US3346504A - Detergent compositions - Google Patents

Detergent compositions Download PDF

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US3346504A
US3346504A US547117A US54711766A US3346504A US 3346504 A US3346504 A US 3346504A US 547117 A US547117 A US 547117A US 54711766 A US54711766 A US 54711766A US 3346504 A US3346504 A US 3346504A
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Prior art keywords
detergent
group
oxide
solubilizing
electrolyte
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US547117A
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English (en)
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Kenneth W Herrmann
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Procter and Gamble Co
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Procter and Gamble Co
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Priority to FR944366A priority Critical patent/FR1449580A/fr
Priority to DE19631467652 priority patent/DE1467652A1/de
Priority to FI1547/63A priority patent/FI41315B/fi
Priority to GB50353/65A priority patent/GB1049734A/en
Priority to GB50354/65A priority patent/GB1049735A/en
Priority to GB31821/63A priority patent/GB1049732A/en
Priority to GB50352/65A priority patent/GB1049733A/en
Priority to GB50355/65A priority patent/GB1049736A/en
Priority to NL6511600A priority patent/NL6511600A/xx
Priority to NL6511599A priority patent/NL6511599A/xx
Priority to BE674560D priority patent/BE674560A/xx
Priority to BE674561D priority patent/BE674561A/xx
Application filed by Procter and Gamble Co filed Critical Procter and Gamble Co
Priority to US547117A priority patent/US3346504A/en
Priority to US549754A priority patent/US3346873A/en
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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
    • C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
    • C11D17/0008—Detergent materials or soaps characterised by their shape or physical properties aqueous liquid non soap compositions
    • C11D17/0017—Multi-phase liquid compositions
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00—Cosmetics or similar toiletry preparations
    • A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/30—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds
    • A61K8/46—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing sulfur
    • A61K8/466—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing sulfur containing sulfonic acid derivatives; Salts
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00—Cosmetics or similar toiletry preparations
    • A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/30—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds
    • A61K8/55—Phosphorus compounds
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
    • A61Q5/00—Preparations for care of the hair
    • A61Q5/02—Preparations for cleaning the hair
    • 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
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/66—Non-ionic compounds
    • C11D1/79—Phosphine oxides
    • 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
    • C11D1/88—Ampholytes; Electroneutral compounds
    • C11D1/92—Sulfobetaines ; Sulfitobetaines
    • 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
    • C11D3/20—Organic compounds containing oxygen
    • C11D3/2075—Carboxylic acids-salts thereof
    • C11D3/2079—Monocarboxylic acids-salts thereof
    • 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
    • C11D3/3765—(Co)polymerised carboxylic acids, -anhydrides, -esters in solid and liquid compositions in liquid compositions

