EP0487169A1 - Konzentrierte flüssige Detergenszusammensetzung mit Alkylbenzolsulfonat und Magnesium - Google Patents

Konzentrierte flüssige Detergenszusammensetzung mit Alkylbenzolsulfonat und Magnesium Download PDF

Info

Publication number
EP0487169A1
EP0487169A1 EP91203044A EP91203044A EP0487169A1 EP 0487169 A1 EP0487169 A1 EP 0487169A1 EP 91203044 A EP91203044 A EP 91203044A EP 91203044 A EP91203044 A EP 91203044A EP 0487169 A1 EP0487169 A1 EP 0487169A1
Authority
EP
European Patent Office
Prior art keywords
weight
composition
magnesium
water
alkyl
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.)
Granted
Application number
EP91203044A
Other languages
English (en)
French (fr)
Other versions
EP0487169B1 (de
Inventor
Gary J. Jakubicki
Dirk Warschewski
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Colgate Palmolive Co
Original Assignee
Colgate Palmolive Co
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Colgate Palmolive Co filed Critical Colgate Palmolive Co
Publication of EP0487169A1 publication Critical patent/EP0487169A1/de
Application granted granted Critical
Publication of EP0487169B1 publication Critical patent/EP0487169B1/de
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

Links

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
    • C11D3/00Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/0005Other compounding ingredients characterised by their effect
    • C11D3/0094High foaming compositions
    • 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
    • C11D1/12Sulfonic acids or sulfuric acid esters; Salts thereof
    • 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
    • C11D1/37Mixtures of compounds all of which are anionic
    • 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
    • C11D1/38Cationic compounds
    • C11D1/65Mixtures of anionic with cationic compounds
    • C11D1/655Mixtures of sulfonated products with alkylolamides of carboxylic acids
    • 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
    • C11D3/00Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/02Inorganic compounds ; Elemental compounds
    • C11D3/04Water-soluble compounds
    • C11D3/046Salts
    • 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
    • C11D3/00Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16Organic compounds
    • C11D3/26Organic compounds containing nitrogen
    • C11D3/32Amides; Substituted amides
    • 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
    • C11D1/12Sulfonic acids or sulfuric acid esters; Salts thereof
    • C11D1/22Sulfonic acids or sulfuric acid esters; Salts thereof derived from aromatic 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
    • C11D1/12Sulfonic acids or sulfuric acid esters; Salts thereof
    • C11D1/29Sulfates of polyoxyalkylene ethers
    • 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
    • C11D1/38Cationic compounds
    • C11D1/52Carboxylic amides, alkylolamides or imides or their condensation products with alkylene oxides
    • C11D1/523Carboxylic alkylolamides, or dialkylolamides, or hydroxycarboxylic amides (R1-CO-NR2R3), where R1, R2 or R3 contain one hydroxy group per alkyl group

