US3351558A - Detergent composition containing organic phosphonate corrosion inhibitors - Google Patents

Detergent composition containing organic phosphonate corrosion inhibitors Download PDF

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US3351558A
US3351558A US577149A US57714966A US3351558A US 3351558 A US3351558 A US 3351558A US 577149 A US577149 A US 577149A US 57714966 A US57714966 A US 57714966A US 3351558 A US3351558 A US 3351558A
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acid
alkyl
corrosion
sodium
carbon atoms
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Zimmerer Roger Earl
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Procter and Gamble Co
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Procter and Gamble Co
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Priority to US577149A priority patent/US3351558A/en
Priority to NL666613889A priority patent/NL152599B/xx
Priority to FR78475A priority patent/FR1510869A/fr
Priority to GB44925/66A priority patent/GB1131738A/en
Priority to BE687958D priority patent/BE687958A/xx
Priority to AT947966A priority patent/AT272482B/de
Priority to DE19661617181 priority patent/DE1617181A1/de
Priority to CH1491866A priority patent/CH539115A/de
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    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F5/00—Softening water; Preventing scale; Adding scale preventatives or scale removers to water, e.g. adding sequestering agents
    • C02F5/08—Treatment of water with complexing chemicals or other solubilising agents for softening, scale prevention or scale removal, e.g. adding sequestering agents
    • C02F5/10—Treatment of water with complexing chemicals or other solubilising agents for softening, scale prevention or scale removal, e.g. adding sequestering agents using organic substances
    • C02F5/14—Treatment of water with complexing chemicals or other solubilising agents for softening, scale prevention or scale removal, e.g. adding sequestering agents using organic substances containing phosphorus
    • 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
    • C11D1/02—Anionic compounds
    • C11D1/34—Derivatives of acids of phosphorus
    • C11D1/342—Phosphonates; Phosphinates or phosphonites
    • 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
    • C11D3/0005—Other compounding ingredients characterised by their effect
    • C11D3/0073—Anticorrosion compositions
    • 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
    • C11D3/36—Organic compounds containing phosphorus
    • C11D3/361—Phosphonates, phosphinates or phosphonites
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
    • C23F11/00—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent
    • C23F11/06—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent in markedly alkaline liquids
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
    • C23F11/00—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent
    • C23F11/08—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent in other liquids
    • C23F11/10—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent in other liquids using organic inhibitors
    • C23F11/167—Phosphorus-containing compounds
    • C23F11/1676—Phosphonic acids

Definitions

  • This invention relates to detergent compositions comprising certain detergent builders which are very corrosive towards aluminum, German silver and Zamac. Specifically, this invention relates to detergent compositions which have been inhibited against the corrosion of Zamac and, optionally, aluminum and/ or Germany silver by the presence of certain corrosion inhibitors including specific organic phosphonate corrosion inhibitors.
  • Zamac is a common alloy containing zinc which is particularly used in washing machine pumps.
  • Zamac is a zinc alloy containing, e.g., 4% aluminum, 0.04% magnesium, balance zinc.
  • Zamac #3 the most commonly used Zamac, is described on page 1169 of Metals Handbook, 8th ed., vol.
  • alkali metal silicates such as sodium silicate having a ratio of SiO :Na O of about 1.6
  • German silver corrosion inhibitor such as benzotriazole.
  • the alkali silicates are extremely eflicient with respect to preventing the corrosion of aluminum and the benzotriazole is very efficient with respect to preventing the corrosion of German silver. Furthermore, they are relatively inexpensive in effective amounts.
  • the sodium silicate and benzotriazole do not prevent these compositions from corroding Zamac and when certain very effective detergency builders and chelating agents such as sodium nitrilotriacetate are present in detergent compositions this Zamac corrosion is completely unacceptable. Therefore, it is necessary to include in such compositions a corrosion inhibitor which will prevent the corrosion of the Zamac especially when the compositions contain the more effective detergency builders such as sodium nitrilotriacetate.
  • a detergent composition comprising (1) from 1% to 98% of the composition of a detergency builder selected from the group consisting of watersoluble amino polycarboxylate, tripolyphosphate and polyphosphonate detergency builders and mixtures thereof; and
  • a corrosion inhibiting compound having the formula wherein R is selected from the group consisting of (l) a straight alkyl chain with the phosphorus atom attached to secondary carbon atoms on the chain, said straight chain alkyl radical containing from about 12 to about 24 carbon atoms and (2) straight chain alkyl benzyl groups wherein the alkyl group contains from about 9 to about 18 carbon atoms and wherein Q is a water-solubilizing cation, said detergent composition being inhibited with respect to the corrosion of Zamac.
  • Alkyl as used herein, includes saturated and unsaturated alkyl groups.
  • a detergency builder selected from the group consisting of Water-soluble amino polycarboxylates, tripolyphosphates, polyphosphonates and mixtures thereof;
  • R is selected from the group consisting of (1) a straight alkyl chain radical with the phosphorus atom attached to secondary carbon atoms on the chain, said straight chain alkyl radical containing from about 12 to about 24 carbon atoms and (2) straight chain alkyl benzyl groups wherein the alkyl group contains from about 9 to about 18 carbon atoms and wherein Q is a water-solubilizing cation, e.g., a cation selected from the group consisting of hydrogen, alkali metal, ammonium and substituted ammonium cations;
  • an organic detergent selected from the group consisting of nonionic, anionic, amphoteric, and zwitterionic detergents, and mixtures thereof;
  • Typical amino polycarboxylate detergency builders include alkali metal (sodium, potassium, etc.), ammonium and substituted ammonium (substituted ammonium, as used herein, includes mono-, diand triethanol ammonium cations) salts of the following acids: ethylenediaminetetraacetic acid, N (2 hydroxyethyl)-ethylenediaminetriacetic acid, N-(2-hydroxyethyl)-nitrilodiacetic acid, diethylenetriaminepentaacetic acid, 1,2 diarninocyclohexanetetraacetic acid and nitrilotriacetic acid.
