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WO1996012001A1 - Tensioactifs biodegradables et leurs melanges en tant qu'auxiliaires de rinçage - Google Patents

Tensioactifs biodegradables et leurs melanges en tant qu'auxiliaires de rinçage Download PDF

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Publication number
WO1996012001A1
WO1996012001A1 PCT/US1995/012286 US9512286W WO9612001A1 WO 1996012001 A1 WO1996012001 A1 WO 1996012001A1 US 9512286 W US9512286 W US 9512286W WO 9612001 A1 WO9612001 A1 WO 9612001A1
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WO
WIPO (PCT)
Prior art keywords
integer
value
carbon atoms
linear
aliphatic hydrocarbon
Prior art date
Application number
PCT/US1995/012286
Other languages
English (en)
Inventor
Theodore Groom
Diane J. Burt
Original Assignee
Olin Corporation
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 Olin Corporation filed Critical Olin Corporation
Priority to EP95935125A priority Critical patent/EP0785979A4/fr
Priority to AU37262/95A priority patent/AU3726295A/en
Publication of WO1996012001A1 publication Critical patent/WO1996012001A1/fr

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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
    • 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
    • C11D1/721—End blocked ethers

Definitions

  • the present invention relates generally to a biodegradable surfactant useful in autodish cleaning applications.
  • Another aspect of this invention concerns a liquid surfactant blend that is useful as a rinse aid in industrial and institutional dishwashing applications.
  • R is a substantially linear hydrocarbon and more particularly an alkyl group having an average of from about 7 to about 10 carbon atoms;
  • R' is a linear, alkyl hydrocarbon of from about 1 to about 4 carbon atoms;
  • R" is a linear, alkyl hydrocarbon of from about 1 to about 4 carbon atoms;
  • x is an integer of about 1 to about 6;
  • y is an integer of about 4 to about 15; and
  • z is an integer of about 4 to 25.
  • 4,925,587 discloses hydroxyalkyl polyethylene glycol and hydroxyalkyl polypropylene glycol ether surfactants corresponding to the following general formula: OH R 3
  • R 1 is a linear C 6 -C 16 alkyl radical
  • R 2 is a linear or branched, saturated or unsaturated C 1 -C 22 alkyl radical
  • R 3 is hydrogen or a methyl group; and n is a number of from 0 to 30.
  • U.S. Patent 4,317,940 discloses biodegradable surfactants described as being useful as agricultural emulsifiers and having the following general formula: RO- (CH 2 -CH-0) ⁇ - (CH 2 -CH 2 -0 ) y - (CH 2 *-CH-0) Z -H
  • R' R" wherein R is a linear, alkyl hydrocarbon chain having an average of from about 6 to about 10 carbon atoms; R' is a linear, alkyl hydrocarbon of 1 to about 4 carbon atoms; R" is a linear, alkyl hydrocarbon of from about 1 to about 4 carbon atoms; x is an integer of from about 8 to about 12; y is an integer from about 19 to about 25; and z is an integer from about 2 to 7.
  • No. 4,827,028 discloses the production of anionic surfactants by reacting an unsaturated dicarboxylic acid such as maleic acid or fumaric acid with at least one epoxy-capped poly(oxyalkylated) alcohol having the formula (A) and (B) :
  • R is a hydrocarbon containing radical having from 1 to about 8 carbon atoms
  • R 1 is a hydrocarbon containing radical having from about 6 to about 18 carbon atoms
  • x is an integer having a value from about 6 to about 40
  • y is an integer having a value from about 8 to about 50.
  • the ratio of x:y is from about 2:8 to about 8:2; and the mole ratio of dicarboxylic acid to epoxy-capped poly(oxylalkylated) alcohol is from about 1:1 to about 10:1.
  • the above-described surfactants typically have high caustic solubility, which can be an important surfactant characteristic.
  • biodegradability characteristics as well as surfactant cleaning performance in the cleaning of tableware, particularly when utilizing detergent compositions having low phosphate concentrations, has resulted in the adoption by detergent manufacturers of stringent surfactant performance standards for surfactants used in autodish (i.e., industrial and institutional cleaning products) .
