Classifications

• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B24—GRINDING; POLISHING
  • B24D—TOOLS FOR GRINDING, BUFFING OR SHARPENING
  • B24D3/00—Physical features of abrasive bodies, or sheets, e.g. abrasive surfaces of special nature; Abrasive bodies or sheets characterised by their constituents
• • 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
  • C11D1/345—Phosphates or phosphites
• • 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
  • C11D3/26—Organic compounds containing nitrogen
  • C11D3/33—Amino carboxylic acids
• • 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
  • C11D3/39—Organic or inorganic per-compounds
• • 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
  • C23F11/1673—Esters of phosphoric or thiophosphoric acids

Definitions

• compositions are provided that are especially formulated with a sequestrant for use in hard water, and optionally, a bleaching agent, and that contain a corrosion in- [52] US. Cl ..252/99, 252/89, 252/95, hibitor lessening the tendency of the composition to attack 252/135 252/389 252/DIG' 1 copper, zinc and aluminum. [51] Int. Cl. ..Clld 7/54 [58] Field of Search ..282/99, 89, 135, 389, DIG.
• Sequestrants of the aminocarboxylic acid type such as ethylene diamine tetraacetic acid and nitriloacetic acid, and their alkali metal and amine salts, are capable of reducing the calcium and magnesium ion concentration in hard water to the desired low level, but they strongly increase the corrosive attack of detergent solutions containing them on copper, zinc and aluminum, as well as metal alloys containing these metals. Such corrosive attack is accentuated if the detergent composition also includes bleaching agents of the peroxide type.
• Phosphoric acid esters of alkyl glyceryl ethers, and phosphoric acid esters of ethylene oxide adducts of fatty alcohols have been proposed as inhibitors of the corrosive effect of detergent compositions containing aminocarboxylic acid chelating agents.
• the effectiveness of these phosphoric acid esters is greatly reduced in the presence of bleaching or oxidizing agents, so that these esters are not capable of imparting a sufficient corrosion inhibiting effect to detergent formulations containing or to be used with a bleaching agent.
• the salts of monocetyl and monostearyl phosphates are good metal corrosion inhibitors in detergent compositions based on nonionic and/or anionic surfactants, but these alkyl phosphates form difficultly soluble calcium and magnesium salts. Consequently, they cannot be employed in detergent formulations intended for use in hard water, unless sequestrants are also present. However, these alkyl phosphates are relatively ineffective in inhibiting the corrosive effect of aminocarboxylic acid sequestrants, such as ethylene diamine 'tetraacetic acid and propylene diamine tetraacetic acid.
• monoalkyl oxypropylene phosphoric acid esters display excellent corrosion-inhibiting properties in synthetic surfactant detergent or washing compositions containing aminocarboxylic acid sequestrants and bleaching or oxidizing agents, such as'peroxides, and demonstrate this effect in both soft and hard water.
• the monoalkyl oxypropylene phosphoric acid esters can be used either in acid form or in salt form. If the acid form is used, the salt form may be formed in situ in the aqueous detergent or washing solution.
• the monoalkyl oxypropylene phosphoric acid ester corrosion inhibitors in accordance with the invention are defined by the following general formula:
• R is a straight or branched chain alkyl radical having from 5 about to about b and preferably from 16 to 18 carbon atoms.
• M is hydrogen, an alkali metal, such as sodium or potassium, ammonium or a strongly basic organic amine, such as tributylamine, monoethanolamine, diethanolamine, or triethanolamine.
• n is a number representing the average number of propylene oxide ether units, and is within the range from about I to about 4, and preferably 1 or 2. It will be understood that when n is greater than 1, mixtures can be present, and probably will be, when propylene oxide is condensed with the alcohol. In such cases, It represents an average number, and can be any fractional number within the range from 1 to 4, for instance, 1.2, 2.5 or 3.3.
• R can be, for example, pentadecyl, palmityl (cetyl), margaryl, stearyl, nonadecyl, and arachidyl.