  • the above amino polycarboxylate detergency builders are amino poly'acetates.
  • NTA water soluble salts of nitrilotriacetic acid
  • EDTA water-soluble salts of ethylenediaminetetraacetic acid
  • Polyphosphonates are also valuable builders in terms of the present invention including specifically sodium and potassium salts of methylene diphosphonic acid, sodium and potassium salts of ethylene diphosphonic acid, sodium and potassium salts of ethane-l-hydroxy-l,1-diphosphonic acid and sodium and potassium salts of ethane-1,1,2-triphosphonic acid.
  • water-soluble salts of ethane- 2-carboxy-1,1-diphosphonic acid hydroxyrnethanediphosphonic acid, carbonyldiphosphonic acid, ethane-l-hydrxy-1,1,2-triphosphonic acid, ethane-Z-hydroxy-1,1,2-triphosphonic acid, propane-1,1,3,3-tetraphosphonic acid, propane-l,1,2,3-tetraphosphonic acid, and propane-1,2,2, 3-tetraphosphonic acid.
  • detergency builders include sodium and potassium tripolyphosphates.
  • detergency builder compounds normally make up from about 1% to about 90%, preferably from about to about 60%, of the composition.
  • the detergency builder compounds are preferably present in a ratio of detergency builder compounds to any detergent surfactant used in the composition of from about 1:2 to about 10:1.
  • These detergency builder compounds attack aluminum, German silver and Zamac when applied as aqueous solutions to these metals.
  • silicate corrosion inhibitor defined hereinbefore is the typical corrosion inhibitor which is well known to those skilled in the art. It'can be present in the detergency compositions of this invention in an amount from about 1% to about preferably from about 2% to about 10%.
  • a typical silicate corrosion inhibitor is sodium silicate having an SiO :Na O ratio of about 1.6.
  • This silicate corrosion inhibitor prevents the corrosion of .aluminum but 'is essentially ineffective in preventing or substantially reducing the "corrosion of zinc alloys such as Zamac by, e.g., NTA regardless of the level at which the silicate corrosion inhibitor 'is used.
  • the silicate corrosion inhibitor is an essential ingredient in the preparation of a general purpose detergent composition at the least cost since the phosphonate corrosion inhibitor is not effective in preventing the corrosion of aluminum and German 'silver at levels below about 2% as specified hereinafter. The phosphonate is more expensive than silicate.
  • silicate corrosion inhibitors which contain more carbon atoms will prevent the corrosion of aluminum and German silver-in addition to Zamac when used at higher levels, e.g., above about 2%. However, in some cases, it would be unduly expensive to provide sufficient phosphonate corrosion inhibitor 'for this purpose. Therefore, some silicate corrosion inhibitor is always preferred for general purpose detergents for inhibition of aluminum corrosion, although with larger amounts of higher molecular Weight phosphonate corrosion inhibitors, silicate is an optional ingredient insofar as aluminum corrosion is concerned.
  • the phosphonate corrosion inhibitors which are effective at higher levels in inhibiting the corrosion of aluminum in addition to Zamac are those alkyl phosphonates and phosphonic acids wherein the alkyl group contains at least about 18 carbon atoms and alkyl benzyl phosphonates and phosphonic acids wherein alkyl benzyl groups contain at least about 20 carbon atoms.
  • These larger, more effective phosphonate corrosion inhibitors when used at levels above about 2%, preferably from about 2% to about 6%, inhibit the corrosion of aluminum and German silver by the effective detergency builders described hereinbefore.
  • the choice of the detergency builders with which the phosphonate corrosion inhibitors of this invention are uniquely effective at higher levels in preventing the corrosion of aluminum is dependent upon two factors.
  • the first factor relates to the efficiency of the detergency builder in sequestering the alkaline earth metal ions, e.g., calcium ions, present in hard water. If the free (not sequestered) calcium ion concentration in the builder solution is sufficiently large to insolubilize the corrosion inhibiting compounds by forming the calcium salt, then the corrosion inhibiting properties of the compounds are destroyed.
  • Builders such as sodium orthophosphate apparently do not sequester calcium ions sufficiently to prevent insolubilization of the corrosion inhibiting compounds.
  • the corrosion inhibiting compounds must be soluble to be etfective.
  • the second factor relates to the size of the detergency builder molecule.
  • the builder molecule is too small (e.g., the alkali metal pyrophosphate builder salts) then it will slip through the film of corrosion inhibitor as hereinafter more fully described.
  • the tripolyphosphate, polyphosphonate, and aminopolycarboxylate builders used in the compositions of this invention have 'suflicient sequestering properties to maintain proper inhibitor solubility and sufficient molecular bulk to permit proper inhibition.
  • the corrosion inhibitors of the present invention are effective with respect to the inhibition of corrosion of Zamac, aluminum, and German silver because the hydrophobic group '(R-) is attached to the 'hydrophilic group 3 when) in a bulky manner.
  • This bulkiness is achievedin several ways.
  • a straight chain alkyl hydrophobic portion (R-) of the corrosion inhibiting compound is attached to the hydrophilic group through a secondary carbon atom.
  • bulkiness is achieved by incorporating an aryl group such as a benzyl group into the hydrophobic group.
  • the alkyl chains can contain a certain amount of unsaturation and/or branching.
  • Random refers to an essentially even distribution of isomers. In some instances there will be essentially no l-isomer and in other instances there may be a slightly greater amount of l-isomer than would be present in a completely random distribution as a result of the processes used in preparing the phosphonates.
  • the most important results of this bulky attachment is to increase the solubility of the compounds in water, especially in the form of their alkaline earth metal (e.g., calcium and magnesium) salts.
  • the bulkier attachments for example, where the hydrophilic group is attached near the center of straight alkyl chains are therefore preferred. If the corrosion inhibiting compound is not sufiiciently soluble, then the compound will precipitate in the presence of free calcium and magnesium ions prior to forming the protective film on the metal.