Definitions

  • This invention relates to liquid detergent compositions. Specifically this invention relates to liquid detergent compositions containing certain detergent surfactants and certain solubilizing electrolytes.
  • liquid detergent compositions are very complex. Ordinarily, it is desirable to keep inert ingredients at a minimum and yet it often becomes necessary to add some compound to the formula which has no active detergent effect or detergency builder effect merely to make the active ingredients compatible with each other and thereby create a homogeneous composition (i.e., a composition in which there is no bulk separation of a phase). It would therefore be desirable to provide, in liquid detergent compositions, effective, low cost solubilizing agents and solvents.
  • aqueous homogeneous liquid detergent compositions of this invention which achieve these objects comprise:
  • a detergent selected from the group consisting of (A) A detergent having the formula (sultaine detergent) wherein R and R are each selected from the group consisting of hydrogen, methyl, and ethyl groups, R is a straight chain alkylene group containing from two to four carbon atoms, and having from 0 to one hydroxyl group substituted on a secondary carbon, and R is an alkyl chain of from about 10 to about 20 carbon atoms;
  • a detergent having the formula R R R N O (amine oxide detergent) wherein R is selected from the group consisting of alkyl, alkylmonohydroxy, and alkoxy monohydroxypropyl radicals wherein the alkyl and alkoxy portions of said radicals contain from about to about 20 carbon atoms and R and R are each selected from the group consisting of alkyl radicals and alkanol radicals containing from one to about three carbon atoms;
  • R A detergent having the formula R' R R P O (phosphine oxide detergent) wherein R is selected from the group consisting of alkyl, and alkyl monohydroxy radicals containing from about 8 to about 16 carbon atoms and R and R are each selected from the group consisting of alkyl radicals and alkanol radicals containing from one to about three carbon atoms;
  • Nonionic detergents produced by condensing ethylene oxide on a hydrophobic base e.g., a detergent havr 3,346,504 Patented Oct. 10, 1967 ing the formula R (C I-I O),,H (nonionic detergent) wherein R represents a hydrophobic base and preferably is selected from the group consisting of (1) alkoxy groups containing from about 8 to about 20 carbon atoms, (2) alkyl phenoxy groups (including dialkyl phenoxy groups) wherein the alkyl group contains from about 6 to about 18 carbon atoms, (3) condensation products of propylene glycol and propylene oxide with a molecular weight of from about 1500 to about 1800, (4) fatty amides containing from about 10 to about 20- carbon atoms, (5) higher alkyl mercaptans containing from about 10 to about 20 carbon atoms, (6) condensation products of propylene oxide and ethylene diamine constituting from about 20% to about 60% by weight of the finished nonionic detergent molecule and
  • a polyvalent electrolyte salt selected from the group consisting of sulfates; carbonates; pyrophosphates; phosphates; hexametaphosphates; ethylenediaminetetraacetates; N-(Z-hydroxyethyl)-ethylenediaminetriacetates; nitrilotriacetates; N-(2-hydroxyethyl)-nitrilodiacetates; phytates; ethane-l-hydroxy 1,1 diphosphonates; methylene diphosphonates; ethylidene, isopropylidene, benzylmethylidene and chloromethylidene diphosphonates; salts of polymers of itaconic acid, aconitic acid, maleic acid, mesaconic acid, fumaric acid, methylene malonic acid and citraconic acid and copolymers with themselves and ethylene; and mixtures thereof, the c
  • M is a water soluble cation (e.g., sodium, potassium, ammonium, and alkanolammonium cations) and R is selected from the group consisting of unsaturated aliphatic radicals containing from about 2 to about 7 .carbon atoms; aromatic, substituted aromatic, and aroelected from the group consisting of chloro, fluoro, and iitro groups and mixtures thereof; and phenyl alkyl 'adicals wherein the above phenyl radicals are attached alkylene radicals selected from the group consisting )f ethylene, propylene, butylene, pentylene, and hexylene groups; branched chain saturated aliphatic radicals conaining from about three to about six carbon atoms; and :hloro-substituted saturated and unsaturated aliphatic radical
  • the solubilizing electrolyte, Component III makes homogeneous those aqueous mixtures of Component 1, surfactant, and any polyvalent electrolyte, e.g., builder, present which otherwise would be nonhomogenous due to the presence of a bulk, separated phase, e.g., a crystalline phase, or a second immiscible isotropic liquid phase as hereinafter more fully described.
  • FIGURE 1 is a representative phase diagram for the sultaine detergents utilized in the compositions of this invention as hereinafter more fully discussed.
  • FIGURE 2 is a representative phase diagram for a detergent of the compositions of this invention and a typical detergency builder electrolyte at about room temperature (80 F).
  • FIGURE 3 is a representative phase diagram for a detergent of the compositions of this invention and a solubilizing electrolyte of the compositions of this invention at about room temperature (80 F.).
  • the first group (A) of the specific detergents, as hereinbefore described, will be referred tohereinafter as sultaines or sultaine detergents.
  • sultaines are solubilized, according to the instant invention, in an aqueous solution by the solubilizing electrolytes hereinbefore named.
  • Sultaines of particular interest are those in which the long alkyl chain (R) is a mixture of alkyl chains derived from naturally occurring substances, whether hydrogenated or not, and the short alkyl chains are methyl groups.
  • R is derived from tallow or coconut oil
  • R contains three carbon atoms with a hydroxyl group substituted on the middle carbon atom, and R and R are methyl groups
  • the sultaines are of particular interest since they are readily prepared.
  • sultaines include 3-(N, N-dimethyl-N-hexadecyl ammonio)-propane-1-sulfonate, 3-(N-hexadecyiammonio)-propane-1-sulfonate, and 3-(N, N-dimethyl-N-hexadecyl ammonio -2-hydroxypropane-1- sulfonate.