Definitions

  • This invention relates to aqueous liquid detergent compositions containing alkyl benzene sulfonate and added detergent boosting levels of magnesium ions.
  • Light-duty liquid detergent compositions such as those suitable for use in washing dishes, are well known. Performance of such compositions is a measurement of both foam mileage, i.e. number of dishes washed, and grease cutting ability.
  • the liquid dishwashing detergent compositions presently on the market are designed to remove oily/greasy soils from glasses, dishes, and other tableware and kitchen utensils while maintaining an acceptable layer of suds.
  • Liquid detergent formulations containing magnesium salts and magnesium surfactants show enhanced performance, as is disclosed in U.S. Patents 2,908,651 and 2,437,253. Certain combinations of active ingredients can also provide a range of enhanced detergent properties.
  • An enhanced performance liquid detergent composition disclosed in U.S.
  • Patent 4,435,317 contains (a) a C10-C16 alkyl sulfate, (b) a C10-C16 alkyl ethoxy sulfate and (c) a linear C10-C16 alkyl benzene sulfonate in a ratio of the total weight of (a) + (b) to the weight of (c) of less than or equal to 33:1, and containing magnesium in a molar amount corresponding to 0.20x-0.70x where x is the number of moles of alkyl sulfate.
  • the amount of magnesium salts that can be added to the compositions disclosed in U.S. Patent 4,435,317 is limited because the salts raise the temperatures at which inorganic salt crystals form in the compositions upon cooling.
  • hydrotropes are fairly expensive and are generally inactive materials and thus do not contribute to detergency but have the effect of rendering the active ingredients water soluble and the composition homogeneous at those temperatures normally encountered in transport and storage. Hydrotropes generally lower the "cloud point" of liquid detergent compositions, thus maintaining a clear liquid composition at temperatures at which a detergent composition lacking hydrotrope would become cloudy and unattractive in appearance.
  • Patent 4,235,758 discloses that the use of a magnesium alkylbenzene sulfonate derived from a linear C10-C13 alkylbenzene of average molecular weight of 220-250 significantly reduces the requirement for hydrotrope at any level of active detergent material.
  • compositions comprised of certain specific detergent active ingredients, in unique combinations and proportions, which are unexpectedly capable of superior performance to other liquid detergents in relation to both foam mileage and grease cutting.
  • Still another object of this invention is to provide a concentrated detergent base composition containing detergency boosting levels of magnesium ions and alkyl benzene sulfonate which may be stored as a concentrated liquid base composition and which may be manufactured using conventional low shear liquid mixing equipment.
  • an aqueous liquid detergent composition especially suitable for use in dishwashing, and containing
  • the present invention also provides a pourable liquid detergent base composition of concentrated light duty liquid detergents containing alkylbenzene sulfonic acid and detergency boosting levels of magnesium ions and which can be stored at ambient temperature for future use without gelling.
  • Detergent compositions in accordance with the present invention comprise a mixture of two or three essential anionic surfactants of defined constitution and proportions and have a specified molar ratio of magnesium ion to alkylbenzene sulfonate ranging from 0.65:1.0 to 1.0:1.0.
  • the first essential surfactant ingredient is a water-soluble salt of alkylbenzene sulfonic acid, which may be linear or branched.
  • the alkyl group preferably contains from about 10 to 18 carbon atoms, most preferably from about 11 to 13, especially about 12 carbon atoms, preferably in a linear chain configuration.
  • the alkyl benzene sulfonate may be present as an alkali metal, amine, ammonium, or alkaline earth metal salt, preferably the magnesium salt.
  • the most preferred alkylbenzene sulfonate is the magnesium salt of linear dodecylbenzene sulfonate.
  • the acid form of alkylbenzene sulfonic acid can be converted to the magnesium salt form either prior to admixture with the other detersive ingredients or thereafter.
  • the conversion may be accomplished either by direct neutralization with magnesium oxide or hydroxide or by ion exchange between, for example, an alkali metal salt or the ammonium salt of alkylbenzene sulfonate and a water-soluble alkaline earth metal salt.
  • a source of magnesium ions is added to the detergent mixture to form the desired salt of alkylbenzene sulfonate.
  • Magnesium chlorides, magnesium sulfates, magnesium acetates or magnesium hydroxides are examples of magnesium sources.
  • the preferred magnesium sources are magnesium oxides or hydroxides and sulfates.
  • the alkylbenzene sulfonate component is present at a level of from about 15 to 35% by weight of the composition, preferably in the range from about 15 to 22%, most preferably in the range from about 19 to 21% by weight.
  • the point of attachment of the alkyl chain to the benzene nucleus referred to as the phenyl isomer distribution, is not critical but, preferably, less than 20% of the alkyl benzene of this invention comprises the 2-phenyl isomer.
