US3764559A - Detergent compositions - Google Patents

Detergent compositions Download PDF

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US3764559A
US3764559A US00112856A US3764559DA US3764559A US 3764559 A US3764559 A US 3764559A US 00112856 A US00112856 A US 00112856A US 3764559D A US3764559D A US 3764559DA US 3764559 A US3764559 A US 3764559A
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percent
weight
salt
copolymer
sodium
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W Mizuno
T Brunelle
L Rue
S Crecelius
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Ecolab Inc
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Economics Laboratory Inc
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    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/37—Polymers
    • C11D3/3746—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • C11D3/3757—(Co)polymerised carboxylic acids, -anhydrides, -esters in solid and liquid compositions

Definitions

  • This invention relates to low foaming detergent compositions for use in automatic dishwashers.
  • laundry detergents for use in automatic dishwashing machines of the type used in homes and in commercial facilities differ from laundry detergents.
  • Laundry detergents usually contain substantial amounts of anionic surface active agents to increase sudsing (foaming) since the fabrics to be washed are immersed in the detergent solution with soil removal being dependent upon emulsification, peptization and mechanical action by tumbling or by means of an agitator.
  • Nitriloacetate salts such as trisodium nitrilotriacetate monohydrate and disodium monohydrogen nitrilotriacetate monohydrate appear to be satisfactory for use in laundry detergents and in non-chlorinated dishwashing detergents.
  • nitriloacetate salts cause rapid degradation of the chlorine releasing agents frequently employed in detergents thus reducing the amount of available chlorine.
  • nitriloacetate salts would be suspected of contributing to nitrogen pollution of rivers and lakes.
  • Dishwashing detergents normally employ a large proportion of inorganic alkaline detergent salts (builders) such as carbonates, bicarbonates, silicates, borates, perborates and phosphates.
  • inorganic salts as sodium chloride and sodium sulfate are also frequently employed as fillers to increase the bulk of the composition.
  • the phosphate salts in addition to providing alkalinity for detergency, serve as water softening agents by chelating or sequestering magnesium and calcium ions present in hard wash water.
  • dishwashing detergents As chelating agents, low molecular weight linear polymers of maleic anhydride with vinylacetate. Structurally these polymeric materials can be represented as follows:
  • M is hydrogen, ammonium or an alkali metal and n is an integer such that the product has a relative viscosity of from 1.0 to 10.0 when determined on a 4 percent aqueous solution at 25 C.
  • the relative viscosity of the said maleic anhydride polymers be relatively low. Since there are certain inherent viscosity differences depending upon the particular polymer product, the preferred relative viscosities will vary; the limiting criteria being that the polymers be susceptible to handling and blending with the other components of the new detergent as well as affording satisfactory performance. For example, with a Vinylacetatemaleic anhydride polymer it is preferred that the relative viscosity range be from 1.0 to 10.0 when determined on a 4 percent aqueous solution at 25 C. (acid form).
  • Vinylacetate-maleic anhydride copolymers are prepared by charging 98.10 grams (1.0 mole) maleic anhydride, 86.06 grams (1.0 mole) vinylacetate, 2.42 grams (0.01 mole benzoyl peroxide and 1,000 milliliters of an organic solvent, such as benzene, toluene, xylene or mixtures thereof, into a suitable reaction vessel.
  • the reaction vessel if not sealed, should be equipped with a reflux condenser, an agitator, a means of heating and a thermometer or other means of determining temperature.
  • the mixture is heated to C. at which time the copolymer begins to form and depending on the solvent system may require cooling.
  • the temperature is maintained at 80-85 C. for l to 5 hours, preferably 2 to 2-V2 hours.
  • the product can be isolated as the anhydride at this stage by filtering the insoluble copolymer. If the acid form of the copolymer is desired, grams of water can be added and the mixture stirred and heated for an additional 30 minutes. The acid form of the copolymer will then precipitate and can be recovered from the solvent. If, for example, the sodium salt form is desired, the addition of sodium hydroxide can be made at the time water is added.
  • the copolymer thus obtained has a relative viscosity at 1.0 to 10.0 (depending on solvent used for the reaction). The viscosity is determined on a 4 percent aqueous solution.