  • Other specific examples include the corresponding decyl, dodecyl, tetradecyl, and octadecyl homologs of the above compounds.
  • solubilizing electrolytes of this invention are relatively water-insoluble sultaines wherein R is an alkyl chain of (1) from about 12 to about 18 carbon atoms when R and R are hydrogens, (2) from about 16 to about 20 carbon atoms when R R and R contain no substituents, and (3) from about 14 to about 18 carbon atoms when R and R are alkyl chains, and R is a three carbon atom alkylene group with a hydroxyl group substituted on the middle carbon atom.
  • the solubilizing electrolytes of this invention solubilize the crystalline phase of these sultaines as hereinafter described.
  • All the detergents of this invention normally contain mixtures of long alkyl chains (R, R R R and R), which can be derived from naturally occurring substances such as tallow and coconut oil, and can also be derived from petroleum fractions, e.g., by polymerizing propylene or cracking waxes to form the proper chain length, e.g., in the form of an olefin.
  • the method of deriving the alkyl chain is immaterial.
  • the alkyl chains can be unsaturated.
  • amines oxided detergents include:
  • phosphine oxide detergents include:
  • nonionic detergents include nonyl phenol condensed with either about 10 or about 30 moles of ethylene oxide per mole of phenol and the condensation products of coconut alcohol with an average of either about 5.5 or about 15 moles of ethylene oxide per mole of alcohol and the condensation product of about 15 moles of ethylene oxide with one mole of tridecanol.
  • Suitable examples include the Well known detergents sold under the tradename Pluronic which are prepared by condensing propylene glycol with propylene oxide to form a hydrophobic base and then condensing said hydrophobic base with ethylene oxide, the hydrophobic base having a molecular weight of from about 1500 to about 1800 and the total molecule having a molecular weight of, e.g., 2000, 3000, and 8000.
  • Pluronic which are prepared by condensing propylene glycol with propylene oxide to form a hydrophobic base and then condensing said hydrophobic base with ethylene oxide, the hydrophobic base having a molecular weight of from about 1500 to about 1800 and the total molecule having a molecular weight of, e.g., 2000, 3000, and 8000.
  • Tetronic Another group of suitable nonionic detergents are sold under the tradename of Tetronic. These are prepared by condensing ethylene diamine with propylene oxide to form a hydrophobic group (molecular weight-from about 2500 to about 3000) and condensing this hydrophobic group with ethylene oxide to give a molecular weight of from about 5000 to 11,000.
  • sulfoxide detergents include:
  • liquid detergent compositions of this invention contain from about 1% to about 40% by weight of the composition of the detergents hereinbefore described.
  • the minimum amount is set by practical product considerations of detergency benefits derived per unit volume.
  • the upper limit is set by several considerations including viscosity, crystalline solubility, and the possibility of forming liquid mesomorphic phases or an insolubilizible, immiscible second isotropic phase.
  • R groups which fit the definition hereinbefore given are unsaturated aliphatic radicals containing from about 2 to about 7 carbon atoms and wherein there is unsaturation selected from the group consisting of one three covalent bond linkage and from one to two two covalent bond linkages; phenyl radicals; naphthyl radicals, substituted phenyl radicals containing from one to three substituents selected from the group consisting of methyl, ethyl, propyl, isopropyl, pentyl, isopentyl, butyl, isobutyl, chloro, fluoro and nitro groups and mixtures thereof; naphthyl radicals containing from one to about three substituents selected from the group consisting of chloro, fluoro, and nitro groups and mixtures thereof; phenyl alkyl radicals wherein the above phenyl radicals, including substituted phenyl radicals, are attached to alkylene radicals selected from the group consisting of ethylene, propylene, buty
  • R groups fitting the definition hereinbefore given include phenyl, benzyl, naphthyl, methylphenyl, dimethylphenyl, ethylphenyl, diethylphenyl, propylphenyl, dipropylphenyl, isopropylphenyl, butylphenyl, isobutylphenyl, 3-phenylpropyl, 2-phenylethyl, methybenzyl, nitrophenyl, dinitrophenyl, chlorophenyl, methylchlorophenyl, ethylfluorophenyl, chloronaphthyl, dichloronaphthyl, nitronaphthyl, dinitronaphthyl, isopropyl, isobutyl, chloroethyl, chloropropyl, chloroisobutyl, 1,2-dichloro-Z-pentene, 4,4-dichloro-2-buten
  • electrolytes as generically defined above which are particularly effective in solubilizing the detergent surfactants of this invention include the ammonium, monoethanolammonium, diethanolammonium, triethanolammonium, sodium, and potassium crotonates; sorbates; benzoates; o-nitrobenzoates; p-chlorobenzoates; phenylacetates; cinnamates; naphthoates; isobutyrates; isovalerates; trimethyl acetates; trichlonoacetates; ethylbenzene phosphonates; and furoates.
  • polyphosphate builder salts such as tetrapotassium pyro-phosphate and polycarboxylate builder salts such as sodium and potassium nitrilotriacetates and ethylenediaminetetraacetates 5 and substituted methylene and ethylene diphosphonate: (e.g., trisodium ethane-l-hydroxy 1,1-diphosphonate).
  • electrolytes are the solubilizing agents of this in vention; they perform the solubilizing function wherea other electrolytes having anions with relatively high charg. densities have generally the opposite effect, i.e., promott separation.
  • electrolytes which tend to caust a separation of a second isotropic liquid phase IHCllldt many of the common ingredients found in detergent com positions such as the polyvalent electrolytes hereinbefori mentioned, e.g., potassium and sodium pyrophosphates sodium and potassium tripolyphosphates, potassium an sodium silicates, potassium and sodium sulfates, potassiurr and sodium ethylenediamine tetraacetates, and sodiurr potassium nitrilo triacetates.
