US3738943A - Biodegradable detergent for automatic car wash systems - Google Patents

Biodegradable detergent for automatic car wash systems Download PDF

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Publication number
US3738943A
US3738943A US00099522A US3738943DA US3738943A US 3738943 A US3738943 A US 3738943A US 00099522 A US00099522 A US 00099522A US 3738943D A US3738943D A US 3738943DA US 3738943 A US3738943 A US 3738943A
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weight
parts
detergent
mixture
alcohol
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US00099522A
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T Kaneko
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BASF Corp
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BASF Wyandotte Corp
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Assigned to BASF CORPORATION reassignment BASF CORPORATION MERGER (SEE DOCUMENT FOR DETAILS). Assignors: BADISCHE CORPORATION, BASF SYSTEMS CORPORATION, BASF WYANDOTTE CORPORATION, A MI CORP., GLASURIT AMERICA, INC., (MERGED INTO), INMONT CORPORATION, (CHANGED TO), LIMBACHER PAINT & COLOR WORKS, INC
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Classifications

    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/66Non-ionic compounds
    • C11D1/83Mixtures of non-ionic with anionic compounds
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/02Anionic compounds
    • C11D1/34Derivatives of acids of phosphorus
    • C11D1/345Phosphates or phosphites
    • FMECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F01MACHINES OR ENGINES IN GENERAL; ENGINE PLANTS IN GENERAL; STEAM ENGINES
    • F01DNON-POSITIVE DISPLACEMENT MACHINES OR ENGINES, e.g. STEAM TURBINES
    • F01D17/00Regulating or controlling by varying flow
    • F01D17/10Final actuators
    • F01D17/12Final actuators arranged in stator parts
    • F01D17/14Final actuators arranged in stator parts varying effective cross-sectional area of nozzles or guide conduits
    • F01D17/146Final actuators arranged in stator parts varying effective cross-sectional area of nozzles or guide conduits by throttling the volute inlet of radial machines or engines