  • a second essential surfactant component of the present composition is a primary alkyl ethoxy sulfate derived from the condensation product of a C10-C16 alcohol with an average of from about 1 to about 6 ethylene oxide groups, preferably about 2 to 4, especially 3 ethylene oxide groups per mole of alcohol.
  • the C10-C16 alcohols may be derived, for example, from natural fats or Ziegler olefin build-up or Oxo synthesis. It is preferable to use alkyl ethoxy sulfates and alkyl sulfates of the same carbon chain length, preferably C12-C13.
  • the level of alkyl ethoxy sulfate in the present composition to achieve the desired foam and detersive properties is about 1-30% by weight, preferably in the range from about 10-20% by weight, based on the total composition.
  • the surfactant system of the detergent of the present invention may optionally also include an amount ranging from 0-20% of the total composition, preferably 10-15% by weight, of an alkali metal or ammonium or amine salt of a linear or branched C10-C18 alkyl sulfate anionic surfactant.
  • the cationic counter-ion of the alkyl sulfate may be taken from the group consisting of alkali metals, ammonia and amines, e.g., triethylammonium, triethanolamine (TEA), diethanolamine or monoethanolamine, etc.
  • the alkali metal may be, for example, sodium or potassium, preferably sodium.
  • the composition of the present invention contains from about 0.027 to about 0.064 moles of total magnesium ion. Generally, 0.023 to about 0.053 moles of magnesium ion are provided through the incorporation of the magnesium alkylbenzene sulfonate. Additional magnesium may be added to the composition in the form of a water-soluble compound, most preferably a salt, such as, for example, magnesium sulfate or magnesium chloride.
  • the preferred magnesium source is magnesium sulfate heptahydrate, added to the composition at about from 1 or 2 to 5% by weight, preferably from about 2.5 to 3.5% by weight, corresponding to 0.01 to 0.014 moles of added magnesium.
  • the total magnesium ion to alkylbenzene sulfonate in the composition is controlled to correspond to a molar ratio of from 0.65:1.0 to 1.0:1.0, preferably from 0.65:1.0 to 0.8:1.0.
  • the additional magnesium ions added in salt form provide improved grease cutting performance and also lower the cloud point of the formula better than the more expensive hydrotropes.
  • the additional magnesium salt also provides better phase stability to the composition.
  • Using magnesium to boost detergency is known in the art, however, when used in a molar ratio of total magnesium ion to alkylbenzene sulfonate in a range of 0.65:1.0 to 0.8:1.0, the excess magnesium salt not only enhances foam mileage but also increases fluidity, allowing for a decrease in hydrotrope and alcohol levels, thus lowering the concentration of inactive ingredients that do not boost detergency of the composition. This decrease in the level of inactive ingredients leaves room in the composition for an even higher level of detersive active ingredients.
  • the level of detersive active ingredients in the compositions of this invention is in the range from 20-70% by weight, preferably from 30 to 55%. This increased level of active ingredients results in enhanced foam mileage, thus providing a superior light duty liquid detergent.
  • the usual problems of increased viscosity, decreased stability and product clouding is avoided by using an increased level of magnesium ions in a molar ratio of magnesium ions to alkylbenzene sulfonate in the range of 0.65:1.0 to 1.0:1.0, preferably from to 0.8:1.0 and none or only a low concentration of hydrotrope.
  • the additional magnesium ions in the compositions of this invention also boosts detergency of the surfactant system.
  • a suds promoting agent such as, for example, a mono- or di-alkanolamide, may, therefore, be added to the present composition at a level of from 0.5 to about 8% by weight, preferably about 1 to 6% and, more preferably about 1 to 5% by weight.
  • the preferred suds promoting agent is a mixture of lauric and myristic monoethanolamides.
  • the alkyl group of the amide may be derived from coconut or palm kernel oil.
  • Suitable alkanolamides include either mono or dialkanolamides having a carbon chain distribution of C1-C5, preferably C1-C3, especially mono- or di-ethanolamide.
  • the alkanolamide may be ethoxylated or may be a mixture of non-ethoxylated alkanolamide and ethoxylated alkanolamide in order to increase the solubility of the alkanolamide in the composition.
  • clarity and homogeneity of the invention compositions may be improved by inclusion of, for example, organic solvents or hydrotropes and these and other non-essential additives may be included in the compositions in amounts that do not adversely effect the desired properties.
  • Organic solvents may be included for their thinning effect, ability to lower the clear point and for solubilization.
  • Organic solvents such as, for example isopropanol, n-propanol, ethanol, propylene glycol or mixtures thereof may be included.
  • the solvent level is usually less than or equal to 10% by weight, preferably less than 8%, more preferably in the range of 5 to 8% by weight. Ethanol is the preferred solvent.
  • hydrotropic substance in the composition such as, for example, urea, sodium xylene sulfonate, potassium xylene sulfonate, sodium cumene sulfonate, and ammonium xylene sulfonate, and the like in order to assist in solubilizing various components of the composition and maintaining a low clear point.