  • stringent surfactant performance standards for surfactants used in autodish i.e., industrial and institutional cleaning products.
  • Prior art surfactants do not always meet these stringent performance standards.
  • U.S. Patent 5,294,365 discloses hydroxypolyethers, made by reacting a monoalkyl ether with an alkyl glycidyl ether, for use as low foam surfactants.
  • the compounds of the '365 patent are disclosed therein as being useful in cleaning compositions and rinse aids, especially in automatic dishwashing machines.
  • new nonionic surfactants have been discovered which provide an excellent combination of biodegradability, low foaming, and rinsing characteristics, as disclosed in PCT Publication No. WO 94/22800, published October 13, 1994.
  • the surfactant compositions disclosed in the '108 application are epoxy-capped poly(oxyalkylated) alcohols represented by the formula: R 1 0[CH 2 CH(CH 3 )0] ⁇ (CH 2 CH 2 0) y [CH 2 CH(OH)R 2 ] z
  • R 1 is a linear, aliphatic hydrocarbon radical having from about 4 to about 18 carbon atoms including mixtures thereof; and R 2 is a linear, aliphatic hydrocarbon radical having from about 2 to about 26 carbon atoms including mixtures thereof; x is an integer having a value from 1 to about 3; y is an integer having a value from 5 to about 30; and z is an integer having a value of from 1 to about 3.
  • the surfactants disclosed in the '108 application are said to provide a significant reduction in spotting and filming of tableware, as compared to conventional surfactants, when used in automatic dishwashers.
  • the present invention relates to a surfactant composition
  • a surfactant composition comprising:
  • R 3 is a linear, aliphatic hydrocarbon radical having an average of from about 4 to about 18 carbon atoms including mixtures thereof;
  • R 4 is hydrogen or a lower alkyl having between 1 and 6 carbon atoms;
  • R 5 is a linear, aliphatic hydrocarbon radical having an average of from about 2 to about 14 carbon atoms including mixtures thereof;
  • x is zero or an integer having a value from 1 to about 5;
  • y is an integer having a value from 1 to about 30;
  • z is an integer having a value of from 1 to about 3.
  • R 1 0[CH 2 CH(CH 3 )0] p (CH 2 CH 2 0) q [CH 2 CH(OH)R 2 ] r
  • R 1 is a linear, aliphatic hydrocarbon radical having an average of from 4 to 12 carbon atoms including mixtures thereof
  • R 2 is a linear, aliphatic hydrocarbon radical having an average of from about 2 to about 4 carbon atoms including mixtures thereof
  • p is an integer having a value from 1 to about 5
  • q is an integer having a value from 1 to about 30
  • r is an integer having a value of from 1 to about 3;
  • R 3 is a linear, aliphatic hydrocarbon radical having an average of from about 4 to about 18 carbon atoms including mixtures thereof; and R 4 is a linear, aliphatic hydrocarbon radical having an average of from about 2 to about 14 carbon atoms including mixtures thereof; x is an integer having a value from 1 to about 5; y is an integer having a value from 1 to about 30; and z is an integer having a value of from 1 to about 3, the weight ratio of component (a) to component (b) being within the range of between about 1:10 and about 10:1, with the proviso that amount of component (a) is sufficient to maintain said blend as a liquid.
  • the present invention relates to a liquid automatic dishwasher composition
  • a liquid automatic dishwasher composition comprising either the above-described surfactant composition or the above-described liquid blend and additionally comprising at least one component selected from the group consisting of detergent builder, bleach, anti-wear agent, and mixtures thereof.
  • the present invention relates to a cleaning composition for cleaning hard surfaces comprising an aqueous or organic solvent and the above-described surfactant composition or liquid blend of epoxy-capped poly(oxyalkylated) alcohols as a surfactant.
  • the present invention relates to a surfactant composition
  • a surfactant composition comprising a liquid or solid carrier and a compound of the formula:
  • R 5 0[CH 2 CH(CH 3 )0] d (CH 2 CH 2 0) e [CH 2 CH(OH) (CH 2 ) 3 CH 3 ] f
  • R 6 is a moiety selected from the group consisting of butyl, hexyl, octyl and decyl, and combinations thereof, d is an integer between 1 and 3 (preferably 1) , e integer between 9 and 11 (preferably 10) , and f is an integer between 1 and 3 (preferably 1) .