  • the dishwashing detergent compositions of this invention comprise a major proportion of an alkaline detergent salt or salts together with a described linear copolymer of maleic anhydride-vinylacetate.
  • phosphate salts are generally considered to be alkaline detergent salts, such phosphate salts can be employed in the compositions of this invention in reduced amounts H LI lZ wherein Z is the oxyalkylatable material, A is the radical derived from the alkylene oxide which can be, for example, ethylene, propylene, butylene oxide, etc., n is z a be i l g t g ermine ⁇ ?
  • m whlgh a 5 a number determined by the moles of alkylene oxide 15 6 6 use a g 051) 15 reacted, for example 10 to 2000 or more and z is a me a sue as car d s ik "ii" g whole number determined by the number of reactive "P perborates an t l epreSemam/F a 9' oxyalkylatable groups.
  • a nonionic as in e above where 2 1 and chain is sodium orthosilicate, potassium b1carbonate, potasterminated with alkyl or benzyl ether, slum silicates, alkaline condensed phosphate salts such A nonionic such as in d but terminated with benzyl as tetrasodium pyrophosphate or tetrapotasslum pyroether group and phosphate and poll/phosphates Such as sodlum mpoly' h.
  • the mclu slon f know? to the The chlorine-releasing agent provides available chloslfch as sod'um mmte f alummates Zmcates] rine during the washing operation and serves to destain d um mer a tobengothiazol e, etc does not constltt t dishware and reduce film formation on glassware. Repa departure from this invention.
  • the inclusion resemative chlorine releasing agents are in general, of fillers known to the art, such as sodium chloride, soalkali metal polychloro isocyanurates, Sulfate and the l not commute a depar' chloroisocyanuric acid, dichloroisocyanuric acid, soture from the mventlon, dium or potassium dichloroisocyanurate, [(mono tri- Preferred COl'flPOSlIlOI'lS of the nvention also include chloro) tetra (monopotassium dichloronpem a deffammg foammg 9 Surfactant and a taisocyanurate, dichlorodimethyl hydantoin, succincblormefrffleasmg agent' The P 1 t chlorimide, chloramine-T, chloromelamine, chlori- Y' addmonal detergencylwhfle,mamilammg f n
  • the nonionic surfactants are that they exhibit a cloud
  • the composition ofthe dishwashing detergents of the of less than about 45 1 percent concentra' present invention can be summarized as follows: tion in water and a surface tension not lower than about Broad Range Preferred Range dynes/centimeter at 0.1 percent concentration 1n 35 by weight by weight water at 25 C.
  • the surfactants should be low-foaming Non-phosphate Alkaline in nature. As determined by the known Ross-Miles omefgemsahs 95 25 60 f l f f t t h. h Alkaline Phosphate Salt 0 to 10 to 30 03m 351,?
  • the detergent compositions of this invention can be a. Alkyl phenoxy polyethenoxy ethanol, compounded as dry powders by mixing the various b.
  • Alkyl phenoxy polyethenoxy benzyl ether components in dry form.
  • Polyethenoxy polypropenoxy polyethenoxy etha- 45 mers can be added in the anhydride, acid or salt forms,
  • Oxyalkylated compounds of the general formula amounts shown being on a weight percentage basis.
  • EXAMPLE 1 Formulation I of Table I was prepared by blending in a food mixer 12 parts of a liquid nonionic surfactant and 19.0 parts of sodium tripolyphosphate followed by the addition of 29.3 parts soda ash. After several min utes of blending, 29.5 parts of sodium metasilicate were added followed by 1.2 parts of sodium dichloroisocyanurate. After the addition of sodium dichloroisocyanurate the blend was mixed for one minute and stored. Subsequently 24.0 grams of the above blend were charged to a dishwashing machine followed by the addition of a concentrated aqueous solution of the soclium salt of a copolymer of vinylacetate-maleic anhydride.
  • the acid form of this copolymer had a relative viscosity of5.07 when determined on a 4 percent aqueous solution at 25 C.
  • This sodium salt polymer solution was employed in an amount to provide 6. 0 grams (anhydrous basis) of the sodium salt polymer and thus the finished product corresponded to Formulation I of Table I.