Definitions

  • Biodegradable detergent for automatic car wash systems, and in particular tunnel-type car wash systems consists essentially of: (a) from about 5 to 12 parts by weight of a nonionic surfactant, (b) from about 2 to 7 parts by weight of an anionic surfactant which is the phosphate ester of nonionic (a), (c) from about 2 to 10 parts by weight of linear alkylbenzene sulfonate anionic surfactant, (d) from about 0 to 10 parts by weight of detergent builder, (e) from about 0 to 2.0 parts by weight of alkali, and (f) from about 91 to 59 parts by weight of water, based on 100 parts by weight of detergent.
  • This detergent is efficaciously deployed in very dilute concentrations in aqueous solutions of up to 1 part of detergent per 400 parts of water.
  • the present invention pertains to detergent compositions, and in particular to biodegradable detergent compositions specifically adapted for use in tunnel-type automatic car wash systems.
  • Tunnel-type vehicular or car wash systems generally comprise a conveyor section having disposed therealong suitable apparatus for performing specified stages of exterior vehicle washing and cleaning. For instance, at one stage there is provided scrubbing brushes which remove dirt from the entire exterior of the vehicle body; another stage washes the hubcaps of the wheels; another stage rinses the vehicle body; another stage air dries, through forced air compressors, the body of the vehicle.
  • This type of conveyor arrangement with the different stages for cleaning the exterior of the vehicle are well known and is not intended to be a part of the invention.
  • the success of the automatic tunnel-type system is directly related to the detergent employed in the scrubbing stage of the system.
  • the detergents generally employed for this purpose have certain inherent drawbacks, among which are: (1) the tendency to leave water spots or breaks on the vehicle body because of deficient sheeting action on the vehicle body; (2) the automotive body is left with a soil residue after cleaning because the wash water is generally recaptured in the reclaim pits and recirculated and reused a multitude of times thereby promoting soil redeposition on the vehicle body; (3) the detergent cannot be employed in very dilute solutions thereby discounting the economic advantages of the automatic vehicle or car wash system.
  • the present invention seeks to overcome these and other drawbacks in detergents for automatic car wash systems while providing other advantages which are elucidated below.
  • the present invention provides for an improved liquid, biodegradable, detergent concentrate composition particularly adapted for tunnel-type automatic car wash systems which consists essentially of a mixture of:
  • This biodegradable composition has been found to be effective in extremely dilute aqueous solutions of up to 1 part of detergent per 400 parts of water. Furthermore, this composition has been found to have the following attributes rendering it extremely efiicacious in its desired application: (1) storage stability at temperatures of up to about F.; (2) non-corrosive to vehicle body and body trim as well as being a non-etchant for the glass portions of the vehicle body; (3) inhibits soil redeposition; (4) obviates the problem of water spots; and (5) lubricates the conventional plastic bristles of the scrubbing brushes.
  • a biodegradable, liquid, detergent composition or detergent concentrate composition consisting essentially of a mixture of (a) a nonionic surfactant, '(b) a phosphate ester anionic surfactant, (c) a linear alkylbenzene sulfonate anionic surfactant, (d) a detergent builder, (e) an alkali, and (f) water.
  • this composition is closely related to that disclosed in the Wyandotte Chemicals Corporation publication entitled, Plurafac Nonionic Surfactants For Use in Biodegradable Formulations, 4th edition, 2nd printing, published in May 1969.
  • This publication discloses on page 14 a car wash formulation specifically designed for use in coin-operated systems containing a nonionic surfactant, a phosphate ester anionic surfactant, a detergent builder and water, and which is eflfective in aqueous solutions at concentrations ranging from 1:35 to 1:50 and which is storage stable up to a temperature of about 120 F.
  • the present compositions ditfer from those of the reference publication by the addition of the linear alkylbenzene sulfonate which enables the present composition to be used in tunnel-type systems. Moreover, it has unexpectedly been found that the addition of the linear alkylbenzene sulfonate provides (a) improved detergency, (b) increases the storage stability of the concentrate to a temperature of about 165 F., and enables the detergent to be effectively employed in dilute concentrations of up to about 1:400 in typical aqueous use solutions.
  • compositions generally consist essentially of (a) from about 5 to 12 parts by weight of the nonionic surfactant, (b) from about 2 to 7 parts by Weight of the phosphate ester anionic surfactant, (c) from about 2 to parts by weight of linear alkylbenzene sulfonate anionic surfactant, (d) from about 0 to 10 parts by weight of detergent builder, (e) from about 0 to 2.0 parts by weight of alkali, and (f) from about 91 to 59 parts by weight of water, based on 100 parts by weight of the compositions.
  • the present compositions consist essentially of (a) from about 9.0 to 11.0 parts of nonionic surfactant, (b) from about 3.0 to 6.0 parts of phosphate ester anionic surfactant, (0) from about 4.0 to 9.0 parts of linear alkylbenzene sulfonate, (d) from about 4.0 to 6.0 parts of detergent builder, (e) from about 0.5 to 1.0 part of alkali and from about 79.5 to 67.0 parts of water, based on 100 parts by weight of the composition.