• Exemplary monoalkyl oxypropylene phosphoric acid esters monopalmityltri(oxypropylene) phosphoric acid, monostearyldi(oxy-propylene)phosphoric acid, monomargaryldi(oxypropylene)phosphoric acid, monononadecyl 0xypropylene phosphoric acid, monoarachidyl oxypropylene phosphoric acid, monostearyltetra(oxypropylene) phosphoric acid, monostearyl tri(oxypropylene) phosphoric acid, monopalmityl(cetyl)tetra(oxypropylene) phosphoric acid,
• the essential ingredients of the detergent compositions of the invention are a synthetic detergent or surfactant, which can be of the anionic and/or nonionic type, and an aminocarboxylic acid chelating agent.
• the monoaklyloxypropylene phosphoric acid ester is intended to be used in the presence of a bleaching or oxidizing agent, such as a peroxide bleaching agent, and this is an optional ingredient, but it can be added later, when the washing solution is prepared.
• a bleaching or oxidizing agent such as a peroxide bleaching agent
• this is an optional ingredient, but it can be added later, when the washing solution is prepared.
• these components which with the monoalkyloxpropylene phosphoric acid ester are the only essential components, there can be included as optional components builders, fillers, optical whitening agents, coloring agents, perfumes, and other conventional detergent formulation components.
• the detergent formulations of the invention have a reduced tendency to corrode copper, zinc and aluminum, and alloys containing such metals.
• the weight ratio of monoalkyl oxypropylene phosphoric acid ester to surfactant should be within the range from about 10:1 to about 1:10.
• the detergent compositions of the invention have the following formulation, based on the solids content:
• the composition is in the form of particles produced by drying an aqueous mixture or slurry of the componcnt.
• Spray-drying is a preferred drying method, since it produces friable light particles which dissolve rapidly and completely in water.
• Other drying methods include suspension-drying and drum drying, the latter procedure being particularly useful in the production of particulate detergent mixtures in flake or large particle form.
• the detergent composition can also be formulated as an aqueous concentrate which forms a washing solution upon dilution with water.
• the concentrate has as high a composition solids content as possible, within the range from 20 to 75 percent, preferably from 30 to 60 percent by weight.
• the upper limit of solids content is normally determined by the solubility of the components in water or other solvent or suspending medium, such as ethyl alcohol, or methyl alcohol.
• solubility in water or other solvent can be increased in the concentrate by the addition of solubilizing agents.
• the monoalkyloxypropylene phosphoric acid esters display a solubilizing effect on the other ingredients. This effect can be increased by the addition of other hydrotropic substances, such as sodium xylene sulfonate and sodium toluene sulfonate.
• Organic solvents can be used, such as ethyl alcohol or methyl alcohol.
• the synthetic detergent or surfactant employed in the compositions of the invention can be of the anionic type, of the nonionic type, or the mixed nonionic-anionic type. Mixtures of anionic and nonionic surfactants can also be employed.
• anionic surfactants which can be employed are the alkyl aryl sulfonates, the alkyl sulfonates, the alpha-olefin sulfonates, the alkyl ether polyglycol sulfates, and the alkyl phenol ether sulfates. These are all known compounds.
• alkyl aryl sulfonates are the alkyl benzene sulfonates, which have the general formula:
• R is a straight or branched chain alkyl radical having from about four to about 18 carbon atoms.
• R is hydrogen or a straight or branched chain alkyl radical having from one to about 12 carbon atoms. The total of the number of carbon atoms in R and R is within the range from about and to about 24.
• M is hydrogen, or an alkali metal, ammonium or organic amine cation.
• alkyl benzene sulfonates examples include sodium dodecylbenzene sulfonate, sodium polypropylene benzene sulfonate (Lewis Pat. No. 2,477,383), sodium tridecylbenzene sulfonate, sodium cetylbenzene sulfonate, potassium dodecyl toluene sulfonate, triethanolamine dodecylbenzene sulfonate, potassium dinonylbenzene sulfonate, sodium didodecylbenzene sulfonate, and ammonium polypropylene benzene sulfonate.
• alkyl sulfonates have the general formula:
• R is a straight or branched chain alkyl group having from about ten to about twenty carbon atoms
• M is hydrogen, or an alkali metal, ammonium or organic amine cation.