  • the surfactant composition of the present invention suitably comprises a surfactant and a carrier or a surfactant blend.
  • the composition is suitably employed in the form of a solution, emulsion or dispersion of the surfactant or surfactant blend.
  • the blend is in the form of a solution without the need for a carrier.
  • the basic components of the blend of the present invention are at least two surfactants comprising (and advantageously consisting essentially of) four components, namely a linear alcohol, propylene oxide, ethylene oxide, and an epoxy cap.
  • the epoxy cap and the linear alcohol serve as a hydrophobic, oil-soluble portion of the molecule.
  • the ethylene oxide groups form the hydrophilic, water-soluble elements of the molecule.
  • a particular surfactant composition as identified in Example 5 hereinbelow, exhibits an unexpectedly high egg soil defoaming efficacy in accordance with standard test protocol CSMA Method DCC-01, as well as a very low foam generating capacity as measured by the Ross Miles Foam Height Test regimen.
  • this product possesses excellent biodegradability, as well as rinse properties as defined by CSMA Method DCC-05A, Glassware Deposition Rinse Test. This combination of properties make it ideal for use as an automatic dishwashing detergent/rinse aid.
  • liquid blends of surfactants within the scope of the present invention provide significant advantages, relative to presently- available commercial surfactants, based upon the performance characteristics of the liquid blends in cleaning tableware, the rinsing characteristics, and the biodegradability of the blends.
  • the present inventors believe the liquid nature of the blends is achieved by virtue of the requirement that the blend contain at least some amount of a surfactant having no more than six (6) carbons contained in the epoxide portion of the molecule.
  • biodegradability and performance characteristics of the blend are believed to be at least partly attributable to the ordered structure of the compositions in which limited numbers of propylene oxide groups are directly attached to the alcohol followed by the addition of the ethylene oxide groups and capping using an 1,2-epoxyalkane. While maintaining this ordered structure, it is desired to also have low ratios of propylene oxide groups to ethylene oxide groups. For example, preferred ratios of propylene oxide groups to ethylene oxide groups are in the range of about 1:5 to about 1:30, and more preferably from about 1:10 to about 1:20.
  • each of the poly(oxyalkylated) alcohols in the blend are suitably produced by condensing an aliphatic alcohol, or mixture of alcohols, having an average chain length of from 4 to about 18 carbon atoms, preferably from about 4 to about 12, and more preferably from about 6 to about 10 carbon atoms, initially with propylene oxide followed by capping this condensation product with ethylene oxide.
  • the methods used for condensing and capping may be any of the well-known methods described in the art.
  • these reactions occur at elevated temperatures in the range of about 120°C to about 180°C, and more preferably at from about 140°C-160°C. It is also preferred to carry out such reactions in the presence of an effective amount (e.g.
  • a suitable alkaline catalyst(s) such as a catalyst selected from the group of hydroxides of alkali metals, alkaline earth metals, alkali metal alcoholates, boron trifluoride (BF 3 ) , and combinations thereof.
  • the preferred catalyst is potassium hydroxide (KOH) .
  • Epoxy compounds useful for making the epoxy-capped poly(oxyalkylated) alcohols of the present invention include any 1,2-epoxyalkanes, or mixtures thereof, having a hydrocarbon chain containing an average of about 2 to about 26 carbon atoms, with the proviso that at least one of the surfactants in the blend (namely the component (a) surfactant described above) contain between two and four carbons on this hydrocarbon chain.
  • the 1,2-epoxyalkane has a linear, aliphatic hydrocarbon chain containing an average of from about 8 to about 20 carbon atoms, and more preferably an average of from about 10 to about 16 carbon atoms.
