à des équipements sanitaires |
Also Published As
Publication number | Publication date |
---|---|
CA2150914A1 (fr) | 1994-06-23 |
MX9307695A (es) | 1994-06-30 |
CA2150914C (fr) | 1999-07-13 |
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