  • the solubilizing electrolytes of this invention are user in an amount from about 0.5% to about 20% by weigh of the liquid detergent composition and sufficient to pro vide a homogeneous composition.
  • the area in each figure defined by the axes and the boundary line is the single (first) isotropic liquid phase region.
  • first isotropic liquid phase aqueous solutions of the detergents utilized in the compositions of this invention
  • the amount of detergent which can be placed in a single homogeneous liquid phase is increased initially because the solubility of the first mesomorphic phase (middle) is initially increased.
  • a second immiscible isotropic liquid (lye) separates as the conventional and highly desirable high electrolyte/ surfactant ratios and it is this phase which normally prevents the formation of a homogeneous liquid composition.
  • solubilizing electrolyte in a water-detergent system gives the phase relationship as shown in FIGURE 3.
  • the separating phase is electrolyte crystals rather than a second liquid phase and the ,amount of electrolyte that can be present before phase separation occurs is much greater than with polyvalent electrolytes alone.
  • Addition of a solubilizing electrolyte to a composition containing builder electrolyte at a given temperature modifies the builder detergent phase diagram (e.g., FIGURE 2) to look more like FIGURE 3 and more builder can be placed in a homogeneous composition. As hereinbefore discussed, this is believed to occur by raising the minimum temperature at vhic-h the second isotropic liquid can exist and thereby lecreasing the area, on a phase diagram, of the second sotropic liquid for a given temperature.
  • a second immiscible isotropic liquid hase is also a function of temperature.
  • a second liquid phase eparates.
  • a polyvalent electrolyte e.g., builder
  • the :olubilizing electrolytes raise the temperature at which his separation occurs.
  • the presence of a temperature-de- )endent second liquid phase which exists without a polylalent electrolyte being present is a function of water iolubility and cannot readily be predicted. In general, with respect to the hydrophobic group, the longer chain lengths 1Y6 less soluble and more prone to exhibit this phenome- 1011.
  • ethylene oxide condensates and phosphine oxide surfacants are more likely to exhibit this phenomenon, whereas amine oxide and sultaine surfactants generally do not.
  • the primary bene- is derived whenever a second liquid phase is the separating phase.
  • the electrolyte solubilizing agents of this invention are present in the liquid detergent composition in an amount from about 0.5% to about by weight of the liquid detergent composition and sufficient to lower the Krafft temperature of the sultaine detergent in the liquid detergent composition below about 70 F. (room temperature), prefer-ably below 40 F., to prevent the crystalline detergent from separating out of solution during normal use and storage.
  • Region B is homogeneous and is commonly referred to as nigre; regions C and C are characterized by the presence of liquid mesomorphic phase; regions D and D are characterized by the presence of another liquid mesomorphic phase; and region E is characterized by the presence of crystals of detergent plus detergent solution.
  • the solubilizing-electrolytes of this invention lowers the Krafft temperature of the sultaine detergent, as hereinbefore described, below the temperature of the liquid detergent composition, the crystalline solubility of the sultaine detergent in water is substantially increased.
  • the practical result is that a greater amount of the sultaine detergent can be used in the detergent composition while maintaining homogeneity.
  • the liquid compositions of this invention containing the relatively water-insoluble sultaines will be to the left of A and A on the accompanying sultainewater phase diagram (FIG. 1).
  • a and A are the crystalline solubility points hereinbefore described.
  • the amount of lowering of the Krafft temperature is dependent upon the amount and, particularly, the type of electrolyte present as well as the molecular structure of the sultaine.
  • the detergent compositions can also contain from 0% to about 40% by weight of the composition of polyvalent electrolytes, but no more than can be dissolved in the compositions.
  • These polyvalent electrolytes can be inert salts, which are associated with the detergent materials, such as sodium sulfate or can be desirable detergent builder electrolytes.
  • water soluble inorganic alkaline detergency builder salts are alkali metal carbonates, phosphates, polyphosphates, and silicates. Specific examples of such salts are sodium and potassium tripolyphosphates, carbonates, pyrophosphates, phosphates, and hexametaphosphates.
  • organic alkaline sequestrant builder salts are (1) alkali metal amino polycarboxylatcs [e.g., sodium and potassium ethylenediaminetetraacetates, N-(2-hydroxyethyl)- ethylene diamine triacetates, nitrilo triacetates, and N-(2- hydroxyethyl)-nitrilo diacetates]; (2) alkali metal salts of phytic acid (e.g., sodium and potassium phytates-see U.S.
  • alkali metal amino polycarboxylatcs e.g., sodium and potassium ethylenediaminetetraacetates, N-(2-hydroxyethyl)- ethylene diamine triacetates, nitrilo triacetates, and N-(2- hydroxyethyl)-nitrilo diacetates
  • alkali metal salts of phytic acid e.g., sodium and potassium phytates-see U.S.
  • Patent 2,739,942 water soluble ethane-1- hydroxy-1,1-diphosphonates (e.g., the trisodium and tripotassium salts); (4) water soluble salts of methylene diphosphonic acid (e.g., trisodium and tripotassium methylene diphosphonate and the other salts described in the copending application of Francis L. Diehl, Ser. No. 266,025 now Patent No. 3,215,030, filed Mar.
  • a polyelectrolyte builder material consisting of water-soluble salts of a polymeric aliphatic polycarboxylic acid selected from the group consisting of (a) water soluble salt of a homopolymer of an aliphatic polycarboxylic acid having the following empirical formula:
  • X, Y, and Z are each selected from the group consisting of hydrogen, methyl, carboxyl, and carboxymethyl,
  • X, Y, and Z being selected from the group consisting of carboxyl and carboxyrnethyl, provided that X and Y can be carboxymethyl only when Z is selected from carboxyl and carboxyrnethyl, wherein only one of X, Y, and Z can be methyl, and wherein n is a Whole integer having a value within a range, the lower limit of which is three and the upper limit of which is determined by the solubility characteristics in an aqueous system;
  • R is selected from the group consisting ofhydrogen, methyl, carboxyl, carboxymethyl, and carboxyethyl;
  • R can be methyl; wherein m is at least 45 mole percent of the copolymer; wherein X, Y, and Z are each selected from the group consisting of hydrogen, methyl, carboxyl, and carboxymethyl,
  • X, Y, and Z being selected from the group of carboxyl and carboxymethyl provided that X and Y can be carboxyrnethyl only when Z is selected from carboxyl and carboxymethyl, wherein only one of X, Y, and Z can be methyl; and wherein n is a 1 about 80, calculated at the acid form (e.g., polymers of itaconic acid, aconitic acid; maleic acid; mesaconic acid; fumaric acid; methylene malonic acid; and citraconic acid and copolymers with themselves and other compatible monomers such as ethylene); and (7) mixtures thereof.
  • acid form e.g., polymers of itaconic acid, aconitic acid; maleic acid; mesaconic acid; fumaric acid; methylene malonic acid; and citraconic acid and copolymers with themselves and other compatible monomers such as ethylene
  • Mixtures of any and all of the organic and/or inorganic builders can be used and are generally desirable. Especially preferred are the mixtures of builders disclosed in the copending application of Burton H. Gedge, Ser. No. 398,705, filed Sept. 23, 1964, e.g., ternary mixtures of sodium tripolyphosphate, sodium nitrilotriacetate, and sodium ethane-l-hydroxy-l,l-diphosphonate.
  • Anti-redeposition agents such as carboxymethylcel l-ulose and anionic, cationic or nonionic detergents can also be added.
  • Typical minor additives which can be present include suds boosters and suppressants, dyes, opacifiers, perfume, corrosion, inhibitors and anti-microbial agents.
  • polyelectrolyte builder material having a minimum molecular Weight of 350 calculated as the 7,
  • any of the following detergent compounds, or mixtures of the following compounds, are substituted for the specific sultaine detergent, either wholly or in part, substantially equivalent results are obtained in that significantly more of the sultaine detergents and/or builder can be added to form a'homogeneous 1 1 solution than can be added Without the solubilizing electrolytes being present: 3- (N,N-dimethyl-N-hexadecylammonio) -propane-1- sulfonate,
  • the figures represent the E I IV maximum amounts of sultaine detergent and builders xamp e which can be solubilized by the respective electrolytes. Homogeneous aqueous liquid compositions were pre- Solubilizing Percent Percent Electrolyte Solubilizing Builder Builder Sultaine Electrolyte Detergent None i. Trisodium nitrilo triacetate Saturatedsoluti0n 1 Sodium isovalerate..- do 13 Sodium cinnamate 6 do 15 10 None Tetrapotassium ethylenediarm'ne- Saturated soluti0n 1 tetraacetate.
  • Example 111 Homogeneous aqueous liquid compositions were prepared containing varying amounts of dodecyl dimethyl amine oxide detergent in combination with potassium pyrophosphate builder (13), tetrasodium ethylenediaminetetraacetate builder (4-5) and sodium nitrilo triacetate builder (68); All percentages are by Weight. The figures represent the maximum amounts of amine oxide and builders which can be solubilized by the respective electrolytes.
  • Electrolyte Oxide (l) None 9 14 (2) c. Potassium sorbate. 9 16 23 (3) Sodium napthoate. 8 14 20 (4), None 12 24 (5) Potassium benzoate 11 18 36 (6),” None 15 30 (7) Sodium phenylacetate.
  • dimethyltetradecylphosphine oxide diethyldecylphosphine oxide; bis-(Z-hydroxyethyl)hexadecylphosphine oxide; dihydroxymethylpentadecyl phosphine oxide; dipropylundecylphosphine oxide; bis-(Z-hydroxypropyl)tetrapropylene phosphine oxide; bis-(3-hydroxypropyl)oleylphosphine oxide;
  • Example V Homogeneous aqueous liquid compositions were prepared with nonionic detergent (nonylphenol polyethoxy ethanol with an average of about 10 ethoxy groups) and potassium pyrophosphate builder (1-3), sodium nitrilotriacetate builder (45), and potassium ethylene diaminetetraacetate builder (6-8) as builders.
  • nonionic detergent nonylphenol polyethoxy ethanol with an average of about 10 ethoxy groups
  • potassium pyrophosphate builder 1-3
  • sodium nitrilotriacetate builder 45
  • potassium ethylene diaminetetraacetate builder 6-8
  • nonionic detergents prepared by condensing propylene glycol with twenty-five, thirty and thirty-five moles 1 respectively of propylene oxide and thereafter condensing the resulting products with twenty, thirty, forty, and
  • Example VI An aqueous homogeneous liquid detergent composition was prepared with the following formula in which all percentages are by weight of the composition.
  • the composition was adjusted to Na:K ratio of 65:35 by the addition of NaOI-I and KOH and the pH of the composition was 12.5. Without the sodium benzoate the composition was not homogeneous.
  • Example VII When in the previous examples any of the following solubilizer compounds, or mixtures thereof, are substituted, either wholly or in part, for the specifically named solubilizing electrolytes, substantially equivalent results are obtained in that more of the detergents and builders can be formed into homogeneous solutions with the solubilizing electrolytes than without: crotonates, sorbates, benzoates, o-nitrobenzoates, p-chlorobenzoates, phenylacetates, cinnamates, naphthoates, chloronaphthoates, fluoronaphthoates, nitronaphthoates, trichloronaphthoates, chlorodinitronaphthoates, chlorofluoron-aphthoates, isobutyrates, isovalerates, trimethylacetates, ethylbenzene phosphonates, furoates, ,B-chloro propiolates, propiolates, a-chloro
  • An aqueous homogeneous liquid detergent composition consisting essentially of:
  • R is selected from the group consisting of alkyl and alkyl monohydroxy radicals containing from about 8 to about 16 carbon atoms and R and R are each selected from the group consisting of alkyl radicals and alkanol radicals containing from one to about three carbon atoms;
  • Nonionic detergents having the formula R (C H O) H wherein R represents a hydrophobic base selected from the group consisting of (1) alkoxy groups containing from about 8 to about 20 carbon atoms, (2) alkyl phenoxy groups wherein the alkyl group contains from about 6 to about 18 carbon atoms, (3) condensation products of propylene glycol and propylene oxide with a molecular weight of from about 1500 to about 1800, (4) fatty amides containing from about 10 to about 20 carbon atoms, (5) higher alkyl mercaptans containing from about 10 to about 20 carbon atoms, (6) condensation products of propylene oxide and ethylene diamine constituting from about 20% to about 60% by Weight of the finished nonionic detergent molecule and (7) condensation products of fatty alcohols containing from about 10 to about 20 carbon atoms and from about three to about 8 propylene oxide units and wherein x is an integer from about 4 to about for (1), (2), (4), and (5), but not less than about 0.4 of the number
  • a polyvalent electrolyte salt selected from the group consisting of a polyvalent electrolyte salt selected from the group consisting of (1) sulfates; (2) carbonates; (3) tripolyphosphates; (4) pyrophosphates; (5) orthophosphates; (6) hexametamula:
  • X, Y, and Z being selected from the group consisting of carboxyl and carboxymethyl, provided that X and Y can be carboxymethyl only when Z is selected from carboxyl and carboxymethyl, wherein only one of X, Y, and Z can be methyl, and wherein n is a whole integer having a value within a range, the lower limit of which is three and the upper limit of which is determined by the solubility charac teristics in an aqueous system; (b) a watersoluble salt of copolymer of at least two of the monomeric species having the emperical, formula described in (a); and (c) a water-soluble salt of a copolymer of a member selected from the group of alkylenes and monocarboxylic acids with the aliphatic polycarboxylic compounds described in (a), said copolymers having the general formula:
  • R is selected from the group consisting of hydrogen
  • X, Y, and Z are each selected from the group consisting of hydrogen, methyl, carboxyl, and carboxymethyl,
  • At least one of X, Y, and Z being selected from the group of carboxyl and carboxymethyl provided that X and Y can be carboxymethyl only when Z is selected from carboxyl and carboxymethyl, wherein only one of X, Y and Z can be methyl;
  • n is a whole integer within a range, the lower limit of which is three and the upper limit of which is determined primarily by the solubility characteristics in an aqueous system; said polyelectrolyte builder material having a minimum molecular weight of 350 calculated as the acid form and an equivalent weight of about 50 to about 80, calculated as the acd form; and (19) mixtures thereof, the cations of the above polyvalent electrolytes being selected from the group consisting of sodium, potassium, ammonium; triethanol ammonium, diethanol ammonium and monoethanol ammonium cations and mixtures thereof;
  • composition of claim 1 wherein the detergent comprises a compound having the formula R R R N O wherein R is selected from the group consisting of alkyl, alkylmonohydroxy, and alkoxy monohydroxypropyl radicals wherein the alkyl and alkoxy contain from about to about 20 carbon atoms and R and R are each selected from the group consisting of alkyl radicals and alkanol radicals containing from one to about three carbon atoms.
  • composition of claim 1 wherein the detergent comprises a surface active agent having the formula R' R R P- O wherein R is selected from the group consisting of alkyl and alkyl monohydroxy radicals containing from about 8 to about 16 carbon atoms and R and R are each selected from the group consisting of alkyl radicals and alkanol radicals containing from one to about three carbon atoms.
  • composition of claim 1 wherein the detergent comprises a compound having the formula 0 R -g-om wherein R is an alkyl radical containing from about 10 to about 20 carbon atoms and contains from O to 1 hydroxyl substituents, and from 0 to five ether linkages.
  • composition of claim 1 wherein the solubilizing electrolyte is selected from the group consisting of crotonates, sorbates, unsubstituted, benzoates, o-nitrobenzoates, p-chlorobenzoates, phenylacetates, cinnamates, naphthoates, isobutyrates, isovalerates, trimethyl acetates, trichloro acetates, ethylbenzene phosphonates, furoates and mixtures thereof.
  • composition of claim 1 wherein the solubilizing electrolyte is a trimethyl acetate.
  • composition of claim 3 wherein the solubilizing electrolyte is a benzoate.
  • composition of claim 1 wherein the detergent has the formula 31 RI I R SOa and wherein R and R are each selected from the group consisting of hydrogen, methyl and ethyl groups, R is selected from the group consisting of an alkylene group containing from two to four carbon atoms and an alkylene group of three carbon atoms with a hydroxyl group substituted on the middle carbon atom, and R is an alkyl chain of (A) from about 12 to about 18 carbon atoms when R and R are hydrogens, (B) from about 16 to about 20 carbon atoms when R and R are each selected from the group consisting of methyl and ethyl groups and R is an unsubstituted alkylene group as hereinbefore described, and (C) from about 14 to about 18 carbon atoms when R and R are selected from the group consisting of methyl and ethyl groups and R is a three-carbon atom alkylene group with a hydroxyl group substituted on the middle carbon atom, as hereinbefore described.
  • composition of claim 1 wherein the solubilizing electrolyte is selected from the group consisting of crotonates, o-nitrobenzoates, p-chlorobenzoates, phenylacetates, cinnamates, naphthoates, isobutyrates, isovalerates, trimethylacetate, trichloroacetates, ethylbenzene phosphonates, furoates and mixtures thereof.