  • Corrosion inhibitors wherein the phosphonate or phosphate group is attached to a relatively unbranched (straight chain) hydrophobic group at a terminal position precipitate in the presence of free calcium and magnesium and hence cannot form a sufficiently tenacious film to prevent the sequestering builders, e.g., STP, from reaching the surface.
  • the phosphonate corrosion inhibitors of this invention can be prepared in several ways. For example, phosphorus trichloride, oxygen and a paraffin containing about 18 carbon atoms can be reacted together and the reaction product hydrolyzed to give the phosphonic acid.
  • Randomly phosphonated octadecane such as the product prepared by reacting diisopropyl phosphite with a random olefin containing an average of 18 carbon atoms in the presence of a free radical initiator and thereafter pyrolyzing the phosphonate ester to give the phosphonic acid.
  • phosphonate corrosion inhibitors include:
  • Alkylbenzylphosphonic acid mixtures wherein the alkyl groups can be derived from (1) a mixture of propylene polymers, (2) olefins derived from cracked petroleum Waxes, or (3) olefins displaced from Ziegler-type buildup reactions of ethylene, said alkyl groups ranging in size from 12 to 21 carbon atoms and averaging from about 14 to 18 carbon atoms;
  • Hexadecylbenzylphosphonic acid wherein the hexadecyl group is derived from polymerized isobutylene;
  • Alkylbenzylphosphonic acids wherein the alkyl group is derived from a chlorinated kerosene fraction averaging from about 15 to about 18 carbon atoms;
  • the mixture of octadecylphosphonic acids prepared by alkylating dibutyl phosphonate anion with the mixture of 2- through 9-octadecyl sulfuric acids obtained by reacting l-octadecene with excess sulfuric acid at 0-10 C. for about two to three hours and hydrolyzing the alkylated dibutyl phosphonate anion (this product is a random octadecylphosphonic acid containing a mixture of 2-9 isomers);
  • hydrolyzed reaction product of l-octadecene, phosphorus trichlon'de and oxygen (these hydrolyzed reaction products are a mixture of saturated and unsaturated phosphonic acids and saturated alkyl phosphates, some of the saturated phosphonic acids contain bound chlorine);
  • hydrolyzed reaction product of l-octadecene, phosphorus trichloride, acetic anhydride and oxygen (this hydrolyzed reaction product is a mixture of saturated and unsaturated octadecylphosphonic acids and saturated octadecylphosphates, some of the saturated phosphonic acids contain bound chlorine); and
  • the phosphonate corrosion inhibitors of this invention are effective at preventing the corrosion of Zamac in extremely small amounts (more than 0.05% and less than 2%, preferably about 0.1%) whereas the corresponding phosphates and, especially, phosphonate esters are relatively ineffective, when used at the same levels. Also, phosphates and phosphonate esters are much less eifective in preventing the corrosion of aluminum when used in amounts above about 2%.
  • the mixture of silicate corrosion inhibitor and phosphonate corrosion inhibitors is more effective than the phosphonate corrosion inhibitor alone in the protection of Zamac. Similarly, the mixture of silicate corrosion inhibtor and phosphonate corrosion inhibitor are more effective than either alone in the protection of aluminum. This is particularly true With respect to die cast aluminum.
  • the corrosion inhibitors effective against German silver are exemplified by benzotriazole. Many other examples of effective compounds are disclosed in US. Patents 2,618,603, 2,618,605, 2,618,606, and 2,618,608. If substantial amounts of, e.g. alkali metal perborate salts are present in the composition the German silver corrosion inhibitor is not required.
  • the corrosion inhibitors of this invention are effective in the presence of a wide variety of detergent surfactants which are optionally utilized with the detergency builders. These detergent surfactants are present in an amount from 0% to about 40%, preferably from about 10% to about 20% of the detergent composition.
  • detergent surfactants which can be used include:
  • Ordinary alkali metal soaps such as the sodium and potassium salts of the higher fatty acids of naturally occurring plant or animal esters (e.g., palm oil, coconut oil, babassu oil, soybean oil, castor oil, tallow, Whale and fish oils, grease and lard, and mixtures thereof) or of synthetically produced fatty acids (e.g., rosin and those resin acids in tall oil) and/or of naphthentic acids.
  • Sodium and potassium soaps can be made by direct saponification of the fats and oils or by the neutralization of the free fatty acids which are prepared in a separate manufacturing process.
  • Synthetic organic detergents characterized by their high solubility in water, their resistance to precipitation by the constituents of hard water and their surface active and effective detergent properties, including:
  • Anionic synthetic detergents (excluding true soaps): This class of synthetic detergents can be broadly described as the water-soluble salts, particularly the alkali metal (sodium, potassium, etc.) salts, of organic sulfuric reaction products having in the molecular structure an alkyl radical containing from about 8 to about 22 carbon atoms and a radical selected from the group consisting of sulfonic acid and sulfuric acid ester radicals.
  • Nonionic synthetic detergents This class of synthetic detergents may be broadly defined as compounds produced by the condensation of alkylene oxide groups (hydrophilic in nature) with an organic hydrophobic compound, which may be aliphatic or alkyl aromatic in nature. The length of the hydrophilic or polyoxyalkylene radical which is condensed with any particular hydrophobic group can be readily adjusted to yield a watersoluble compound having the desired degree of balance between hydrophilic and hydrophobic elements.
  • Pluronic a well known class of nonionic synthetic detergents is made available on the market under the trade name of Pluronic. These compounds are formed by condensing ethylene oxide Wth a hydrophobic base formed by the condensation of propylene oxide with propylene glycol.
  • Wth a hydrophobic base formed by the condensation of propylene oxide with propylene glycol.
  • the hydrophobic portion of the molecule which, of course, exhibits water insolubility has a molecular weight of from about 1500 to 1800.
  • the addition of polyoxyethylene radicals to this hydrophobic portion tends to increase the water solubility of the molecule as a whole and the liquid character of the products is retained up to the point where the polyoxyethylene content is about 50% of the .total weight of the condensation product.