  • Various 1,2-epoxyalkane compounds are commercially available from Atochem North America Inc., Philadelphia, PA under the product names VIKALOX 11-14, VIKALOX 12, VIKALOX 16 and others.
  • novel surfactant compositions of the present invention provide improved surface treatment of the tableware by the rinse water and subsequently reduces spotting and filming.
  • These epoxy-capped poly(oxyalkylated) alcohols can be formulated in powder and liquid detergent products for automatic dishwashers or in hard surface cleaning products, such as bathroom tile, using methods commercially practiced in the detergent industry.
  • These formulations can include, for example, detergent builders, chelating agents, bleaches, anti-wear agents, and combinations thereof, among others.
  • Suitable detergent builders include inorganic builders such as sodium tripolyphosphate (STPP) , sodium carbonate, zeolites and mixtures thereof.
  • the STPP may be employed in the compositions in a range of about 8 to 35 wt.%, preferably about 20 to 30 wt%, and should preferably be free of heavy metal which tends to decompose or inactivate the preferred sodium hypochlorite and other chlorine bleach compounds.
  • the STPP may be anhydrous or hydrated, including the stable hexahydrate with a degree of hydration of 6 corresponding to about 18% by weight of water or more.
  • Organic builders can also be used including nitrilotriacetic acid and alkali metal salts of tartaric or citric acid.
  • a chelating agent can be any one of a wide range of organic or inorganic sequestering agents, examples including phosphoric acid, amino polycarboxylic acids such as ethylene diamine tetraacetic acid (EDTA) , NTA and DETPA, and polycarboxylic acids such as lactic acid, citric acid, tartaric acid, gluconic acid, glucoheptonic acid, mucic acid, galactonic acid, saccharic acid, fumaric acid, succinic acid, glutaric acid, adipic acid and their alkali metal or ammonium salts.
  • Citric or tartaric acid are preferred chelating acids.
  • the chelating agent if included is present in an amount of up to about 30% and normally lies in the range from about 5% to about 20% by weight.
  • compositions use from about 5% to about 10% by weight of chelating agent in order to minimize any attack by the chelating agent on the glass.
  • the bleach may be an organic chlorine containing bleach, for example, trichloroisocyanuric acid, dichloroisocyanuric acid or a salt of dichloroisocyanuric acid.
  • a sodium or potassium salt such as trichloroisocyanuric acid and is employed in an amount of, for example, 1 to 5% and more preferably 2 to 3% by weight in the cleaning composition.
  • Inorganic bleaching compounds such as chlorinated trisodium polyphosphate (TSPP) or lithium hypochlorite may also be used.
  • the dishwasher formulations may also include anti-wear or anti-corrosion agents such as an alkali metal silicate, preferably sodium silicate, and may be present in a ratio of 0.1 to 3 and preferably 0.2 to 1 mole per mole of alkali in the cleaning composition.
  • Alkalinity may be provided by an alkali metal compound, for example, sodium or potassium hydroxide and/or carbonate.
  • hydrotropic agents such as xylene sulfonates, alcohols, perfumes and coloring agents.
  • the present invention as described herein provides liquid blends useful as nonionic surfactant/rinse aids and characterized by excellent cleaning efficacy and biodegradability. These products are suitable for use in both industrial and institutional and automatic dishwashing applications, since the liquid blends provide an excellent combination of low foaming, excellent rinsing, and efficient removal of high protein soil. These results are particularly surprising since, in general, prior art linear alcohol alkoxylates capped with 1,2-epoxyalkanes which are efficacious with regards to defoaming in high protein soils are either relatively insoluble in water, thus forming cloudy dispersions, or possess relatively poor rinsing properties.