  • a hydrotropic substance such as, for example, urea, sodium xylene sulfonate, potassium xylene sulfonate, sodium cumene sulfonate, and ammonium xylene sulfonate, and the like in order to assist in solubilizing various components of the composition and maintaining a low clear point.
  • urea sodium xylene sulfonate
  • potassium xylene sulfonate sodium cumene sulfonate
  • ammonium xylene sulfonate and the like in order to assist in solubilizing various components of the composition
  • ingredients may also be included in the composition for their desirable aesthetic or functional characteristics.
  • Such ingredients include, for example, opacifying agents to make the composition appear pearly, such as behenic acid or ethylene glycol distearate; perfumes; heavy metal chelating agents such as EDTA; bactericides such as trichlorocarbanilide, tetrachlorosalicylanilide, hexachlorophene, or chlorobromosalicylanilide; antioxidants; thickeners such as quar gum, polyacrylates, polyacrylamide or Irish moss; dyes, water dispersible pigments; preservatives, such as formaldehyde or hydrogen peroxide; pH modifiers, etc.
  • opacifying agents to make the composition appear pearly such as behenic acid or ethylene glycol distearate
  • perfumes such as behenic acid or ethylene glycol distearate
  • heavy metal chelating agents such as EDTA
  • bactericides such as trichlorocarban
  • these optional adjuvants may be present in total amounts up to about 10% by weight, preferably up to about 3% by weight, based on the total composition.
  • the pH of the compositions may be within the range from 6 to 8, preferably from about 6.5 to 7.5, and may be adjusted if necessary by addition of suitable acids or bases, such as HCl, NaOH, and the like. Excellent greasy soil removal is attained when an effective amount of the instant compositions is dissolved in an aqueous dishwashing solution. Typical use concentrations are usually at least about 0.05% by weight in water. Of course, this can be adjusted, depending on the soil level and type and desires of the user.
  • compositions of the present invention employ high levels of anionic surfactants, which are, in general, less water-soluble than nonionic surfactants.
  • anionic surfactants which are, in general, less water-soluble than nonionic surfactants.
  • the decreased solubility of the anionic surfactants coupled with the increased concentration of active ingredients often results in thick pastes with very high viscosities, thereby necessitating the use of heavy duty or high shear mixing equipment. Accordingly, in a preferred mode for carrying out the present invention a non-conventional process is used for the manufacture of the compositions of the present invention.
  • a detergent base comprising magnesium alkylbenzene sulfonate and amide foam booster is preferably manufactured by a process wherein alkanolamide, in the specified amount, is added to an aqueous slurry containing magnesium oxide or hydroxide, hydrotropes, and any inorganic salts or organic solvents of the liquid detergent compositions of this invention, in the specified amounts, and the alkylbenzene sulfonic acid, is added after the alkanolamide has been dissolved in the slurry.
  • compositions are prepared with conventional low shear mixing equipment by mixing the materials in the proportions as listed.
  • the composition of Run No. 2 is a physically stable liquid upon accelerated aging at elevated temperature.
  • Each of the compositions of Runs 1 and 2 are evaluated by the following performance criteria: (1) Grease Removal Test
  • This test is used to measure grease removal of the composition at a concentration of 1% liquid detergent at 50 ppm water hardness, at 80°F, with 600 dipping cycles at 60 rpm.
  • 0.5 grams of lard at room temperature is evenly applied to a frosted glass microscope slide using a serrated knife blade. The results are calculated as milligrams of lard removed.
  • a modified version of the Grease Removal test is used to measure grease removal of a 0.05% solution of liquid detergent at 50 ppm water hardness and 108°F, with 600 dipping cycles at 60 rpm. For this test, 0.1 ⁇ 0.02 grams of lard is applied to plastic test tubes by dipping the pre-weighed tubes in melted lard and blotting off any excess grease before it solidifies. The tubes are then re-weighed and used the same day they are prepared.
  • test solution prepared using 50 ppm water at 120°F is delivered to a dish pan from a separatory funnel suspended above the pan to generate a layer of foam. Plates soiled with 5.4 grams lard are washed to a foam end point. This test measures the total number of plates that can be washed with the detergent composition until the foam completely disappears.
  • This test is used to determine the dynamic foam stability of a liquid detergent composition at 50 ppm water hardness at 113°F.
  • a diluted (0.05 or 0.04%) test solution is titrated with constant delivery of mixed soil to a foam end point under constant agitation.
  • the test measures the amount of mixed soil required to deplete the surfactants of the composition.
  • This test is used to determine the sudsing ability of a liquid detergent composition at 50 ppm water hardness at 113°F.
  • a stable pourable liquid detergent composition is prepared by mixing the following ingredients using a conventional low shear liquids mixing apparatus.
  • the proportion of each ingredient is as follows:

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)
  • Inorganic Chemistry (AREA)
  • Detergent Compositions (AREA)
  • Steroid Compounds (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Cosmetics (AREA)
EP91203044A 1990-11-21 1991-11-20 Konzentrierte flüssige Detergenszusammensetzung mit Alkylbenzolsulfonat und Magnesium Expired - Lifetime EP0487169B1 (de)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US61649690A 1990-11-21 1990-11-21
US616496 1990-11-21

Publications (2)

Publication Number Publication Date
EP0487169A1 true EP0487169A1 (de) 1992-05-27
EP0487169B1 EP0487169B1 (de) 1996-08-21

Family

ID=24469709

Family Applications (1)

Application Number Title Priority Date Filing Date
EP91203044A Expired - Lifetime EP0487169B1 (de) 1990-11-21 1991-11-20 Konzentrierte flüssige Detergenszusammensetzung mit Alkylbenzolsulfonat und Magnesium

Country Status (23)

Country Link
EP (1) EP0487169B1 (de)
KR (1) KR920009963A (de)
CN (1) CN1061993A (de)
AT (1) ATE141638T1 (de)
AU (1) AU654508B2 (de)
BR (1) BR9105056A (de)
CA (1) CA2055340A1 (de)
DE (1) DE69121524T2 (de)
DK (1) DK0487169T3 (de)
FI (1) FI915473A (de)
GR (1) GR1001194B (de)
HU (1) HU211779B (de)
IE (1) IE914032A1 (de)
MW (1) MW7091A1 (de)
MX (1) MX9102048A (de)
NO (1) NO179796C (de)
NZ (1) NZ240394A (de)
PL (1) PL292456A1 (de)
PT (1) PT99542B (de)
YU (1) YU47539B (de)
ZA (1) ZA918752B (de)
ZM (1) ZM4391A1 (de)
ZW (1) ZW15191A1 (de)

Cited By (14)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5415801A (en) * 1993-08-27 1995-05-16 The Procter & Gamble Company Concentrated light duty liquid or gel dishwashing detergent compositions containing sugar
US5415814A (en) * 1993-08-27 1995-05-16 The Procter & Gamble Company Concentrated liquid or gel light duty dishwashing detergent composition containing calcium xylene sulfonate
US5417893A (en) * 1993-08-27 1995-05-23 The Procter & Gamble Company Concentrated liquid or gel light duty dishwashing detergent compositions containing calcium ions and disulfonate surfactants
GB2288409A (en) * 1993-12-15 1995-10-18 Albright & Wilson Structured surfactants
US5474710A (en) * 1993-08-27 1995-12-12 Ofosu-Asanta; Kofi Process for preparing concentrated surfactant mixtures containing magnesium
EP0719320A1 (de) * 1993-09-14 1996-07-03 The Procter & Gamble Company Handgeschirrspülmittelzusammensetzungen
USH1632H (en) * 1994-08-15 1997-02-04 Shell Oil Company Liquid laundry detergent formulations
WO1997035947A1 (en) * 1996-03-25 1997-10-02 Colgate-Palmolive Company Light duty liquid cleaning compositions
US6083893A (en) * 1994-05-16 2000-07-04 The Proctor And Gamble Co. Shaped semi-solid or solid dishwashing detergent
US6166095A (en) * 1993-12-15 2000-12-26 Albright & Wilson Uk Limited Method of preparing a drilling fluid comprising structured surfactants
WO2003016446A1 (en) * 2001-08-21 2003-02-27 Colgate-Palmolive Company Liquid cleaning compositions
KR100397421B1 (ko) * 2001-01-11 2003-09-13 씨제이 주식회사 선형 알킬벤젠설폰산 마그네슘염을 함유하는 액체세제조성물
ES2279729A1 (es) * 2006-02-13 2007-08-16 Universidad De Cadiz Nuevo tensioactivo anionico y procedimiento de obtencion.
WO2021108307A1 (en) * 2019-11-27 2021-06-03 The Procter & Gamble Company Improved alkylbenzenesulfonate surfactants