  • nonionic synthetic detergents include:
  • the polyethylene oxide condensates of alkyl phenols, e.-g., the condensation products of alkyl phenols having an alkyl group containing from about 6 to 12 'carbon atoms in either a straight chain or branched chain configuration, with ethylene oxide, the said ethylene oxide being present in amounts equal to to 25 moles of ethylene oxide per mole of alkyl phenol.
  • the alkyl substituent in such compounds may be derived from polymerized propylene, diisobutylene, octane, or nonane, for example.
  • R R R N- O Long chain tertiary amine oxides (nonionic detergents) corresponding to the following general formula, R R R N- O, wherein R contains an alkyl alkenyl or monohydroxy alkyl radical of from about 8 to about 18 carbon atoms from 0 to about 10 ethylene oxide moieties, and from 0 to 1 glyceryl moiety, and R and R contain from 1 to about 3 carbon atoms and from 0 to about 1 hydroxy group, e.g., methyl, ethyl, propyl, hydroxy ethyl, or hydroxy propyl radicals.
  • the arrow in the formula is a conventional representation of a semi-polar bond.
  • amine oxides suitable for use in this invention include dimethyldodecyl amine oxide, oleyldi(2-hydroxyethyl) amine oxide, dimethyloctylamine oxide, dimethyldecylamine oxide, dimethyltetradecylamine oxide, 3,6,9-trioxaheptadecyldiethylamine oxide, di.(2.-hydroxy.- ethyl) tetradecylamine oxide, 2-dodecoxy ethyl dimethy lamine oxide, 3-dodecoxy-2-hydroxy propyl di( 3-hydroxypropyl)-amine oxide, dimethylhexadecylamine oxide.
  • RRR"P O Long chain tertiary phosphine oxides (nonionic detergents) corresponding to the following general formula RRR"P O wherein R contains an alkyl, alkenyl or monohydroxyalkyl radical ranging from 8 .to 18 carbon atoms in chain length, from 0 to about 10 ethylene oxide moieties and from 0 to 1 glyceryl moiety and R and R" are each alkyl or monohydroxyalkyl groups containing from 1 to 3 carbon atoms.
  • R and R" are each alkyl or monohydroxyalkyl groups containing from 1 to 3 carbon atoms.
  • the arrow in the formula is a conventional representation of a semi-polar bond. Examples of suitable phosphine oxides are:
  • Ampholytic synthetic detergents can be broadly described as derivatives of aliphatic secondary and tertiary amines in which the aliphatic radical can be straight chain or branched and wherein one of the aliphatic substituents contains from about 8 to about 18 carbon atoms and one contains an anionic water solubilizing group, e.g., carboxy, sulfonate, sulfate,
  • Examples of compounds falling within this definition are sodium 3-dodecylaminopropionate, sodium 3- dodecylaminopropane sulfonate, dodecyl beta alanine, N-alkyl-taurines such as the one prepared by reacting dodecylamine with sodium isethionate according to the teaching of US. 2,658,072, N-higher alkyl aspartic acids such as those produced according to the teaching of US. 2,438,091, and the products sold under the trade name Miranol and described in US. Patent 2,528,378.
  • Zwitterionic synthetic detergents can be broadly described as derivatives of aliphatic quaternary ammonium, phosphonium, and sulfonium compounds, in which the aliphatic radicals can be straight chain or branched, and wherein one of the aliphatic substituents contains from about 8 to 18 carbon atoms and one contains an anionic water solubilizing group, e.g., carboxy, sulfonate, sulfate, phosphate, or phosphonate.
  • a general formula for these compounds is:
  • R contains an alkyl, alkenyl, or hydroxy alkyl radical of from about 8 to about 18 carbon atoms, from to about 10 ethylene oxide moieties and from 0 to 1 glyceryl moiety;
  • Y is selected from the group consisting of nitrogen, phosphorous, and sulfur atoms;
  • R is an alkyl or monohydroxy alkyl group containing 1 to about 3 carbon atoms;
  • x is 1 when y is a sulfur atom and 2 when y is a nitrogen or phosphorous atom,
  • R is an alkylene or hydroxy alkylene of from 1 to about 4 carbon atoms and
  • Z is a radical selected from the group consisting of carboxylate, sulfonate, sulfate, phosphonate, and phosphate groups.
  • Examples of compounds falling within this definition are 3-(N,N-dimethyl-N-hexadecylammonio) propane-l-sulfonate and 3-(N,N-dimethyl-N-hexadecylammonio)-2-hydroxy propane-l-sulfonate which are especially preferred for their excellent cool water detergency characteristics.
  • the alkyl groups contain in said detergent surfactants can be straight or branched preferably straight and saturated or unsaturated as desired.
  • the above list of detergent surfactants is exemplary and not limiting. Mixtures of the above detergent surfactants can be used.
  • the detergent compositions of this invention can be 10 prepared in any suitable physical form such as granules (e.g., either spray dried or mechanically mixed), tablets, pastes or liquids.
  • compositions can contain particulate inorganic salts which are inert to the formula to act as fillers.
  • examples of such salts include sodium sulfate and sodium chloride.
  • Soil suspending agents such as sodium carboxymethylcellulose, optical brighteners, dyes, germicidal agents, suds depressants, and suds boosters, can each be added in amounts up to about 10% by weight of the composition.
  • the products of this invention can be used in aqueous solutions at levels of from about 0.05% to about 1.0% and when articles made from Zamac are contacted with these solutions there is considerably less corrosion than when similar compositions which do not contain the specific phosphonate corrosion inhibitor of this invention are used.
  • a spray dried granular detergent having the following composition was prepared by mixing the individual ingredients in a conventional manner with sufiicient water to form a detergent slurry and spray drying the slurry to remove excess moisture and to form detergent granules.