  • the formulation of the product blends with desirable properties in accordance with the present invention was determined based upon statistical experimental design techniques involving individual compositions of a wide range of molecular structure. This insured the potential for providing blends over a reasonable range of cloud points and possessing the desirable properties of excellent machine defoaming, rinsing efficacy, and solution stability. Although binary mixtures were prepared in the working examples provided hereinbelow, terinary or quaternary mixtures are suitably employed, if desired, within the scope of the present invention.
  • liquid blend products of the present invention are suitably formulated to meet were then formulated to meet the performance requirements for industrial and institutional (so- called "I&I") surfactants, as well as the performance requirements for automatic dishwashing surfactants and rinse aids.
  • I&I industrial and institutional
  • the temperature was maintained at 120 ⁇ 3°C for Ik hours. The temperature was then raised to 155°C. At the end of this time 93.i3 grams (0.597 moles) of 1,2- epoxydecane (Atochem) was added through the dropping funnel. The addition took place over less than 10 minutes. The reaction mixture was post-reacted at 155 ⁇ 3°C for hours. At the end of this time the product was cooled and removed from the flask. The cloud point of a one percent solution of the product in water was 3°C. The hydroxyl number was 55.4 and the % primary hydroxyl was 17.7%.
  • the reaction vessel was supplied with a heating mantle and the temperature was brought to 120 ⁇ 3°C. The temperature was maintained at 120+3°C for 1 ⁇ hours. The temperature was then raised to 155°C. At the end of this time 42.98 grams (0.597 moles) of 1,2-epoxybutane (Dow Chemical) was added through the dropping funnel. The addition took place over approximately 1 hour. A slow rate of gentle reflux of the butyleneoxide was maintained. The reaction mixture was post-reacted at 155 ⁇ 3°C for hours. At the end of this time the product was cooled and removed from the flask. The cloud point of a one percent solution of the product in water was 72°C. The hydroxyl number was 58.6 and the % primary hydroxyl was 16.1%.
  • Example 2 To 70 grams of the product described in Example 1 was added 30 grams of the product described in Example 2. The cloud point of a one percent solution of the product in water was 28°C.
  • Example 2 To 80 grams of the product described in Example 1, Part C, was added 20 grams of water, and the resulting product was a clear, aqueous liquid.
  • Glassware was evaluated for spotting, streaking and filming on a scale of 1 to 5, where 1 shows no spots, streaks or film and 5 indicates a glass completely covered with spots, streaks and film.
  • R 3 0[CH 2 CH(CH 3 )0] (CH 2 CH 2 O) 10 [CH 2 CH(OH) (CH 2 )CH 3 ] wherein R 3 is a mixture of butyl, hexyl, octyl and decyl.
  • CSMA DCC- 01 An Automatic Dishwashing Foam Test (CSMA DCC- 01) and Glassware Deposition Rinse Test (CSMA DCC- 05A) were used to evaluate the product of this invention. Comparisons were made to SLF-18, a proprietary Olin Product, Cascade, a commercial dishwashing detergent (Procter and Gamble) , and to a "biodegradable" auto-dish product as described in U.S. Patent No. 4,925,587 (Henkel) .
  • Glassware was evaluated for spotting, streaking and filming on a scale of 1 to 5 where l shows no spots, streaks or film and 5 indicates complete covering of the item with spots, streaks or film.
  • This methodology uses an exponential scale, not a linear one.
  • Example 5 shows the performance characteristics of a preferred surfactant composition within the scope of the present invention. More specifically, the data presented above shows that the compound of Example 5 exhibits an unexpectedly high egg soil defoaming efficacy as defined by CSMA Method DCC-01, as well as a very low foam generating capacity as defined by Ross Miles
  • Foam Height Test observed for this product type and excellent biodegradability as measured by standardized biodegradability test regimens OECD 301B and OECD 302A.
  • the compound of Example 5 showed greater than 90% mineralization within 28 days using activated sludge in a modified Sturm Test.
  • SCAS semi-continuous activated sludge
  • this product possesses excellent rinse properties as defined by CSMA Method DCC-05A, Glassware Deposition Rinse Test. This combination of properties make it ideal for use as an automatic dishwashing detergent/rinse aid.
  • AtoChem 1,2-epoxydodecane