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US547117A 1962-08-10 1966-03-25 Detergent compositions Expired - Lifetime US3346504A (en)

Priority Applications (14)

Application Number Priority Date Filing Date Title
FI1547/63A FI41315B (de) 1962-08-10 1963-08-09
FR944366A FR1449580A (fr) 1962-08-10 1963-08-09 Compositions détergentes liquides renfermant des détergents surfactifs et des électrolytes solubilisants
DE19631467652 DE1467652A1 (de) 1962-08-10 1963-08-09 Fluessiges Waschmittel
GB31821/63A GB1049732A (en) 1962-08-10 1963-08-12 Detergent compositions
GB50352/65A GB1049733A (en) 1962-08-10 1963-08-12 Detergent compositions
GB50355/65A GB1049736A (en) 1962-08-10 1963-08-12 Detergent compositions
GB50353/65A GB1049734A (en) 1962-08-10 1963-08-12 Detergent compositions
GB50354/65A GB1049735A (en) 1962-08-10 1963-08-12 Detergent compositions
NL6511600A NL6511600A (de) 1962-08-10 1965-09-06
NL6511599A NL6511599A (de) 1962-08-10 1965-09-06
BE674560D BE674560A (de) 1962-08-10 1965-12-30
BE674561D BE674561A (de) 1962-08-10 1965-12-30
US547117A US3346504A (en) 1962-08-10 1966-03-25 Detergent compositions
US549754A US3346873A (en) 1962-08-10 1966-04-21 Liquid detergent composition containing solubilizing electrolytes

Applications Claiming Priority (8)

Application Number Priority Date Filing Date Title
US21611962A 1962-08-10 1962-08-10
GB50352/65A GB1049733A (en) 1962-08-10 1963-08-12 Detergent compositions
GB50355/65A GB1049736A (en) 1962-08-10 1963-08-12 Detergent compositions
GB50354/65A GB1049735A (en) 1962-08-10 1963-08-12 Detergent compositions
US42114264A 1964-12-14 1964-12-14
NL6511600A NL6511600A (de) 1962-08-10 1965-09-06
NL6511599A NL6511599A (de) 1962-08-10 1965-09-06
US547117A US3346504A (en) 1962-08-10 1966-03-25 Detergent compositions

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NL (2) NL6511600A (de)

Cited By (16)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3424689A (en) * 1964-08-28 1969-01-28 Kao Corp Heavy-duty liquid detergent composition
US3520818A (en) * 1966-12-20 1970-07-21 Procter & Gamble Abrasive liquid detergent compositions
US3537993A (en) * 1966-06-21 1970-11-03 Procter & Gamble Detergent compositions
US3627845A (en) * 1968-08-09 1971-12-14 Dow Chemical Co Polyloxy alkylene sulfides
FR2121697A1 (de) * 1971-01-15 1972-08-25 Helios Kemisk Tekniska Ab
US3932316A (en) * 1974-11-13 1976-01-13 The Procter & Gamble Company Free flowing detergent compositions containing benzoate salts
US3933673A (en) * 1970-01-08 1976-01-20 Lever Brothers Company Detergent compositions containing polymeric builders
US4018720A (en) * 1975-07-14 1977-04-19 The Procter & Gamble Company Laundry detergent compositions in emulsion/suspension
US4169817A (en) * 1971-12-23 1979-10-02 Midwest Biochemical Corporation Liquid cleaning composition containing stabilized enzymes
US4246125A (en) * 1979-05-04 1981-01-20 Edwin Cooper, Inc. Lubricating oil and fuel composition
US4284532A (en) * 1979-10-11 1981-08-18 The Procter & Gamble Company Stable liquid detergent compositions
US4311618A (en) * 1977-03-18 1982-01-19 Schaefer Burkhard Werner Cleanser with ionic and nonionic surfactants
US4515704A (en) * 1982-02-05 1985-05-07 Albright & Wilson Limited Pourable non-sedimenting aqueous based detergent composition having an organic lamellar structural component
EP0175485A2 (de) * 1984-08-21 1986-03-26 Reckitt And Colman Products Limited Haarwaschmittelzusammensetzungen
LT3962B (en) 1993-12-21 1996-05-27 Albright & Wilson Funcional fluids
CN111519193A (zh) * 2020-06-03 2020-08-11 江苏久茂精密电子科技有限公司 一种电子产品外壳生产用酸洗剂及其制备方法