  • Percent Sodium straight chain alkyl benzene sulfonate having an average chain length of about 13 carbon A similar detergent composition was prepared which contained as an additional ingredient 0.3% or random octadecylphosphonic acid prepared by adding phosphorous acid to a random mixture of octadecenes using gamma radiation as a source of radicals.
  • the random olefins were prepared by isomerizing l-octadecene with 10% iron pentacarbonyl at about 150 C. for approximately one hour.
  • the added octadecylphosphonic acid replaced proportionate percentages of the ingredients in the first detergent composition.
  • compositions are useful as detergents at a level of about 0.1% in water detergents and are inhibited against the corrosion of Zamac.
  • EXAMPLE XV Aluminum plates were allowed to stand in an aqueous solution containing 0.35% of a detergent composition consisting of sodium tetrapropylene benzene sulfoate, 5 0% sodium tripolyphosphate, sodium sulfate and 5% of the below-named inhibitors. All percents herein are "by weight.
  • the aluminum plates were exposed to the aqueous detergent solution for a period of three hours at 140 F. and pH 9.5. The water was not agitated. After the three-hour period, the aluminum plates were rinsed with water, the corrosion products removed with cone. HNO then rinsed with water and alcohol, dried and the weight l ss det r ed in mil i ams pe quare n meter. Results were obtained for both soft water and water containing hardness (equivalent to calcium carona o 7 ra ns pe g l on.
  • This hydrolyzed reaction product is a mix-, ture of saturated and unsaturated octadecylphosphonic acids and saturated octadecylphosphates. Some of the saturated phosphoni'c acids contain bound chlorine)" *The saturated alkyl phosphonic acid content was greater thanBOZ, of the reaction product.
  • alkylbenzylphosphonic acid mixtures wherein the alkyl groups can be derived from (1) a mixture of propylene polymers, (2) olefins derived from cracked petroleum waxes, or (3) olefins displaced from Ziegler-type buildup reactions of ethylene, said alkyl groups ranging in size from 12 to 21 carbon atoms and averaging 14, 15, 16, Or 18 carbon atoms;
  • Hexadecylbenzylphosphonic acid wherein the hexadecyl group is derived from polymerized isobutylene;
  • Alkylbenzylphosphonic acids wherein the alkyl group is derived from a chlorinated kerosene fraction averaging 15, 16, 17, or 18 carbon atoms;
  • the mixture of octadecylphosphonic acids prepared by alkylating dibutyl phosphonate anion with the mixture of 2'- through 9-octadecyl sulfuric acids obtained by reacting l-octadecene with excess sulfuric acid at 0-l0 C. for about two to three hours and hydrolyzing the alkylated dibutyl phosphonate anion;
  • anionic synthetic detergents wherein the cations are sodium, potassium, ammonium, monoethanolammonium, diethanolammonium, triethanolammoniurn cations.
  • N-higher alkyl aspartic acids wherein the alkyl group contains about 12 carbon atoms;
  • Detergent compositions consisting essentially of: (1) from 1% to about 98% of the composition of a detergency builder selected from the group consisting of water-soluble amino polyacetate, tri olyphosphate and polyphosphonate detergency builders and mixtures thereof; (2) more than 0.05% and less than about 25% by weight of the total detergent composition of a corrosion inhibitor having the formula wherein R is selected from the group consisting of (1) a straight alkyl chain with the phosphorus atom attached to secondary carbon atoms on the chain, said straight chain alkyl radical containing from about 24 carbon atoms and (2) straight chain alkyl benzyl groups wherein the alkyl group contains from about 9 to about 18 carbon atoms and wherein Q is a water-solubilizing cation selected from the group consisting of hydrogen, alkali metal, ammonium, monoethanol-ammoniurn, diethanolamrnonium, and triethanolammonium cations;
  • an organic detergents selected from the group consisting of nonionic, anionic, amp holytic and zwitterionic detergents and mixtures thereof in an amount
  • Such t h ratio o tot-a si c sc ty bu s to organic detergent ranges from about 1:2 to about 10 1 and in an ount .nqtsteate n bo of the composition, said detergent composition being inhibited with respect to the cQrrosion of Zamac.
  • the detergent composition of claim 1 consisting essentially of:
  • composition of a detergency'builder selected from the group consisting of water-soluble amino polyacetate, tripolyphosphate and polyphosphonate detergency builders andmixtures thereof;
  • R is el stssl from the: oup cons t ng of ('1) a straight alkyl chain radical with the phosphorous atom attached to secondary carbon atoms on the chain, saidstraight chain alkyl radical containing from about 12 to about 24 carbon atoms and (2) s a h 9 i a k b nz g u s whe ei the alkyl group contains from about 9 to about 18 carbon a oms;
  • detergency builders selected from the group consisting of alkali metal pyrophosphates, orthophosphates, tetrabo-rates, perborates, hexaphosphates, sesquicarbonates and bicarbon-ates and mixtures thereof;
  • an organic detergent in an amount such that the ratio of total detergency builders to organic detergent ranges from about 1:2 to about 10:1 and in an amount not greater than about 40% of the composition;
  • the detergency builder (1) is selected from the group consisting of the alkali metal, ammonium and substituted ammonium salts of the following acids wherein said substituted ammonium salts are selected from the group consisting of monoethanolammonium, diethanolarrnnonium and triethanolammonium salts: ethylenediaminetetraacetic acid; N-(Z-hydroxyethyl)-ethylenediaminetriacetic acid; N-(2-hydroxyethyl)-nitrilodiacetic acid; diethylenctriaminepentaacetic acid; 1,2-diamin-ocyclohexanetetraacetic acid; nitrilotriacetic acid; ethylene diphosphonic acid; ethane-l-hydroxy-l,l-diphosphonic acid; ethane- 1,1,2-triphos-phonic acid; ethane-Z-carboxy-1,1-diphosphonic acid; hydroxymethane-di
  • the detergent composition of claim 2 containing as an organic detergent from about 10% to about 20% of a synthetic anionic organic detergent.