  • EXAMPLE 2 1.2 parts of a liquid nonionic defoamer were blended with 30.1 parts of soda ash. After several minutes mixing the blend was free-flowing and uniform and then 29.5 parts of sodium metasilicate were added followed by 1.2 parts of sodium dichloroisocyanurate. The blend was mixed for 1 minute and stored. Subsequently 18.6 grams of the above blend were charged into a dishwater followed by the addition of a concentrated aqueous solution of a sodium vinylacetate maleic copolymer. The acid form of this copolymer had a relative viscosity of 5.07 when determined on a 4 percent aqueous solution at 25 C. This polymer solution was employed in an amount to provide 1 1.4 grams (anhydrous basis) of the polymer and thus the finished product corresponded to Formulation II of Table I.
  • EXAMPLE 3 A formulation corresponding to Formulation VIII of Table I was prepared by blending 25.8 parts of sodium metasilicate and 21.0 parts caustic soda. After the mixture appeared uniform, 3.2 parts of sodium dichloroisocyanurate were added and mixed for an additional 1 minute. Subsequently grams of the above blend were charged into a dishwasher followed by the addition of a concentrated solution of sodium vinylacetate maleate copolymer. This polymer solution was employed in an amount to provide 15 grams of the solid polymer (anhydrous basis) and thus the finished detergent corresponded to Formulation VIII of Table 1.
  • EXAMPLE 4 25.8 parts of sodium metasilicate and 21.0 parts of caustic soda and 25.0 parts of sodium tripolyphosphate were blended together for several minutes until the mixture was uniform. Then 3.2 parts of sodium dichloroisocyanurate were added and the mixture blended for an additional 1 minute. Subsequently, 22.5 grams of the above blend were charged into a dishwasher followed by the addition of a concentrated solution of a sodium vinylacetate maleate copolymer. The acid form of this copolymer had a relative viscosity of 1.42 when determined on a 4 percent aqueous solution at 25 C. This polymer solution was employed in an amount to provide 7.5 grams of the solid and thus the detergent correspond to Formulation IX of Table 1.
  • Formulation I of Table I was prepared by blending in a food mixer 1.2 parts of a liquid nonionic surfactant and 19. 0 parts of sodium tripolyphosphate followed by the addition of 29.3 parts soda ash. After several minutes of blending 29.5 parts of sodium metasilicate and 19.8 parts ofa sodium vinyl-acetate maleate copolymer were added. The acid form of this copolymer had a relative viscosity of 1.42 when determined on a 4 percent aqueous solution at 25 C. When the blend appeared uniform, 1.2 parts of sodium dichloroisocyanurate were added and the blend was mixed for 1 minute and stored. For the evaluation in an automatic dishwashing machine 30 grams of the above blend were charged into the machine. The finished product correspond to Formulation I of Table 1.
  • Formulation VIII of Table I was prepared by blending in a food mixer 50 parts of sodium vinylacetate maleate copolymer, 21 parts of caustic soda, and 25.8 parts of sodium metasilicate. After several minutes of blending 3.2 parts of sodium dichloroisocyanurate were added and the blend was mixed for one minute and transferred to a glass jar for storage. The acid form of the copolymer had a relative viscosity of 1.42 when determined on a 4 percent aqueous solution at 25 C. For evaluation in an automatic dishwashing machine 30 grams of the above blend were charged into the machine. The finished product corresponded to Formulation VIII of Table I.
  • the performance of chelating agents in dishwashing detergents is best evaluated by testing the detergents under dishwashing conditions. This test consisted of racking a home type dishwashing machine with dummy" dishes and glasses plus four clean test glasses racked in appropriate positions. Forty grams of soil (2 lbs. olemargarine creamed with 227 grams of non-fat dried milk solids) are spread equally and uniformly on four 10-inch dinner plates. The dishwashing machine is filled with hot water (l40 F.), charged with 30 grams of test detergent and operated in the wash portion of the cycle for 5 minutes; the machine is emptied and refilled for a 3-minute rinse, followed by another 3-minute rinse. The dishes are allowed to air-dry. This completes a dishwashing cycle. After completion of five such cycles, the glasses are evaluated for filming and spotting. The transparent nature of the glasses makes them more amenable to grading than opaque dishware and furthermore a filmed glass is more conspicuous than a filmed dish.
  • chelating agents employed in dishwashing detergents should not adversely affect chlorinereleasing agents employed therein so as to significantly reduce the amount of available chlorine.