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  • 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

Composition tensio-active comprenant: (a) un support pouvant être de l'eau, des solvants organiques ou leurs combinaisons, la quantité totale dudit support représentant entre environ 0,01 et 30 % en poids de la composition, et (b) un polyalcool(oxyalcoylé) à coiffe époxyde représenté par la formule: R3O[CH2CH(CH3)O]x(CH2CHR4O)y[CH2CH(OH)R5]z dans laquelle R3 représente un radical linéaire d'hydrocarbure aliphatique présentant une moyenne d'environ 4 à environ 18 atomes de carbone, et ses mélanges; R4 représente hydrogène ou un alkyle inférieur présentant entre 1 et 6 atomes de carbone; R5 représente un radical linéaire d'hydrocarbure aliphatique présentant une moyenne d'environ 2 à environ 14 atomes de carbone et ses mélanges; x représente 0 ou un entier compris entre 1 et environ 5, y représente un entier compris entre 1 et environ 30, et z représente un entier compris entre 1 et environ 3.
PCT/US1995/012286 1994-10-14 1995-09-25 Tensioactifs biodegradables et leurs melanges en tant qu'auxiliaires de rinçage WO1996012001A1 (fr)

Priority Applications (2)

Application Number Priority Date Filing Date Title
EP95935125A EP0785979A4 (fr) 1994-10-14 1995-09-25 Tensioactifs biodegradables et leurs melanges en tant qu'auxiliaires de rin age
AU37262/95A AU3726295A (en) 1994-10-14 1995-09-25 Biodegradable surfactant and blends thereof as a rinse aid

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US32332394A 1994-10-14 1994-10-14
US323,323 1994-10-14

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WO1996012001A1 true WO1996012001A1 (fr) 1996-04-25

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EP (1) EP0785979A4 (fr)
AU (1) AU3726295A (fr)
TW (1) TW387937B (fr)
WO (1) WO1996012001A1 (fr)