  • the detergent composition of claim 2 containing from 0.05% to about 2% of the phosphonate corrosion inhibiting compound (3) and from about 2% to about 10% of said alkali metal silicate.
  • compositions of claim 1 wherein there is at least about 2% by weight of the total detergent composition of corrosion inhibiting compound, said phosphonate corrosion inhibiting compound being selected so that the straight alkyl chain (1) contains at least 18 carbon atoms and the straight chain alkyl benzyl .(2) groups contain at least 20 carbon atoms, the composition being inhibited against the corrosion of aluminum and German silver.
  • compositions of claim 2 wherein there is at least about 2% by weight of the total detergent composition of corrosion inhibiting compound, said corrosi n inhibiting compound being selected so that the straight alkyl chain (1) contains at least 18 carbon atoms and the straight chain alkyl benzyl (2) groups contain at least 20 carbon atoms, the composition being inhibited against the corrosion of aluminum and German silver.
  • the detergent composition of claim 6 wherein the detergency builder is a mixture of water soluble tripolyphosphate and water soluble nitrilotriacetate in a molar ratio of from about 4:1 to about 1:4.
  • the detergent composition of claim 9 wherein the detergency builder is a mixture of sodium tripoly phost phate sodium nitrilotriacetate in a molar ratio of from about 3 :1 to about 1:3.

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US577149A 1966-09-06 1966-09-06 Detergent composition containing organic phosphonate corrosion inhibitors Expired - Lifetime US3351558A (en)

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CA813301A CA813301A (en) 1966-09-06 Detergent composition
US577149A US3351558A (en) 1966-09-06 1966-09-06 Detergent composition containing organic phosphonate corrosion inhibitors
NL666613889A NL152599B (nl) 1966-09-06 1966-09-30 Werkwijze voor het bereiden van een wasmiddel.
FR78475A FR1510869A (fr) 1966-09-06 1966-10-01 Composition détergente comprenant des adjuvants et des inhibiteurs de corrosion
GB44925/66A GB1131738A (en) 1966-09-06 1966-10-07 Detergent composition
BE687958D BE687958A (en)) 1966-09-06 1966-10-07
AT947966A AT272482B (de) 1966-09-06 1966-10-10 Detergensmischung
DE19661617181 DE1617181A1 (de) 1966-09-06 1966-10-14 Detergensmischung
CH1491866A CH539115A (de) 1966-09-06 1966-10-17 Detergensmischung

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Cited By (32)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3617575A (en) * 1966-12-16 1971-11-02 Procter & Gamble Process of treating aqueous solutions with an ethane triphosphonic acid compound
US3622401A (en) * 1970-01-20 1971-11-23 American Cyanamid Co Chemical treatment of metal
US3893943A (en) * 1971-01-20 1975-07-08 Caw Ind Inc Novel catalyst and process for preparing the same
US3923456A (en) * 1973-08-16 1975-12-02 Caw Ind Inc Method of washing textile materials with surface-active agent and catalyst-containing micelles
FR2280706A1 (fr) * 1974-08-01 1976-02-27 Hoechst Ag Concentres d'agents de nettoyage
US4067714A (en) * 1975-07-07 1978-01-10 Caw Industries, Inc. Method of watering plants and/or feeding nutrients to plants
US4070309A (en) * 1976-07-27 1978-01-24 The Procter & Gamble Company Detergent composition
US4105573A (en) * 1976-10-01 1978-08-08 The Procter & Gamble Company Dishwasher detergent composition
US4108889A (en) * 1976-11-19 1978-08-22 The Procter & Gamble Company Preparing alkane phosphonic acids and intermediates
DE2841641A1 (de) * 1978-09-25 1980-04-03 Henkel Kgaa Korrosionsinhibitor fuer saure loesungen
US4239643A (en) * 1979-01-02 1980-12-16 Monsanto Company Peroxide stabilization
US4329396A (en) * 1980-05-27 1982-05-11 Minnesota Mining And Manufacturing Company Corrosion-resistant reflective or transparent-reflective sheet material
EP0151813A3 (en) * 1984-02-16 1985-09-25 Amchem Products, Inc. Compositions and methods for removing selant compositions
US4798675A (en) * 1987-10-19 1989-01-17 The Mogul Corporation Corrosion inhibiting compositions containing carboxylated phosphonic acids and sequestrants
US5225098A (en) * 1992-03-20 1993-07-06 The Procter & Gamble Company Neutral pH freezer bar and process
US5225097A (en) * 1992-03-20 1993-07-06 The Procter & Gamble Company Skin pH freezer bar and process
US5227086A (en) * 1992-03-20 1993-07-13 The Procter & Gamble Company Framed skin pH cleansing bar
US5262079A (en) * 1992-03-20 1993-11-16 The Procter & Gamble Company Framed neutral pH cleansing bar
US5340492A (en) * 1990-11-26 1994-08-23 The Procter & Gamble Company Shaped solid made with a rigid, interlocking mesh of neutralized carboxylic acid
US5425892A (en) * 1991-07-15 1995-06-20 The Procter & Gamble Company Personal cleansing freezer bar made with a rigid, interlocking mesh of neutralized carboxylic acid
US5972860A (en) * 1996-12-11 1999-10-26 Kao Corporation Framed soap composition containing non-ionic surfactant and inorganic salt
US6156715A (en) * 1997-01-13 2000-12-05 Ecolab Inc. Stable solid block metal protecting warewashing detergent composition
US6177392B1 (en) * 1997-01-13 2001-01-23 Ecolab Inc. Stable solid block detergent composition