  • a comparison of detergents containing various chelating agents is graphically illustrated in FIGS. 1 and 2.
  • the data plotted in FIG. 1 was determined on detergent formulations dissolved in water at 140 F. at a pH of 11.7. The detergent concentration was 0.5 percent by weight/volume of the test solution.
  • the data plotted in FIG. 2 was determined on formulations dissolved in water at 140 F. at a pH of 12.1. The detergent concentration was 0.5 percent by weight/volume of the test solution.
  • Curve A is a plot of the chlorine available at various times with respect to a detergent formulation similar to Formulation I (Table I) except that all of the maleic anhydride polymer 19.8 parts) was replaced with sodium tripolyphosphate.
  • Curve C is a plot of the chlorine available at various times with respect to a detergent formulation similar to Formulation I (Table I) wherein the chelating polymer is sodium vinylacetate maleate having a relative viscosity of 6.9 when measured in a 4 percent aqueous solution in the acid form.
  • Curve D is a plot of the chlorine available at various times with respect to a detergent formulation similar to Formulation I (Table I) except that the chelating agent employed is trisodium nitriloacetate monohydrate.
  • Curve E is a plot of the chlorine available at various times with respect to a detergent formulation similar to Formulation IX (Table I) except that parts of the maleic anhydride copolymer was replaced with sodium tripolyphosphate.
  • Curve G is a plot of the chlorine available at various times with respect to a detergent formulation-similar to Formulation IX (Table I) wherein the chelating polymer is sodium vinylacetate maleate having a relative viscosity of 6.9 (4 percent aqueous solution of the acid form of the copolymer).
  • Curve H is a plot of the chlorine available at various times with respect to a detergent formulation similar to Formulation IX (Table I) wherein the maleic anhydride copolymer was replaced by an equal weight of trisodium nitriloacetate monohydrate.
  • the low molecular weight linear polymers of maleic anhydride with vinylacetate are employed in dishwashing detergent compositions in accordance with this invention to serve as chelating or sequestering agents for magnesium and calcium ions present in hard water. By serving this important function, it is possible to eliminatc or significantly reduce the amount of phosphate salts normally employed for this purpose.
  • the chelating ability of the polymers employed herein is shown by a comparison with various agents known to possess chelating properties for magnesium and calcium ions.
  • a method for determining the relative chelation values of various chelating agents consists of weighing a known amount of the chelating agent (0.25 to 1 gram), dissolving the agent in about milliliters of distilled water in a 250 milliliter beaker, adding 10 milliliters of 2 percent sodium carbonate, adjusting the pH of the solution to the desired level (if the sample is an anhydride, it is first heated to l00 C.
  • ferric hydroxide is known to form an insoluble precipitate when a ferric salt such as ferric chloride is made alkaline.
  • Many municipal and home supply waters contain varying degrees of iron. Many municipal waters contain on the order of 0.3 parts per million iron, and as high as 1.0 parts per million iron. Many well waters contain as high as several parts per million iron.
  • the iron exists in natural water as ferrous salt and is quickly oxidized by air or oxidizing agents such as hypochlorite to ferric form which then forms insoluble ferric hydroxide when the water is made alkaline such as in an alkaline detergent solution.
  • the iron may discolor clothes or stain dishes. In the latter case where the dishes are rewashed frequently, such as in eating establishments, iron stain may occur when the iron level is as low as 0.2 parts per million.
  • Presently such stained dishes must be processed by immersion in strong, mineral acids muriatic acid being frequently used.
  • the use of an iron sequestering agent in a washing compound is of substantial benefit in such waters containing even a relatively small amount of iron to minimize the need for processing of dishware for iron stain removal.
  • the maleic anhydride derivatives employed in accordance with this invention have been found to possess an unusual ability to prevent ferric hydroxide precipitation.
  • the detergent compositions of this invention are admirably adapted for use in automatic dishwashing equipment of all types.
  • these detergents can be advantageously utilized in laboratory glassware washers, for in-place cleaning of dairy plant equipment and the like and in spray cleaning operations where non-foaming or defoaming detergents are required.
  • the use of the maleic anhydride copolymers in dishwashing detergents affords numerous advantages including l) the ability to sequester hardness ions in water thereby softening the water and improving dishwashing efficiency, 2) reduction in phosphate or nitrogen pollution of lakes and rivers, 3) do not dissipate available chlorine when used in chlorine-containing detergents.