  • the nonionic surfactant which may be used in the practice of the present invention is an alkylene oxide condensate of linear aliphatic alcohols, i.e. alkanols, having (from 8 to carbon atoms or mixtures thereof.
  • These surfactants are prepared by conventional oxyalkylene condensation reactions well known in the art. Generally, they are prepared by reacting an alkylene oxide with the linear aliphatic alcohol in the presence of a suitable oxyalkylation catalyst, such as sodium hydroxide, potassium hydroxide, and the like at a temperature of about 125 C. and at the pressure of about 34 to 90 p.s.i.g.
  • Preferred alkylene oxides for the condensation reaction herein are ethylene oxide, propylene oxide or mixtures thereof.
  • ethylene oxide and propylene oxide When both ethylene oxide and propylene oxide are utilized, they are generally used in a weight ratio of ethylene oxide to propylene oxide ranging from about 0.521 to 6: 1.
  • the total alkylene oxide content of the nonionic surfactant generated by the condensation reaction ranges (from about 40 to 85% 0f the total weight of the surfactant, and preferably from about 60 to 85 of the total weight of the surfactant.
  • the alcohols which are reacted with the alkylene oxides generally have from 8 to 20 carbon atoms, and preferably from 10 to 18 carbon atoms. They are essentially linear primary aliphatic alcohols and wherein at least seventy weight percent of the alcohol reactant should comprise an alcohol or mixture of alcohols having from 12 to 16 carbon atoms.
  • suitable alcohols include decyl alcohol, undecyl alcohol, dodecyl alcohol, tridecyl alcohol, tetradecyl alcohol, pentadecyl alcohol, cetyl alcohol, heptadecyl alcohol, stearyl alcohol, hydrogenated tallow alcohol, and mixtures thereof.
  • alcohols may be naturally derived, such as, from coconut oil, or they may be synthetically derived, such as, from linear alkanes or linear alkenes. Small amounts of branchchained alcohols may be used in conjunction with the linear alcohols so long as there is no interference with the biodegradability of the resulting product.
  • An example of the type of alcohol herein contemplated is commercially available from Shell Oil Company under the name Neodol 25 (a mixture of C C alcohols). It is advantageous herein to employ a mixture of alcohols to prepare the surfactants because of the good balance of properties imparted to the resulting products.
  • the preferred nonionic surfactant contemplated herein can be represented by the formula:
  • R is an alcoholic residue or alkyl group having from 10 to 18 carbon atoms or mixtures thereof
  • A is either oxyethylene groups or a mixture of oxyethylene and oxypropylene groups in an ethylene oxide to propylene oxide weight ratio of from 0.5 :1 to 6: 1
  • n is an integer sufficiently large to ensure that A constitutes from 40 to 85 of the total weight of the surfactant.
  • the phosphate ester anionic surfactant which is contemplated herein is the phosphate ester of the abovedefined nonionic surfactant. It is prepared by reacting the nonionic surfactant with polyphosphoric acid. Generally, the polyphosphoric acid is used in excess over stoichiometric requirements. The phosphate ester obtained by this reaction is, rather, a mixture of monoand diesters corresponding to the formulae:
  • R A and n have the meanings ascribed to R, A and n, above, and wherein the mixture comprises from to 100% by weight of monoester and from 40 to 0% by weight of diester and A constitutes from about 30 to of the total weight of the ester.
  • This anionic surfactant is an excellent solubilizing agent for the nonionic surfactant and thereby promotes the storage stability of the present composition.
  • Linear alkylbenzene sulfonate (LAS) anionic surfactants are widely known compounds in the detergent arts. They are generally prepared by the Friedel-Crafts reaction of an olefin and benzene or derivative thereof followed by the sulfonation of the intermediate 2-benzylalkylate.
  • the olefin or alkene employed in the preparation of these compounds generally has from 10 to 118 carbon atoms and usually is an a-olefin. They are commonly available in alkali metal salt form, such as, the potassium or sodium salt of the linear alkylbenzene sulfonate.
  • Suitable representative compounds of the type herein contemplated can be found in McCutcheons Detergents and Emulsifiers, 1970 edition.
  • the linear alkylbenzene sulfonate anionic surfactant of the present invention has been found to be critical hereto since it not only enables the use of the present composition in tunnel-type systems, but, also, increases the storage stability of the composition up to a temperature of about 165 'LF. Moreover, by incorporating the linear alkylbenzene sulfonate into the composition it is possible to provide an excellent detergent in extremely dilute aqueous solutions of up to 1 part of detergent concentration per 400 parts of water. This result was unexpected since conventional compositions have much greater concentrations of detergent therein. For instance, the nonionic surfactant employed herein is usually efiicacious only in solutions having concentrations of 1:50 and usually from about 1:35 to 1:50.
  • Linear alkylbenzene sulfonates can only be diluted to a minimum concentration in solution of 1:200.
  • the combination of the nonionic and linear alkylbenzene sulfonate can be diluted to a minimum of 1:400, thereby providing a very important economic benefit.
  • the linear alkylbenzene sulfonate is a lubricant for the plastic bristles of the brushes usually deployed in the scrubbing stage of the tunnel-type automatic car wash system.
  • a typical linear alkylbenzene sulfonate as contemplated herein is sold by Arco Chemical under the name Ultrawet which is a sodium salt of a linear alkylbenzene sulfonate.