• sulfonates are obtained by sulfonating paraffmic hydrocarbons with a mixture of sulfur dioxide and oxygen using energy rich radiation. Exemplary are sodium cetyl sulfonate, potassium stearyl sulfonate, and triethanolamine myristyl sulfonate.
• alpha-olefin sulfonates have the formula:
• R is an alkylene (ethylenically unsaturated) radical having from about 10 to about 20 carbon atoms, and M is hydrogen, or an alkali metal, ammonium or organic amine cation.
• sulfonates are obtained by sulfonation of aIpha-olefins of the general formula:
• R is an alkyl radical having from about nine to about 19 carbon atoms.
• exemplary is the sodium salt of the alpha-olefin sulfonic acid obtained by the sulfonation of a mixture of alpha-olefins having from 14 to 18 carbon atoms.
• alkyl sulfates which have the formula:
• R is an alkyl radical having from about 10 to about 22 carbon atoms
• M is hydrogen, an alkali metal, ammonium, or an organic amine cation.
• exemplary are sodium coconut oil fatty alcohols sulfate, potassium cetyl alcohol sulfate, ammonium stearyl alcohol sulfate, and triethanolamine lauryl alcohol sulfate.
• alkyl oxyalkylene sulfates have the general formula:
• R is an alkyl radical having from about 12 to about 20 carbon atoms.
• R is hydrogen or methyl.
• M is hydrogen, or an alkali metal, ammonium or organic amine cation.
• 11 is an integer representing the average number of the oxyalkylene units indicated, and is within the range from 2 to 6. It will be understood that n can represent an average number, such as 2.5.
• Exemplary are the sodium salt of sulfonated lauryl alcohol condensed with 3 moles of ethylene oxide, and the potassium salt of sulfonated cetyl stearyl alcohol condensed with 2 moles of propylene oxide, and then 2 moles of ethylene oxide.
• alkyl phenol oxyalkylene sulfates are examples of mixed nonioniczanionic surfactants.
• alkyl phenol oxyalkylene sulfates have the general formula:
• R is as above.
• R is a straight or branched alkyl radical having from four to about 16 carbon atoms
• R is hydrogen or a straight or branched alkyl radical having from one to about 14 carbon atoms, the total number of carbon atoms in R and R being within the range from eight to 24.
• n represents the number of units enclosed by the brackets, and is a number from 1 to 6. It will be understood that n can be an average value, such as 3.5.
• Exemplary are sodium nonyl phenol oxyethylene sulfate (condensed with 4 moles of ethylene oxide), potassium dinonyl phenol oxyethylene sulfate (condensed with 6 mole of ethylene oxide), ammonium dibutyl phenol oxyethylene sulfate (condensed with 3 mole of ethylene oxide), and triethanolamine dodecylcresol oxyethylene sulfate (condensed with 4 moles of ethylene oxide).
• nonionic surfactants which can be employed include the polyoxyalkylene glycol monoethers, monoamines, monoamides, monocarboxylic acid esters and monothiocarboxylic acid esters.
• alkyl oxyalkylene ether and ester and thioether and ester derivatives have the following general formula:
• R is as above, and R is a straight or branched chain saturated or unsaturated hydrocarbon group having from about five to about 18 carbon atoms, or an aralkyl group having an aryl nucleus to which is attached a straight or branched chain saturated or unsaturated hydrocarbon group having from about eight to about 18 carbon atoms, linked through A to the aryl nucleus.
• A is either oxygen, thioether, amino, arnido, a carboxylic acid ester or a thiocarboxylic acid ester group.
• n is a number from 8 to 35, and can represent an average number, such as 10.5.
• R radicals include amyl, octyl, nonyl, decyl, tetradecyl, lauryl, myristyl, cetyl, or stearyl.
• exemplary aralkyl groups include octylphenyl, nonylphenyl, decylphenyl, and stearylphenyl. These compounds are prepared by condensation of the corresponding alcohol, mercaptan, amine, oxy or thio fatty acids or esters with ethylene oxide. Exemplary are the condensation products of oleyl or lauryl alcohol, mercaptan or amine, or oleic or lauric acid, with from 8 to 17 moles of ethylene oxide, and the polyoxyethylene ester of tall oil fatty acids.
• the polyoxyalkylene surfactants have the formula:
• R is as above.