Families Citing this family (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
NZ240395A (en) * 1990-11-21 1993-10-26 Colgate Palmolive Co Process for manufacture of concentrated liquid detergent containing magnesium alkylbenzene sulphonate and alkanolamide suds booster
KR100340230B1 (ko) * 1999-04-10 2002-06-12 (주)한국자원재활유지 세제용 비누 제조방법
KR100317948B1 (ko) * 1999-06-01 2001-12-22 손 경 식 알킬벤젠설폰산마그네슘염을 함유하는 알카리성 액체세제 조성물
CN101538512B (zh) * 2009-03-11 2011-06-08 上海九盛实业有限公司 水基清洗剂
AU2010330800B2 (en) 2009-12-17 2014-07-17 Stepan Company Foaming light duty liquid detergent compositions, methods of making and uses thereof
MX2013001062A (es) * 2010-07-27 2013-02-21 Unilever Nv Composicion de detergente.
CN105062712B (zh) * 2015-07-29 2018-01-12 广州立白企业集团有限公司 一种泡沫型果蔬餐具洗涤剂组合物

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5424906A (en) * 1977-07-26 1979-02-24 Lion Corp Novel liquid detergent composition
US4435317A (en) * 1980-04-24 1984-03-06 The Procter & Gamble Company Dishwashing liquid including alkyl sulfate, alkyl ether sulfate, alkylbenzene sulfonate and magnesium
FR2588013A1 (fr) * 1985-10-01 1987-04-03 Zschimmer Schwarz France Compositions tensio-actives liquides aptes a former des dilutions aqueuses visqueuses notamment pour le nettoyage de la vaisselle

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5424906A (en) * 1977-07-26 1979-02-24 Lion Corp Novel liquid detergent composition
US4435317A (en) * 1980-04-24 1984-03-06 The Procter & Gamble Company Dishwashing liquid including alkyl sulfate, alkyl ether sulfate, alkylbenzene sulfonate and magnesium
FR2588013A1 (fr) * 1985-10-01 1987-04-03 Zschimmer Schwarz France Compositions tensio-actives liquides aptes a former des dilutions aqueuses visqueuses notamment pour le nettoyage de la vaisselle

Cited By (20)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5415814A (en) * 1993-08-27 1995-05-16 The Procter & Gamble Company Concentrated liquid or gel light duty dishwashing detergent composition containing calcium xylene sulfonate
US5417893A (en) * 1993-08-27 1995-05-23 The Procter & Gamble Company Concentrated liquid or gel light duty dishwashing detergent compositions containing calcium ions and disulfonate surfactants
US5474710A (en) * 1993-08-27 1995-12-12 Ofosu-Asanta; Kofi Process for preparing concentrated surfactant mixtures containing magnesium
US5415801A (en) * 1993-08-27 1995-05-16 The Procter & Gamble Company Concentrated light duty liquid or gel dishwashing detergent compositions containing sugar
EP0719320A1 (de) * 1993-09-14 1996-07-03 The Procter & Gamble Company Handgeschirrspülmittelzusammensetzungen
EP0719320A4 (de) * 1993-09-14 1996-10-02 Procter & Gamble Handgeschirrspülmittelzusammensetzungen
GB2288409B (en) * 1993-12-15 1997-12-03 Albright & Wilson Structured surfactants
GB2288409A (en) * 1993-12-15 1995-10-18 Albright & Wilson Structured surfactants
US6166095A (en) * 1993-12-15 2000-12-26 Albright & Wilson Uk Limited Method of preparing a drilling fluid comprising structured surfactants
US6083893A (en) * 1994-05-16 2000-07-04 The Proctor And Gamble Co. Shaped semi-solid or solid dishwashing detergent
USH1632H (en) * 1994-08-15 1997-02-04 Shell Oil Company Liquid laundry detergent formulations
WO1997035947A1 (en) * 1996-03-25 1997-10-02 Colgate-Palmolive Company Light duty liquid cleaning compositions
KR100397421B1 (ko) * 2001-01-11 2003-09-13 씨제이 주식회사 선형 알킬벤젠설폰산 마그네슘염을 함유하는 액체세제조성물
WO2003016446A1 (en) * 2001-08-21 2003-02-27 Colgate-Palmolive Company Liquid cleaning compositions
ES2279729A1 (es) * 2006-02-13 2007-08-16 Universidad De Cadiz Nuevo tensioactivo anionico y procedimiento de obtencion.
WO2007093651A1 (es) * 2006-02-13 2007-08-23 Universidad De Cádiz Nuevo tensioactivo amónico y procedimiento de obtención.
WO2021108307A1 (en) * 2019-11-27 2021-06-03 The Procter & Gamble Company Improved alkylbenzenesulfonate surfactants
CN114667335A (zh) * 2019-11-27 2022-06-24 宝洁公司 改进的烷基苯磺酸盐表面活性剂
JP2022553562A (ja) * 2019-11-27 2022-12-23 ザ プロクター アンド ギャンブル カンパニー 改善されたアルキルベンゼンスルホネート界面活性剤
US11879110B2 (en) 2019-11-27 2024-01-23 The Procter & Gamble Company Alkylbenzenesulfonate surfactants