Cited By (22)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1998011186A1 (fr) * 1996-09-11 1998-03-19 The Procter & Gamble Company Compositions pour lave-vaisselle, contenant des tensioactifs non ioniques faiblement moussants et agissant en conjonction avec des enzymes
WO1998011190A1 (fr) * 1996-09-11 1998-03-19 The Procter & Gamble Company Compositions faiblement moussantes pour lave-vaisselle
WO1999013035A1 (fr) * 1997-09-05 1999-03-18 Cognis Deutschland Gmbh Melanges tensio-actifs moussant peu et contenant des hydroxyethers mixtes
EP0916717A1 (fr) * 1997-11-14 1999-05-19 HENKEL-ECOLAB GmbH & CO. OHG Agent de nettoyage de surfaces dures
WO1999027047A1 (fr) * 1997-11-22 1999-06-03 Henkel-Ecolab Gmbh & Co. Ohg Produit pour le nettoyage de surfaces dures
WO2000034424A1 (fr) * 1998-12-08 2000-06-15 Henkel Kommanditgesellschaft Auf Aktien Detergent pour surfaces dures
WO2001055288A1 (fr) * 2000-01-28 2001-08-02 Cognis Deutschland Gmbh & Co. Kg Agents de rincage
WO2001077276A1 (fr) * 2000-04-07 2001-10-18 Basf Aktiengesellschaft Alcoxylates d'alcool utilises comme tensioactifs a faible production de mousse ou a effet antimousse
EP1167499A1 (fr) * 2000-06-29 2002-01-02 Cognis Deutschland GmbH Compositions détergentes liquides contenant des hydroxyéthers mélangés
EP1229104A2 (fr) * 2001-02-01 2002-08-07 Cognis Deutschland GmbH & Co. KG Produit de rinçage et de nettoyage
US6506945B2 (en) 1999-12-08 2003-01-14 The Procter & Gamble Company Process for preparing ether-capped poly(oxyalkylated) alcohol surfactants
US6593287B1 (en) 1999-12-08 2003-07-15 The Procter & Gamble Company Compositions including ether-capped poly(oxyalkylated) alcohol surfactants
US6660706B1 (en) 1998-12-09 2003-12-09 Cognis Deutschland Gmbh & Co. Kg General purpose cleaners
US6686330B2 (en) 1999-12-08 2004-02-03 The Procter & Gamble Company Compositions including ether-capped poly (oxyalkylated) alcohol wetting agents
US6844309B1 (en) 1999-12-08 2005-01-18 The Procter & Gamble Company Ether-capped poly(oxyalkylated) alcohol surfactants
DE102004015392A1 (de) * 2004-03-26 2005-10-20 Henkel Kgaa Maschinelles Geschirrspülmittel
DE102004045685A1 (de) * 2004-09-17 2006-04-06 Henkel Kgaa Reinigungsmittelkomponente
US7098178B2 (en) 2000-03-16 2006-08-29 Henkel Kommanditgesellschaft Auf Aktien (Henkel Kgaa) Silicic acid ester mixtures
US7871971B1 (en) 1998-11-09 2011-01-18 Cognis Ip Management Gmbh Machine dishwashing rinse agents and methods of using the same
US8334323B2 (en) 2008-01-11 2012-12-18 Dow Global Technologies Llc Alkylene oxide-capped secondary alcohol alkoxylates useful as surfactants
US8357823B2 (en) 2008-09-24 2013-01-22 Dow Global Technologies Llc Alkylene oxide capped secondary alcohol ethoxylates as fermentation foam control agents
US10774291B2 (en) 2016-06-16 2020-09-15 Dow Global Technologies Llc Automatic dishwashing compositions with spot prevention surfactant

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Cited By (31)