• R is a straight or branched chain saturated or unsaturated hydrocarbon group having at least five carbon atoms up to about 18 carbon atoms.
• A is oxygen or sulfur, and n is a number within the range from 8 to 35.
• R may, for example, be a straight or branched chain amyl, octyl, nonyl, dodecyl, tetradecyl, lauryl, cetyl, myn'styl or stearyl group.
• exemplary are condensation products of octyl and nonyl phenol and thiophenol with from 8 to 17 moles of ethylene oxide.
• Organic compounds suitable for forming Y are compounds in which the hydrogen atoms are activated by an oxygen atom, such as in a hydroxyl group, a phenol group or a carboxyl group, or by a basic nitrogen atom, such as in an amine group and amide group, a sulfamide group, a carbamide group, and a thiocarbamide group, or by a sulfur atom, such as in a mercaptan.
• an oxygen atom such as in a hydroxyl group, a phenol group or a carboxyl group
• a basic nitrogen atom such as in an amine group and amide group, a sulfamide group, a carbamide group, and a thiocarbamide group
• sulfur atom such as in a mercaptan.
• Exemplary Y compounds are glycerol, ethylene glycol, propylene glycol, methanol, ethanol, isopropanol, nbutanol, Z-ethylhexanol, lauryl alcohol, cetyl alcohol, stearyl alcohol, eicosanol, oleyl alcohol, so-called OXO-alcohol mixtures, butanediol, pentaerythritol, oxalic acid, triethanolamine, aniline, resorcinol, triisopropanolamine, sucrose, ethylenediamine, diethylenetriamine, acetamide, coconut oil fatty amine, methyl mercaptan, dode'cyl mercaptan, hexadecyl mercaptan, 61C.
• polyoxyalkylene glycol ether surfactants has the formula:
• Y is an organic residue as defined above, and R, R R and R are selected from the group consisting of hydrogen, aliphatic and aromatic radicals, at least one of these substituents not being hydrogen.
• n is a number greater than 6.4, as determined by hydroxyl number, and X is a water-solubilizing group, as defined in U.S. PAT. Nos. 2,674,691 and 2,677,700.
• Exemplary of this type of compound are the fatty alcohol styrene oxide condensates containing 7 moles of styrene oxide, with the water-solubilizing group X being 70 moles of ethylene oxide.
• the sequestrant employed in accordance with the invention to capture calcium and magnesium ions in hard water is an amino polycarboxylic acid or salt having the general formula:
• N- (CzHdTUnCHzCO OM A is CH COOM or CH CH OH.
• M is hydrogen or an alkali metal, such as sodium and potassium or ammonium, and n is a number from 0 to 5.
• nitrilotriacetic acid ethylenediamine tetraacetic acid
• the mono-, di-, triand tetra-sodium salts of ethylene diamine tetraacetic acid the mono-, diand tri-sodium salts of nitrilotriacetic acid
• the mono-, di-, tri-, tetraand penta-sodium salts of diethylenetriamine pentaacetic acid and the mono-, diand tri-potassium salts of hydroxethylethylenediamine triacetic acid.
• the detergent compositions of the invention may also contain or are for use with a bleaching or oxidizing agent, such as an inorganic peroxide which serves as a bleaching agent.
• a bleaching or oxidizing agent such as an inorganic peroxide which serves as a bleaching agent.
• Suitable peroxides are the perborates, persulfates, percarbonates and perpyrophosphates, in the form of their watersoluble salts, preferably their alkali metal salts.
• Exemplary are sodium perborate, potassium persulfate, potassium percarbonate, K C O and sodium perpyrophosphate Na i-1 11 O2'2H2O.
• tetrasodium pyrophosphate sodium carbonate, sodium sulfate, potassium carbonate, potassium sulfate, sodium silicate, potassium silicate.
• Optical whitening agents, coloring agents and perfumes can also be added.
• Soil-suspending agents can also be incorporated, such as sodium carboxymethyl cellulose, hydroxyethyl cellulose, and ethylhydroxy-ethyl cellulose, as well as starch, polyethylene glycols, and polyvinyl alcohol.