  • the detergent builders are preferably sequestering agents which promote the solubility of the surfactants in water. These builders are well known and widely reported in the available patents and literature.
  • Typical compounds are the alkali metal compounds, such as, alkali metal silicates, alkali metal carbonates, alkali metal phosphates, and the like.
  • Representative of the alkali metal compounds which are sequestrants are sodium tripolyphosphate, tetrapotassium pyrophosphate, tetrasodium pyrophosphate, trisodium phosphate, sodium hexametaphosphate, and the like.
  • Other useful compounds are sodium metasilicate, sodium metasilicate pentahydrate, soda ash, potassium carbonate, sodium bicarbonate, and the like.
  • alkali metal hydroxides such as, sodium hydroxide, potassium hydroxide, lithium hydroxide, and the like
  • any of the Well known builders can be employed herein. However, it is preferred to employ the builders which function as sequestrants and, in particular, tetrapotassium pyrophosphate.
  • the alkali component of the concentrate is used to adjust the pH of the composition.
  • the pH should be in the range of 9.0 to 10.0.
  • alkali as used herein is meant either caustic soda (sodium hydroxide) or potassium hydroxide. Either of these materials, if deployed in the requisite amount, will impart the preferred pH to the system.
  • the alkali can be eliminated from the composition for pH adjustment if it is used as the builder.
  • the present composition is prepared at room temperature and pressure by adding the ingredients together, with agitation, in the following sequence. Initially, the sequestrant is added to the water and mixed therewith until dissolved. Then, the solubilizing agent or phosphate ester anionic surfactant and the linear alkylbenzene sulfonate are added contemporaneously to the Water and sequestrant solution. The pH of the mixture is then adjusted by adding the alkali, if needed. The last ingredient incorporated into the composition is the nonionic surfactant. After all the ingredients are in solution, the concentrate is ready for use.
  • the concentrate is added with agitation to an aqueous medium in a weight ratio of from 1:300 to 1:400 and preferably from 1:350 to 1:400.
  • freezing point depressants such as, propylene glycol, isopropanol, and the like can be used in amounts up to about from 5 to by weight of the composition without deleteriously aifecting the properties of the compositions in respect to flash point, glass smearing and the like.
  • these freezing point depressants are also hydrotropes, and, therefore, their presence may be very worthwhile.
  • the composition is biodegradable, noncorrosive, non-etching, a lubricant for the bristles of mechanical brushes, storage stable, eflicient in very dilute solutions, and does not leave wate spots on the vehicle body.
  • a car wash composition adapted for tunnel-type car wash systems and in accordance with the present invention is prepared from the following:
  • Nonionic surfactant A 1 405.46 Phosphate ester W 2 190.00 Linear alkylbenzene sulfonate M 3 354.50 Tetrapotassium pyrophosphate 182.40 Caustic soda 4 31.80 Water 2,652.40 Sodium benzoate 5 15.20
  • composition is prepared by mixing the tetrapotassium pyrophosphate into the water until dissolved. Then the linear alkylbenzene sulfonate and phosphate ester are added to the solution. The pH of the solution is then adjusted to 9.35 by the addition of the caustic soda. Lastly, the nonionic surfactant and the sodium benzoate are incorporated into the composition.
  • the product has a pH of about 9.3 and is storage stable at a temperature of about F.
  • Nonionio surfactant B Nonionic surfactant 0
  • Nonionic surfactant D Phosphate ester W Phosphate ester X 4 Linear alkylbenzene sulfonato Linear alkylbenzenc sulfonatc N Tetrapotassium pyrophosphate Freezing point depressant Water 1
  • reaction product about 1.25 moles of polyphosphoric acid per mole of a condensation product of a 05:1 weight mixture of ethylene oxide and propylene oxide and the mixture of 0 1-015 alcohols defined in footnote 1, the resulting condensation product containing about 75% by weight of ethylene oxide and propylene oxide.
  • Each of these compositions has a pH of about 9.3 and exhibits storage stability up to about 160 F.
  • R--O (A) -H wherein R is the alcoholic residue of a linear aliphatic alcohol having from 10 to 18 carbon atoms and mixtures thereof, A is either oxyethylene groups or a mixture of oxyethylene and oxypropylene groups being present in a weight ratio of oxyethylene to oxypropylene groups ranging from about 0.5 :1 to 6:1, and n is an integer sufficiently large such that A constitutes from about 60 to 85% of the weight of the surfactant;
  • R is the alcoholic residue of a linear aliphatic alcohol having from 10 to 18 carbon atoms and mixtures thereof, A is either oxyethylene groups or a mixture of oxyethylene groups and oxypropylene groups in a weight ratio of oxyethylene to oxypropylene groups ranging from about 0.5:1 to 6: 1, and n is an integer sufficiently large such that A constitutes from about 30 to by weight of the ester, and wherein the mixture of monoand diester consists of from about 60 to by weight of monoester and from about 40 to 0% by weight of diester;
  • R is the residue of a mixture of linear aliphatic alcohols having from 12 to 15 carbon atoms.
  • R is the residue of a mixture of linear aliphatic alcohols having from 10 to 12 carbon atoms.
  • R is the residue of a mixture of linear aliphatic alcohols having from 12 to 15 carbon atoms.
  • a and A are each, respectively, the mixture of oxypropylene groups and oxyethylene groups.
  • composition has a pH ranging from about 9 to 10.
  • composition further includes sodium benzoate as a moldicide.
  • composition further includes propylene glycol or isopropanol as a freezing point depressant.