  • a machine dishwashing composition consisting essentially of from about 10 to percent by weight of a non-phosphate alkaline detergent salt, from 0 to 40 percent by weight of an alkaline detergent phosphate salt, from 0 to 8 percent by weight ofa nonionic surfactant which in the Ross-Miles foam test provides an initial foam of not more than about 45 milliliters in height and not more than about 15 milliliter foam height after five minutes, from 0 to 10 percent by weight of a chlorine-releasing agent, from 0 to 40 percent by weight of a neutral inorganic salt, and an amount sufficient for chelation of magnesium and calcium ions ranging from 5 to 65 percent by weight of a copolymer in the acid or salt form of maleic anhydride and vinylacetate in a 1:1 molar ratio, said copolymer having a relative viscosity of from about 1 to 10 when determined at 25 C. on a four weight percent aqueous solution thereof.
  • a machine dishwashing composition consisting essentially of from about 10 to 95 percent by weight of a non-phosphate alkaline detergent salt, from O to 40 percent by weight of an alkaline detergent phosphate salt, from 0 to 8 percent by weight ofa nonionic surfactant which in the Ross-Miles foam test provides an initial foam of not more than about 45 milliliters in height and not more than about 15 milliliter foam height after 5 minutes, from O to 10 percent by weight ofa chlorinereleasing agent, from to 40 percent by weight of a neutral inorganic salt, and an amount sufficient for chelation of magnesium and calcium ions ranging from to 65 percent by weight of an alkali metal salt of a copolymer of maleic anhydride with vinylacetate in a 1:1 ratio, said copolymer having a relative viscosity of from about 1 to when determined at C. on a four weight percent aqueous solution thereof.
  • a machine dishwashing composition consisting essentially of from about 25 to 60 percent by weight of a non-phosphate alkaline detergent salt, from 10 to percent by weight of an alkaline detergent phosphate a copolymer in the acid or salt form of maleic anhydride and vinylacetate in a 1:1 molar ratio, said copolymer having a relative viscosity of from about I to 10 when determined at 25 C. on a four weight percent aqueous solution thereof.

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Cited By (22)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3850832A (en) * 1971-12-17 1974-11-26 Henkel & Cie Gmbh Washing, rinsing and cleansing agent compositions containing furan-maleic anhydride copolymer sequestering agents
US4009110A (en) * 1974-07-16 1977-02-22 Ciba-Geigy Corporation Copolymers of maleic anhydride, diketene and alkyl ethers, process for their manufacture and their use
US4123375A (en) * 1975-11-22 1978-10-31 Henkel Kommanditgesellschaft Auf Aktien Dishwasher detergent with clear rinsing effect and method of machine washing dishes
US4203858A (en) * 1976-05-28 1980-05-20 Gaf Corporation Phosphate-free machine dishwashing composition
US4326979A (en) * 1979-11-09 1982-04-27 Lever Brothers Company Non-aqueous, built liquid detergent composition and method for preparing same
US4388205A (en) * 1980-10-11 1983-06-14 Sandoz Ltd. Phosphate-free cleaning compositions
US4608188A (en) * 1985-04-12 1986-08-26 Basf Corporation Dishwashing composition
US4826618A (en) * 1984-02-22 1989-05-02 Diversey Corporation Stable detergent emulsions
US5266237A (en) * 1992-07-31 1993-11-30 Rohm And Haas Company Enhancing detergent performance with polysuccinimide
US5545348A (en) * 1994-11-02 1996-08-13 Church & Dwight Co., Inc. Non-Phosphate high carbonate machine dishwashing detergents containing maleic acid homopolymer
WO1997043395A1 (en) * 1996-05-10 1997-11-20 The Clorox Company Sequesterants as hypochlorite bleach enhancers
US5714450A (en) * 1996-03-15 1998-02-03 Amway Corporation Detergent composition containing discrete whitening agent particles
US5714451A (en) * 1996-03-15 1998-02-03 Amway Corporation Powder detergent composition and method of making