• Pentasodium tripolyphosphate 15.2% 0.5 g/l Bleaching agent Sodium perborate Builders Sodium carbonate Sodium silicate Nonionic surfactant Condensation product of tallow fatty alcohol and 8 moles ethylene oxide 30.3% r g/l TABLE VI Alkyl oxypropylcnc Copper Example no. phosphoric ncid dissolved (mg/l) Control D None [03 it Mono-cetyl oxypropylcne phosphoric acid was effective in inhibiting copper corrosion.
• EXAMPLE 9 A detergent formulation'was prepared, as shown in Table VIII. This composition was dissolved in water of 5 dH, to the solution concentration shown in the Table.
• the detergent compositions prepared according to the invention show a very substantial decrease in the corrosion of copper, zinc and aluminum. Copper, aluminum and zinc corrosion is inhibited even when hard water is used in the preparation of the detergent solution. It, furthermore, was proved by test washing that the compositions according to the invention provide very good washing results and that, in addition, the resulting detergents are low foaming, which is important where the detergents are used in automatic washing machines.
• Tetrasodium salt of ethylenediamine tetraaoetic acid 22. 9 1. 6 Pentasodium tripolyphosphate 11.5 0.8 Bleaching agent:
• compositions were each dissolved in water of 15 of hardness (l/ Mg-hardness, 4/5 Ca-hardness) to the solution concentration indicated.
• alkyl oxypropylene phosphoric acid esters were effective in inhibiting copper corrosion by the sodium ethylenediaminetetraacetic acid and the peroxide bleaching agent.
• a detergent composition for use in hard and soft water consisting essentially of an organic surfactant selected from the group consisting of anionic and nonionic organic surfactants, an aminocarboxylic acid or salt sequestrant in an amount to sequester calcium and magnesium ions in hard water and a mono-alkyl oxypropylene phosphoric acid ester of the formula OM R0(Ca e )no OM wherein R is an alkyl group having from 15 to 20 carbon atoms and M is selected from the group consisting of hydrogen, alkali metals, ammonium and strongly basic organic amine cations, and n is a number within the range from 1 to 4, in an amount to lessen the corrosive effect of the aminocarboxylic acid on copper, zinc and aluminum, in the presence of a bleaching or oxidizing agent.
• an organic surfactant selected from the group consisting of anionic and nonionic organic surfactants, an aminocarboxylic acid or salt sequestrant in an amount to sequester calcium and magnesium
• a detergent composition according to claim 1 consisting essentially of a bleaching or oxidizing agent in an amount within the range from about 5 to about 40 percent by weight.
• a detergent composition according to claim 1, in which the aminocarboxylic acid or salt sequestrant has the general formula:
• A is CH COO1-l OR -CH CH Ol-l
• M is hydrogen, or an alkali metal, ammonium or organic amine cation
• n is a number from 0 to 5.
• a detergent composition according to claim 1 consisting essentially of one or more of builders, in an amount within the range from about 10 to about percent of the total weight of the detergent composition.
• a detergent composition according to claim 1 in which 16.
• a detergent composition according to claim 1, in the form of a concentrated aqueous solution having a solids conthe phosphoric acid ester is monostearyl di(oxypropylene) 5 tent offi'om about to about 75 percent by weightorthophosphoric acid ester.

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Citations (5)

• 0
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• 1968
  • 1968-08-08 SE SE10699/68A patent/SE313629B/xx unknown
• 1969
  • 1969-07-30 DE DE1938718A patent/DE1938718B2/de active Granted
  • 1969-08-05 FR FR696926919A patent/FR2015278B1/fr not_active Expired
  • 1969-08-06 NO NO3221/69A patent/NO130687C/no unknown
  • 1969-08-06 US US848084A patent/US3655569A/en not_active Expired - Lifetime
  • 1969-08-06 GB GB1267217D patent/GB1267217A/en not_active Expired
  • 1969-08-07 CH CH1201869A patent/CH512582A/fr not_active IP Right Cessation
  • 1969-08-08 NL NL6912138.A patent/NL163822C/xx not_active IP Right Cessation
  • 1969-08-08 DK DK428069AA patent/DK130747B/da not_active IP Right Cessation
  • 1969-08-08 FI FI692333A patent/FI51366C/fi active

Patent Citations (5)

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