Also Published As

Publication number Publication date
MX9102048A (es) 1992-07-08
NO179796C (no) 1996-12-18
GR910100471A (en) 1992-10-08
HU913627D0 (en) 1992-02-28
PT99542B (pt) 1999-04-30
AU654508B2 (en) 1994-11-10
CN1061993A (zh) 1992-06-17
NO179796B (no) 1996-09-09
NO914544L (no) 1992-05-22
GR1001194B (el) 1993-06-07
ZA918752B (en) 1992-05-04
MW7091A1 (en) 1993-08-11
ATE141638T1 (de) 1996-09-15
AU8770691A (en) 1992-05-28
BR9105056A (pt) 1992-06-23
DE69121524D1 (de) 1996-09-26
PT99542A (pt) 1992-09-30
CA2055340A1 (en) 1992-05-22
PL292456A1 (en) 1992-08-10
YU47539B (sh) 1995-10-03
FI915473A0 (fi) 1991-11-20
KR920009963A (ko) 1992-06-26
EP0487169B1 (de) 1996-08-21
NO914544D0 (no) 1991-11-20
HUT59720A (en) 1992-06-29
ZM4391A1 (en) 1992-05-29
IE914032A1 (en) 1992-06-03
DE69121524T2 (de) 1997-03-27
YU181191A (sh) 1994-01-20
FI915473A (fi) 1992-05-22
HU211779B (en) 1995-12-28
NZ240394A (en) 1994-01-26
ZW15191A1 (en) 1993-03-03
DK0487169T3 (de) 1997-02-10

Similar Documents

Publication Publication Date Title
EP0487169B1 (de) Konzentrierte flüssige Detergenszusammensetzung mit Alkylbenzolsulfonat und Magnesium
US4923635A (en) Liquid detergent composition containing alkylbenzene sulfonate, alkyl ethanol ether sulfate, alkanolamide foam booster and magnesium and triethanolammonium ions
EP0214868B1 (de) Oberflächenaktive Stoffe und deren Verwendung in Reinigungsmitteln
JP2527428B2 (ja) 液体洗剤組成物
SK25393A3 (en) Liquid detergent compositions
NL8502670A (nl) Sterk schuinende, vloeibare detergens op basis van een niet-ionogene oppervlakactieve verbinding.
MXPA06002286A (es) Composiciones liquidas para limpieza de platos.
RU2095402C1 (ru) Пенящее жидкое моющее средство для облегченного режима работы и способ его приготовления
US5480586A (en) Light duty liquid detergent compostion comprising a sulfosuccinamate-containing surfactant blend
JPH0689356B2 (ja) 液体洗剤組成物
EP0193386A2 (de) Milde Reinigungsmittel
US5096622A (en) Liquid detergent composition containing alkylbenzene sulfonate, alkyl ethonal ether sulfate, alkanolamide foam booster and magnesium and triethanolammonium ions
WO1990002164A1 (en) Light duty liquid detergent compositions
US6815406B1 (en) Liquid dish cleaning compositions
EP0573329B1 (de) Flüssiges Reinigungsmittel auf der Basis von starkschäumenden, nichtionischen, oberflächenaktiven Mitteln
EP0243685A2 (de) Konzentrierte, verdünnbare Reinigungsmittelzusammensetzung
JPH05156281A (ja) 洗浄剤組成物
US5906972A (en) Liquid detergent composition
JP2017078098A (ja) 食器用液体洗浄剤
JPH08503236A (ja) 液体食器洗い用洗剤組成物
JPH08157870A (ja) 液体洗浄剤組成物
JPH0572956B2 (de)
JPH0447000B2 (de)
JP3819152B2 (ja) N置換βアラニン又はその塩の製造方法及びN置換βアラニン又はその塩を含有する界面活性剤組成物
JPH0631405B2 (ja) 液体洗浄剤組成物