US6436893B1 (en) 1997-01-13 2002-08-20 Ecolab Inc. Alkaline detergent containing mixed organic and inorganic sequestrants resulting in improved soil removal
US6632291B2 (en) 2001-03-23 2003-10-14 Ecolab Inc. Methods and compositions for cleaning, rinsing, and antimicrobial treatment of medical equipment
US6638902B2 (en) 2001-02-01 2003-10-28 Ecolab Inc. Stable solid enzyme compositions and methods employing them
US6653266B2 (en) 1997-01-13 2003-11-25 Ecolab Inc. Binding agent for solid block functional material
US20080108537A1 (en) * 2006-11-03 2008-05-08 Rees Wayne M Corrosion inhibitor system for mildly acidic to ph neutral halogen bleach-containing cleaning compositions
DE102007040247A1 (de) 2007-08-25 2009-03-05 Evonik Goldschmidt Gmbh Korrosionsinhibitor
US7517846B2 (en) 1991-05-14 2009-04-14 Ecolab Inc. Solid, two part chemical concentrate
WO2009000820A3 (de) * 2007-06-28 2009-06-18 Siemens Ag Korrosionsschützender zusatz für flüssigkeiten
WO2020264234A1 (en) * 2019-06-28 2020-12-30 Ecolab Usa Inc. Surfactant stabilization of hygroscopic species

Families Citing this family (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE2461612C3 (de) * 1974-12-27 1981-08-20 Hoechst Ag, 6000 Frankfurt Rostlösende Reinigungsmittel sowie ein Verfahren zu deren Herstellung
US4582636A (en) * 1984-12-18 1986-04-15 Colgate-Palmolive Co. Concentrated homogeneous built liquid detergent composition
GB2227997B (en) * 1988-12-20 1992-04-15 Grace W R & Co Scale control
DE4237915A1 (de) * 1992-11-10 1994-05-11 Mohndruck Reinhard Mohn Ohg Wischwasserzusammensetzung für das Offsetdruckverfahren
US5888954A (en) * 1993-05-08 1999-03-30 Henkel Kommanditgesellschaft Auf Aktien Corrosion inhibitors for silver
DK2966161T3 (en) 2014-07-08 2019-02-25 Dalli Werke Gmbh & Co Kg ENZYME BLENDIC CATALYST CATEGRANULATE SUITABLE FOR DETERGENT COMPOSITIONS
PL3053997T5 (pl) 2015-02-05 2021-04-06 Dalli-Werke Gmbh & Co. Kg Kompozycja czyszcząca obejmująca katalizator bielenia i karboksymetylocelulozę
EP3075832B1 (en) 2015-03-30 2021-04-14 Dalli-Werke GmbH & Co. KG Manganese-amino acid compounds in cleaning compositions
WO2016177439A1 (en) 2015-05-07 2016-11-10 Novozymes A/S Manganese bleach catalyst / enzyme granules for use in dishwash detergents
EP3190168B1 (en) 2016-01-06 2019-04-10 Dalli-Werke GmbH & Co. KG. Coated bleach catalyst
EP3754003A1 (en) 2019-06-21 2020-12-23 Dalli-Werke GmbH & Co. KG Detergent package unit with a handle
US20230109638A1 (en) 2020-02-28 2023-04-06 Basf Se Automatic dishwashing composition comprising at least one imidazole-based compound

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2618604A (en) * 1949-11-25 1952-11-18 Procter & Gamble Polyphosphate-containing detergent compositions having decreased corrosivity toward aluminum
US2765279A (en) * 1949-03-11 1956-10-02 Metallgesellschaft Ag Shaped mixture of soap and phosphonate
US2892796A (en) * 1956-10-05 1959-06-30 Procter & Gamble Detergent composition containing phosphated alkyl glyceryl ether corrosion and tarnish inhibitor
US3001945A (en) * 1959-04-29 1961-09-26 Procter & Gamble Liquid detergent composition
US3054821A (en) * 1960-05-25 1962-09-18 Standard Oil Co Phosphonic acid esters and preparation thereof
US3159581A (en) * 1962-04-13 1964-12-01 Procter & Gamble Detergency composition

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2765279A (en) * 1949-03-11 1956-10-02 Metallgesellschaft Ag Shaped mixture of soap and phosphonate
US2618604A (en) * 1949-11-25 1952-11-18 Procter & Gamble Polyphosphate-containing detergent compositions having decreased corrosivity toward aluminum
US2892796A (en) * 1956-10-05 1959-06-30 Procter & Gamble Detergent composition containing phosphated alkyl glyceryl ether corrosion and tarnish inhibitor
US3001945A (en) * 1959-04-29 1961-09-26 Procter & Gamble Liquid detergent composition
US3054821A (en) * 1960-05-25 1962-09-18 Standard Oil Co Phosphonic acid esters and preparation thereof
US3159581A (en) * 1962-04-13 1964-12-01 Procter & Gamble Detergency composition

Cited By (51)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3617575A (en) * 1966-12-16 1971-11-02 Procter & Gamble Process of treating aqueous solutions with an ethane triphosphonic acid compound
US3622401A (en) * 1970-01-20 1971-11-23 American Cyanamid Co Chemical treatment of metal
US3893943A (en) * 1971-01-20 1975-07-08 Caw Ind Inc Novel catalyst and process for preparing the same
US3923456A (en) * 1973-08-16 1975-12-02 Caw Ind Inc Method of washing textile materials with surface-active agent and catalyst-containing micelles
US3931031A (en) * 1973-08-16 1976-01-06 Caw Industries, Inc. Surface active compositions
FR2280706A1 (fr) * 1974-08-01 1976-02-27 Hoechst Ag Concentres d'agents de nettoyage
US4067714A (en) * 1975-07-07 1978-01-10 Caw Industries, Inc. Method of watering plants and/or feeding nutrients to plants
US4067713A (en) * 1975-07-07 1978-01-10 Caw Industries, Inc. Method of improving the fertility of soil and the soil thus prepared
US4067712A (en) * 1975-07-07 1978-01-10 Caw Industries, Inc. Method of growing plants in soil