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  • Engineering & Computer Science (AREA)
  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Wood Science & Technology (AREA)
  • Organic Chemistry (AREA)
  • Mechanical Engineering (AREA)
  • General Engineering & Computer Science (AREA)
  • Detergent Compositions (AREA)
US00099522A 1970-12-18 1970-12-18 Biodegradable detergent for automatic car wash systems Expired - Lifetime US3738943A (en)

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BE (1) BE776126A (enExample)
CA (1) CA936782A (enExample)
DE (1) DE2161658A1 (enExample)
FR (1) FR2118472A5 (enExample)
GB (1) GB1354957A (enExample)
IT (1) IT945058B (enExample)
NL (1) NL7117384A (enExample)

Cited By (19)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3897357A (en) * 1972-12-06 1975-07-29 American Home Prod Bacteriostatic toilet bowl cleaner compositions
US3951826A (en) * 1972-07-25 1976-04-20 Colgate-Palmolive Company All purpose liquid detergent
US3957661A (en) * 1972-07-25 1976-05-18 Colgate-Palmolive Company Fabric softening laundry detergent containing organic esters of phosphoric acid
US4049558A (en) * 1972-07-25 1977-09-20 Colgate-Palmolive Co. Free flowing phosphate ester compositions for post addition to detergents
US4198308A (en) * 1973-07-23 1980-04-15 Colgate Palmolive Company Manufacture of free-flowing fabric softening detergent
US4244840A (en) * 1977-05-10 1981-01-13 Colgate-Palmolive Company Self-opacified liquid hard surface cleaning compositions
US4362642A (en) * 1976-01-23 1982-12-07 Lever Brothers Company Alkyl phosphoric acid polyvalent salts-mineral oil lather controlled detergent compositions
US4465613A (en) * 1976-01-23 1984-08-14 Lever Brothers Company Alkyl phosphoric salt-hydrocarbon wax lather controlled detergent compositions
US4578208A (en) * 1983-05-07 1986-03-25 Henkel Kommanditgesellschaft Auf Aktien Compositions and processes for cleaning and passivating metals
US4683008A (en) * 1985-07-12 1987-07-28 Sparkle Wash, Inc. Method for cleaning hard surfaces
US4752411A (en) * 1984-05-28 1988-06-21 Cotelle, S.A. Liquid composition for cleaning hard surfaces
US5167872A (en) * 1985-10-31 1992-12-01 The Procter & Gamble Company Comprising anionic surfactant polymeric nonionic surfactant and betaine surfactant
US5192461A (en) * 1991-08-23 1993-03-09 Enthone-Omi, Inc. Aqueous degreasing solution having high free alkalinity
US5372741A (en) * 1991-11-27 1994-12-13 Ethone-Omi, Inc. Aqueous degreasing composition and process
US5529890A (en) * 1992-05-12 1996-06-25 Eastman Kodak Company Addenda for an aqueous photographic stabilizing solution
US5569411A (en) * 1986-08-08 1996-10-29 Colgate-Palmolive Co. Liquid household cleaning composition with insect repellent
US5573700A (en) * 1986-08-08 1996-11-12 Colgate-Palmolive Co. Liquid household cleaning composition with insect repellent
US6258772B1 (en) 1999-10-12 2001-07-10 Bay Technologies, Inc. Cleaning compositions comprising perfluorinated alkylphosphates
CN105820887A (zh) * 2016-04-18 2016-08-03 袁玉珍 汽车外饰清洗剂及其制备方法