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WO1998011190A1 (fr) * 1996-09-11 1998-03-19 The Procter & Gamble Company Compositions faiblement moussantes pour lave-vaisselle
WO1998011186A1 (fr) * 1996-09-11 1998-03-19 The Procter & Gamble Company Compositions pour lave-vaisselle, contenant des tensioactifs non ioniques faiblement moussants et agissant en conjonction avec des enzymes
EP1757676A1 (fr) * 1996-09-11 2007-02-28 The Procter and Gamble Company Composition peu moussante pour le lavage de la vaisselle en machine
JP3299979B2 (ja) 1996-09-11 2002-07-08 ザ、プロクター、エンド、ギャンブル、カンパニー 低発泡性自動食器洗浄組成物
US7332466B2 (en) 1997-09-05 2008-02-19 Cognis Deutschland Gmbh & Co. Kg Lightly-foaming tenside mixtures with hydroxy mixed ethers
WO1999013035A1 (fr) * 1997-09-05 1999-03-18 Cognis Deutschland Gmbh Melanges tensio-actifs moussant peu et contenant des hydroxyethers mixtes
EP0916717A1 (fr) * 1997-11-14 1999-05-19 HENKEL-ECOLAB GmbH & CO. OHG Agent de nettoyage de surfaces dures
WO1999027047A1 (fr) * 1997-11-22 1999-06-03 Henkel-Ecolab Gmbh & Co. Ohg Produit pour le nettoyage de surfaces dures
US7871971B1 (en) 1998-11-09 2011-01-18 Cognis Ip Management Gmbh Machine dishwashing rinse agents and methods of using the same
WO2000034424A1 (fr) * 1998-12-08 2000-06-15 Henkel Kommanditgesellschaft Auf Aktien Detergent pour surfaces dures
US6660706B1 (en) 1998-12-09 2003-12-09 Cognis Deutschland Gmbh & Co. Kg General purpose cleaners
US6506945B2 (en) 1999-12-08 2003-01-14 The Procter & Gamble Company Process for preparing ether-capped poly(oxyalkylated) alcohol surfactants
US6593287B1 (en) 1999-12-08 2003-07-15 The Procter & Gamble Company Compositions including ether-capped poly(oxyalkylated) alcohol surfactants
US6844309B1 (en) 1999-12-08 2005-01-18 The Procter & Gamble Company Ether-capped poly(oxyalkylated) alcohol surfactants
US6686330B2 (en) 1999-12-08 2004-02-03 The Procter & Gamble Company Compositions including ether-capped poly (oxyalkylated) alcohol wetting agents
WO2001055288A1 (fr) * 2000-01-28 2001-08-02 Cognis Deutschland Gmbh & Co. Kg Agents de rincage
US6732748B2 (en) 2000-01-28 2004-05-11 Cognis Deutschland Gmbh & Co. Kg Clear rinsing agents
US7098178B2 (en) 2000-03-16 2006-08-29 Henkel Kommanditgesellschaft Auf Aktien (Henkel Kgaa) Silicic acid ester mixtures
JP2003530368A (ja) * 2000-04-07 2003-10-14 ビーエーエスエフ アクチェンゲゼルシャフト 気泡の少ない界面活性剤または起泡抑制界面活性剤としてのアルコールアルコキシレート
US6680412B2 (en) 2000-04-07 2004-01-20 Basf Aktiengesellschaft Alcohol alkoxylates used as low-foam, or foam inhibiting surfactants
KR100863757B1 (ko) * 2000-04-07 2008-10-16 바스프 에스이 저 폼 또는 폼 억제 계면활성제로서 사용되는 알콜알콕실레이트
WO2001077276A1 (fr) * 2000-04-07 2001-10-18 Basf Aktiengesellschaft Alcoxylates d'alcool utilises comme tensioactifs a faible production de mousse ou a effet antimousse
JP4898060B2 (ja) * 2000-04-07 2012-03-14 ビーエーエスエフ ソシエタス・ヨーロピア 気泡の少ない界面活性剤または起泡抑制界面活性剤としてのアルコールアルコキシレート
EP1167499A1 (fr) * 2000-06-29 2002-01-02 Cognis Deutschland GmbH Compositions détergentes liquides contenant des hydroxyéthers mélangés
EP1229104A3 (fr) * 2001-02-01 2002-09-04 Cognis Deutschland GmbH & Co. KG Produit de rinçage et de nettoyage
EP1229104A2 (fr) * 2001-02-01 2002-08-07 Cognis Deutschland GmbH & Co. KG Produit de rinçage et de nettoyage
DE102004015392A1 (de) * 2004-03-26 2005-10-20 Henkel Kgaa Maschinelles Geschirrspülmittel
DE102004045685A1 (de) * 2004-09-17 2006-04-06 Henkel Kgaa Reinigungsmittelkomponente
US8334323B2 (en) 2008-01-11 2012-12-18 Dow Global Technologies Llc Alkylene oxide-capped secondary alcohol alkoxylates useful as surfactants
US8357823B2 (en) 2008-09-24 2013-01-22 Dow Global Technologies Llc Alkylene oxide capped secondary alcohol ethoxylates as fermentation foam control agents
US10774291B2 (en) 2016-06-16 2020-09-15 Dow Global Technologies Llc Automatic dishwashing compositions with spot prevention surfactant

Also Published As

Publication number Publication date
EP0785979A4 (fr) 1999-06-16
TW387937B (en) 2000-04-21
EP0785979A1 (fr) 1997-07-30
AU3726295A (en) 1996-05-06

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