US5990068A (en) * 1996-03-15 1999-11-23 Amway Corporation Powder detergent composition having improved solubility
US5998351A (en) * 1996-03-15 1999-12-07 Amway Corporation Discrete whitening agent particles method of making, and powder detergent containing same
US6177397B1 (en) 1997-03-10 2001-01-23 Amway Corporation Free-flowing agglomerated nonionic surfactant detergent composition and process for making same
US20050003979A1 (en) * 2003-07-02 2005-01-06 Ecolab Inc. Warewashing composition for use in automatic dishwashing machines, comprising a mixture of aluminum and zinc ions
US20050020464A1 (en) * 2003-07-02 2005-01-27 Smith Kim R. Warewashing composition for use in automatic dishwashing machines, and methods for manufacturing and using
US20080020960A1 (en) * 2006-07-24 2008-01-24 Smith Kim R Warewashing composition for use in automatic dishwashing machines, and method for using
US20090227485A1 (en) * 2002-11-22 2009-09-10 Schneider Advanced Technologies, Inc. Process for stain removal
US9138393B2 (en) 2013-02-08 2015-09-22 The Procter & Gamble Company Cosmetic compositions containing substituted azole and methods for improving the appearance of aging skin
US9144538B2 (en) 2013-02-08 2015-09-29 The Procter & Gamble Company Cosmetic compositions containing substituted azole and methods for alleviating the signs of photoaged skin

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GB1414918A (en) * 1973-02-14 1975-11-19 Ciba Geigy Uk Ltd Treatment of water to prevent the deposition of scale
DE3818660A1 (de) * 1987-06-05 1988-12-15 Colgate Palmolive Co Freifliessendes, pulvriges geschirrwaschmittel und verfahren zur herstellung desselben
GB2234980A (en) * 1989-07-25 1991-02-20 Unilever Plc Detergent composition for machine dishwashers

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US3235505A (en) * 1961-09-20 1966-02-15 Monsanto Co Detergent processes
US3579455A (en) * 1968-08-02 1971-05-18 Grace W R & Co Machine dishwashing compositions containing sodium polyacrylate

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US3579455A (en) * 1968-08-02 1971-05-18 Grace W R & Co Machine dishwashing compositions containing sodium polyacrylate

Cited By (40)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3850832A (en) * 1971-12-17 1974-11-26 Henkel & Cie Gmbh Washing, rinsing and cleansing agent compositions containing furan-maleic anhydride copolymer sequestering agents
US4009110A (en) * 1974-07-16 1977-02-22 Ciba-Geigy Corporation Copolymers of maleic anhydride, diketene and alkyl ethers, process for their manufacture and their use
US4123375A (en) * 1975-11-22 1978-10-31 Henkel Kommanditgesellschaft Auf Aktien Dishwasher detergent with clear rinsing effect and method of machine washing dishes
US4203858A (en) * 1976-05-28 1980-05-20 Gaf Corporation Phosphate-free machine dishwashing composition
US4326979A (en) * 1979-11-09 1982-04-27 Lever Brothers Company Non-aqueous, built liquid detergent composition and method for preparing same
US4388205A (en) * 1980-10-11 1983-06-14 Sandoz Ltd. Phosphate-free cleaning compositions
US4826618A (en) * 1984-02-22 1989-05-02 Diversey Corporation Stable detergent emulsions
US4608188A (en) * 1985-04-12 1986-08-26 Basf Corporation Dishwashing composition
US5266237A (en) * 1992-07-31 1993-11-30 Rohm And Haas Company Enhancing detergent performance with polysuccinimide
US5545348A (en) * 1994-11-02 1996-08-13 Church & Dwight Co., Inc. Non-Phosphate high carbonate machine dishwashing detergents containing maleic acid homopolymer
US6008174A (en) * 1996-03-15 1999-12-28 Amway Corporation Powder detergent composition having improved solubility
US5714450A (en) * 1996-03-15 1998-02-03 Amway Corporation Detergent composition containing discrete whitening agent particles
US5714451A (en) * 1996-03-15 1998-02-03 Amway Corporation Powder detergent composition and method of making
US5990068A (en) * 1996-03-15 1999-11-23 Amway Corporation Powder detergent composition having improved solubility