Families Citing this family (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4070309A (en) * 1976-07-27 1978-01-24 The Procter & Gamble Company Detergent composition
DE2727382A1 (de) * 1977-06-18 1979-01-04 Basf Ag Mono- und/oder dialkylphosphate enthaltende schaumdaempfer
GR1002362B (el) * 1995-07-12 1996-06-11 Απορρυπαντικες συνθεσεις απο συμπολυμερη αιθυλενο και προπυλενο οξειδιων και πολυαιθερες των λιπαρων αλκοολων.
DE19711040A1 (de) * 1996-03-06 1998-02-05 Gerard Pieper Verfahren und Maschine zum Behandeln ebener Flächen

Cited By (19)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3951826A (en) * 1972-07-25 1976-04-20 Colgate-Palmolive Company All purpose liquid detergent
US3957661A (en) * 1972-07-25 1976-05-18 Colgate-Palmolive Company Fabric softening laundry detergent containing organic esters of phosphoric acid
US4049558A (en) * 1972-07-25 1977-09-20 Colgate-Palmolive Co. Free flowing phosphate ester compositions for post addition to detergents
US3897357A (en) * 1972-12-06 1975-07-29 American Home Prod Bacteriostatic toilet bowl cleaner compositions
US4198308A (en) * 1973-07-23 1980-04-15 Colgate Palmolive Company Manufacture of free-flowing fabric softening detergent
US4362642A (en) * 1976-01-23 1982-12-07 Lever Brothers Company Alkyl phosphoric acid polyvalent salts-mineral oil lather controlled detergent compositions
US4465613A (en) * 1976-01-23 1984-08-14 Lever Brothers Company Alkyl phosphoric salt-hydrocarbon wax lather controlled detergent compositions
US4244840A (en) * 1977-05-10 1981-01-13 Colgate-Palmolive Company Self-opacified liquid hard surface cleaning compositions
US4578208A (en) * 1983-05-07 1986-03-25 Henkel Kommanditgesellschaft Auf Aktien Compositions and processes for cleaning and passivating metals
US4752411A (en) * 1984-05-28 1988-06-21 Cotelle, S.A. Liquid composition for cleaning hard surfaces
US4683008A (en) * 1985-07-12 1987-07-28 Sparkle Wash, Inc. Method for cleaning hard surfaces
US5167872A (en) * 1985-10-31 1992-12-01 The Procter & Gamble Company Comprising anionic surfactant polymeric nonionic surfactant and betaine surfactant
US5569411A (en) * 1986-08-08 1996-10-29 Colgate-Palmolive Co. Liquid household cleaning composition with insect repellent
US5573700A (en) * 1986-08-08 1996-11-12 Colgate-Palmolive Co. Liquid household cleaning composition with insect repellent
US5192461A (en) * 1991-08-23 1993-03-09 Enthone-Omi, Inc. Aqueous degreasing solution having high free alkalinity
US5372741A (en) * 1991-11-27 1994-12-13 Ethone-Omi, Inc. Aqueous degreasing composition and process
US5529890A (en) * 1992-05-12 1996-06-25 Eastman Kodak Company Addenda for an aqueous photographic stabilizing solution
US6258772B1 (en) 1999-10-12 2001-07-10 Bay Technologies, Inc. Cleaning compositions comprising perfluorinated alkylphosphates
CN105820887A (zh) * 2016-04-18 2016-08-03 袁玉珍 汽车外饰清洗剂及其制备方法

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CA936782A (en) 1973-11-13
DE2161658A1 (de) 1972-08-24
NL7117384A (enExample) 1972-06-20
FR2118472A5 (enExample) 1972-07-28
BE776126A (fr) 1972-06-01
IT945058B (it) 1973-05-10
GB1354957A (en) 1974-06-05

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Effective date: 19860409

Owner name: BASF CORPORATION

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Effective date: 19860409