US4067715A (en) * 1975-07-07 1978-01-10 Caw Industries, Inc. Method of transplanting plants
US4070309A (en) * 1976-07-27 1978-01-24 The Procter & Gamble Company Detergent composition
FR2359893A1 (fr) * 1976-07-27 1978-02-24 Procter & Gamble Composition detergente liquide pour lavages delicats
US4105573A (en) * 1976-10-01 1978-08-08 The Procter & Gamble Company Dishwasher detergent composition
US4108889A (en) * 1976-11-19 1978-08-22 The Procter & Gamble Company Preparing alkane phosphonic acids and intermediates
DE2841641A1 (de) * 1978-09-25 1980-04-03 Henkel Kgaa Korrosionsinhibitor fuer saure loesungen
US4239643A (en) * 1979-01-02 1980-12-16 Monsanto Company Peroxide stabilization
US4329396A (en) * 1980-05-27 1982-05-11 Minnesota Mining And Manufacturing Company Corrosion-resistant reflective or transparent-reflective sheet material
EP0151813A3 (en) * 1984-02-16 1985-09-25 Amchem Products, Inc. Compositions and methods for removing selant compositions
US4798675A (en) * 1987-10-19 1989-01-17 The Mogul Corporation Corrosion inhibiting compositions containing carboxylated phosphonic acids and sequestrants
US5340492A (en) * 1990-11-26 1994-08-23 The Procter & Gamble Company Shaped solid made with a rigid, interlocking mesh of neutralized carboxylic acid
US7517846B2 (en) 1991-05-14 2009-04-14 Ecolab Inc. Solid, two part chemical concentrate
US5425892A (en) * 1991-07-15 1995-06-20 The Procter & Gamble Company Personal cleansing freezer bar made with a rigid, interlocking mesh of neutralized carboxylic acid
US5227086A (en) * 1992-03-20 1993-07-13 The Procter & Gamble Company Framed skin pH cleansing bar
US5225097A (en) * 1992-03-20 1993-07-06 The Procter & Gamble Company Skin pH freezer bar and process
US5225098A (en) * 1992-03-20 1993-07-06 The Procter & Gamble Company Neutral pH freezer bar and process
US5262079A (en) * 1992-03-20 1993-11-16 The Procter & Gamble Company Framed neutral pH cleansing bar
US5972860A (en) * 1996-12-11 1999-10-26 Kao Corporation Framed soap composition containing non-ionic surfactant and inorganic salt
US20050119149A1 (en) * 1997-01-13 2005-06-02 Ecolab Inc. Stable solid block detergent composition
US7087569B2 (en) 1997-01-13 2006-08-08 Ecolab Inc. Stable solid block metal protecting warewashing detergent composition
US6410495B1 (en) 1997-01-13 2002-06-25 Ecolab Inc. Stable solid block metal protecting warewashing detergent composition
US6436893B1 (en) 1997-01-13 2002-08-20 Ecolab Inc. Alkaline detergent containing mixed organic and inorganic sequestrants resulting in improved soil removal
US6503879B2 (en) 1997-01-13 2003-01-07 Ecolab Inc. Alkaline detergent containing mixed organic and inorganic sequestrants resulting in improved soil removal
US6583094B1 (en) 1997-01-13 2003-06-24 Ecolab Inc. Stable solid block detergent composition
US6653266B2 (en) 1997-01-13 2003-11-25 Ecolab Inc. Binding agent for solid block functional material
US6660707B2 (en) 1997-01-13 2003-12-09 Ecolab Inc. Stable solid block metal protecting warewashing detergent composition
US6831054B2 (en) 1997-01-13 2004-12-14 Ecolab Inc. Stable solid block detergent composition
US6835706B2 (en) 1997-01-13 2004-12-28 Ecolab Inc. Alkaline detergent containing mixed organic and inorganic sequestrants resulting in improved soil removal
US6156715A (en) * 1997-01-13 2000-12-05 Ecolab Inc. Stable solid block metal protecting warewashing detergent composition
US6177392B1 (en) * 1997-01-13 2001-01-23 Ecolab Inc. Stable solid block detergent composition
US7094746B2 (en) 1997-01-13 2006-08-22 Ecolab Inc. Stable solid block detergent composition
US7341987B2 (en) 1997-01-13 2008-03-11 Ecolab Inc. Binding agent for solid block functional material
US8906839B2 (en) 1997-01-13 2014-12-09 Ecolab Usa Inc. Alkaline detergent containing mixing organic and inorganic sequestrants resulting in improved soil removal
US6638902B2 (en) 2001-02-01 2003-10-28 Ecolab Inc. Stable solid enzyme compositions and methods employing them
US6632291B2 (en) 2001-03-23 2003-10-14 Ecolab Inc. Methods and compositions for cleaning, rinsing, and antimicrobial treatment of medical equipment
US20080108537A1 (en) * 2006-11-03 2008-05-08 Rees Wayne M Corrosion inhibitor system for mildly acidic to ph neutral halogen bleach-containing cleaning compositions
WO2009000820A3 (de) * 2007-06-28 2009-06-18 Siemens Ag Korrosionsschützender zusatz für flüssigkeiten
DE102007040247A1 (de) 2007-08-25 2009-03-05 Evonik Goldschmidt Gmbh Korrosionsinhibitor
EP2033964A2 (de) 2007-08-25 2009-03-11 Evonik Goldschmidt GmbH Korrosionsinhibitor
WO2020264234A1 (en) * 2019-06-28 2020-12-30 Ecolab Usa Inc. Surfactant stabilization of hygroscopic species
AU2020304637B2 (en) * 2019-06-28 2023-01-12 Ecolab Usa Inc. Surfactant stabilization of hygroscopic species
US12269941B2 (en) 2019-06-28 2025-04-08 Ecolab Usa Inc. Surfactant stabilization of hygroscopic species

Also Published As

Publication number Publication date
FR1510869A (fr) 1968-01-26
BE687958A (en)) 1967-04-07
NL152599B (nl) 1977-03-15
DE1617181A1 (de) 1971-02-18
GB1131738A (en) 1968-10-23
AT272482B (de) 1969-07-10
NL6613889A (en)) 1968-04-01
CH539115A (de) 1973-08-31
CA813301A (en) 1969-05-20

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