US5998351A (en) * 1996-03-15 1999-12-07 Amway Corporation Discrete whitening agent particles method of making, and powder detergent containing same
US6080711A (en) * 1996-03-15 2000-06-27 Amway Corporation Powder detergent composition and method of making
US6211131B1 (en) 1996-05-10 2001-04-03 The Clorox Company Sequesterants as hypochlorite bleach enhancers
US6297209B1 (en) * 1996-05-10 2001-10-02 The Clorox Company Sequesterants as hypochlorite bleach enhancers
WO1997043395A1 (en) * 1996-05-10 1997-11-20 The Clorox Company Sequesterants as hypochlorite bleach enhancers
US6177397B1 (en) 1997-03-10 2001-01-23 Amway Corporation Free-flowing agglomerated nonionic surfactant detergent composition and process for making same
US20090227485A1 (en) * 2002-11-22 2009-09-10 Schneider Advanced Technologies, Inc. Process for stain removal
US7824448B2 (en) * 2002-11-22 2010-11-02 Schneider David J Process for stain removal
US20050003979A1 (en) * 2003-07-02 2005-01-06 Ecolab Inc. Warewashing composition for use in automatic dishwashing machines, comprising a mixture of aluminum and zinc ions
US20050020464A1 (en) * 2003-07-02 2005-01-27 Smith Kim R. Warewashing composition for use in automatic dishwashing machines, and methods for manufacturing and using
US7196045B2 (en) 2003-07-02 2007-03-27 Ecolab Inc. Warewashing composition comprising a corrosion inhibitor with Al and Zn ions
US7196044B2 (en) 2003-07-02 2007-03-27 Ecolab, Inc. Warewashing composition for use in automatic dishwashing machines, comprising a zinc ion and aluminum ion corrosion inhibitor
US20070149431A1 (en) * 2003-07-02 2007-06-28 Lentsch Steven E Warewashing composition for use in automatic dishwashing machines, and methods for manufacturing and using
US7829516B2 (en) 2003-07-02 2010-11-09 Ecolab Usa Inc. Warewashing composition comprising a Zn/Al corrosion inhibitor for use in automatic dishwashing machines
US7452853B2 (en) 2003-07-02 2008-11-18 Ecolab Inc. Warewashing composition comprising zinc and aluminum ions for use in automatic dishwashing machines
US20090038649A1 (en) * 2003-07-02 2009-02-12 Ecolab Inc. Warewashing composition for use in automatic dishwashing machines, and methods for manufacturing and using
US7524803B2 (en) 2003-07-02 2009-04-28 Ecolab Inc. Warewashing composition for use in automatic dishwashing machines comprising an aluminum/zinc ion mixture
US7135448B2 (en) * 2003-07-02 2006-11-14 Ecolab Inc. Warewashing composition for use in automatic dishwashing machines, comprising a mixture of aluminum and zinc ions
US7638473B2 (en) 2003-07-02 2009-12-29 Ecolab Inc. Warewashing composition for use in automatic dishwashing machines, and methods for manufacturing and using
US20060270580A1 (en) * 2003-07-02 2006-11-30 Ecolab Inc. Warewashing composition for use in automatic dishwashing machines, and methods for manufacturing and using
US20100242997A1 (en) * 2006-07-24 2010-09-30 Ecolab Usa Inc. Method for using warewashing composition in automatic dishwashing machines
US7759299B2 (en) 2006-07-24 2010-07-20 Ecolab Inc. Warewashing composition for use in automatic dishwashing machines
US20080020960A1 (en) * 2006-07-24 2008-01-24 Smith Kim R Warewashing composition for use in automatic dishwashing machines, and method for using
US7858574B2 (en) 2006-07-24 2010-12-28 Ecolab Usa Inc. Method for using warewashing composition comprising AI and Ca or Mg IONS in automatic dishwashing machines
US9138393B2 (en) 2013-02-08 2015-09-22 The Procter & Gamble Company Cosmetic compositions containing substituted azole and methods for improving the appearance of aging skin
US9144538B2 (en) 2013-02-08 2015-09-29 The Procter & Gamble Company Cosmetic compositions containing substituted azole and methods for alleviating the signs of photoaged skin

Also Published As

Publication number Publication date
DE1961959A1 (de) 1970-11-26
FR2025760A1 (enrdf_load_stackoverflow) 1970-09-11
GB1292120A (en) 1972-10-11
SE366340B (enrdf_load_stackoverflow) 1974-04-22

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