Legal Events

Date Code Title Description
PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

AK Designated contracting states

Kind code of ref document: A1

Designated state(s): AT BE CH DE DK ES FR GB IT LI LU NL SE

17P Request for examination filed

Effective date: 19921123

17Q First examination report despatched

Effective date: 19950227

GRAG Despatch of communication of intention to grant

Free format text: ORIGINAL CODE: EPIDOS AGRA

GRAH Despatch of communication of intention to grant a patent

Free format text: ORIGINAL CODE: EPIDOS IGRA

GRAH Despatch of communication of intention to grant a patent

Free format text: ORIGINAL CODE: EPIDOS IGRA

GRAA (expected) grant

Free format text: ORIGINAL CODE: 0009210

AK Designated contracting states

Kind code of ref document: B1

Designated state(s): AT BE CH DE DK ES FR GB IT LI LU NL SE

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: ES

Free format text: THE PATENT HAS BEEN ANNULLED BY A DECISION OF A NATIONAL AUTHORITY

Effective date: 19960821

Ref country code: IT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT;WARNING: LAPSES OF ITALIAN PATENTS WITH EFFECTIVE DATE BEFORE 2007 MAY HAVE OCCURRED AT ANY TIME BEFORE 2007. THE CORRECT EFFECTIVE DATE MAY BE DIFFERENT FROM THE ONE RECORDED.

Effective date: 19960821

Ref country code: AT

Effective date: 19960821

Ref country code: LI

Effective date: 19960821

Ref country code: NL

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 19960821

Ref country code: CH

Effective date: 19960821

REF Corresponds to:

Ref document number: 141638

Country of ref document: AT

Date of ref document: 19960915

Kind code of ref document: T

REF Corresponds to:

Ref document number: 69121524

Country of ref document: DE

Date of ref document: 19960926

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: SE

Effective date: 19961121

Ref country code: GB

Effective date: 19961121

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: LU

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 19961130

ET Fr: translation filed
NLV1 Nl: lapsed or annulled due to failure to fulfill the requirements of art. 29p and 29m of the patents act
REG Reference to a national code

Ref country code: DK

Ref legal event code: T3

REG Reference to a national code

Ref country code: CH

Ref legal event code: PL

PLBE No opposition filed within time limit

Free format text: ORIGINAL CODE: 0009261

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: NO OPPOSITION FILED WITHIN TIME LIMIT

GBPC Gb: european patent ceased through non-payment of renewal fee

Effective date: 19961121

26N No opposition filed
PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: DE

Payment date: 19970929

Year of fee payment: 7

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: DK

Payment date: 19971127

Year of fee payment: 7

Ref country code: FR

Payment date: 19971127

Year of fee payment: 7

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: BE

Payment date: 19971231

Year of fee payment: 7

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: BE

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 19981130

Ref country code: DK

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 19981130

BERE Be: lapsed

Owner name: COLGATE-PALMOLIVE CY (A DELAWARE CORP.)

Effective date: 19981130

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: FR

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 19990730

REG Reference to a national code

Ref country code: FR

Ref legal event code: ST

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: DE

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 19990901

REG Reference to a national code

Ref country code: DK

Ref legal event code: EBP