Families Citing this family (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
AT356316B (de) * 1976-09-17 1980-04-25 Hrovat Horst Mag Pharm Aufbewahrungskasten fuer sortiert aufzube- wahrende kleinteile
JPS5851991B2 (ja) * 1976-08-24 1983-11-19 花王株式会社 低刺激性シヤンプ−組成物
EP0243927A3 (de) * 1986-05-01 1988-08-17 Kao Corporation Flüssiges Reinigungsmittel
US4900467A (en) * 1988-05-20 1990-02-13 The Clorox Company Viscoelastic cleaning compositions with long relaxation times
CN108998257A (zh) * 2018-06-15 2018-12-14 河北晨晨环境科技股份有限公司 全能清洗剂及其制备方法

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US2441341A (en) * 1946-05-27 1948-05-11 American Cyanamid Co Dialkyl sulfosuccinate composition
US2768143A (en) * 1953-03-31 1956-10-23 Hercules Powder Co Ltd Water-soluble gum having improved properties
US2787595A (en) * 1955-07-11 1957-04-02 Union Oil Co Sulfoxide containing detergent compositions
FR1219570A (fr) * 1958-04-01 1960-05-18 Unilever Nv Compositions détergentes
US3001945A (en) * 1959-04-29 1961-09-26 Procter & Gamble Liquid detergent composition
US3086943A (en) * 1959-06-10 1963-04-23 Procter & Gamble Shampoo containing amine oxide
US3159581A (en) * 1962-04-13 1964-12-01 Procter & Gamble Detergency composition
US3213030A (en) * 1963-03-18 1965-10-19 Procter & Gamble Cleansing and laundering compositions

Patent Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2441341A (en) * 1946-05-27 1948-05-11 American Cyanamid Co Dialkyl sulfosuccinate composition
US2768143A (en) * 1953-03-31 1956-10-23 Hercules Powder Co Ltd Water-soluble gum having improved properties
US2787595A (en) * 1955-07-11 1957-04-02 Union Oil Co Sulfoxide containing detergent compositions
FR1219570A (fr) * 1958-04-01 1960-05-18 Unilever Nv Compositions détergentes
US3001945A (en) * 1959-04-29 1961-09-26 Procter & Gamble Liquid detergent composition
US3086943A (en) * 1959-06-10 1963-04-23 Procter & Gamble Shampoo containing amine oxide
US3159581A (en) * 1962-04-13 1964-12-01 Procter & Gamble Detergency composition
US3213030A (en) * 1963-03-18 1965-10-19 Procter & Gamble Cleansing and laundering compositions

Cited By (18)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3424689A (en) * 1964-08-28 1969-01-28 Kao Corp Heavy-duty liquid detergent composition
US3537993A (en) * 1966-06-21 1970-11-03 Procter & Gamble Detergent compositions
US3520818A (en) * 1966-12-20 1970-07-21 Procter & Gamble Abrasive liquid detergent compositions
US3627845A (en) * 1968-08-09 1971-12-14 Dow Chemical Co Polyloxy alkylene sulfides
US3933673A (en) * 1970-01-08 1976-01-20 Lever Brothers Company Detergent compositions containing polymeric builders
FR2121697A1 (de) * 1971-01-15 1972-08-25 Helios Kemisk Tekniska Ab
US4169817A (en) * 1971-12-23 1979-10-02 Midwest Biochemical Corporation Liquid cleaning composition containing stabilized enzymes
US3932316A (en) * 1974-11-13 1976-01-13 The Procter & Gamble Company Free flowing detergent compositions containing benzoate salts
US4018720A (en) * 1975-07-14 1977-04-19 The Procter & Gamble Company Laundry detergent compositions in emulsion/suspension
US4311618A (en) * 1977-03-18 1982-01-19 Schaefer Burkhard Werner Cleanser with ionic and nonionic surfactants
US4246125A (en) * 1979-05-04 1981-01-20 Edwin Cooper, Inc. Lubricating oil and fuel composition
US4284532A (en) * 1979-10-11 1981-08-18 The Procter & Gamble Company Stable liquid detergent compositions
US4515704A (en) * 1982-02-05 1985-05-07 Albright & Wilson Limited Pourable non-sedimenting aqueous based detergent composition having an organic lamellar structural component
US4659497A (en) * 1982-02-05 1987-04-21 Albright & Wilson Limited Liquid detergent compositions
EP0175485A2 (de) * 1984-08-21 1986-03-26 Reckitt And Colman Products Limited Haarwaschmittelzusammensetzungen
EP0175485A3 (de) * 1984-08-21 1987-11-25 Reckitt And Colman Products Limited Haarwaschmittelzusammensetzungen
LT3962B (en) 1993-12-21 1996-05-27 Albright & Wilson Funcional fluids
CN111519193A (zh) * 2020-06-03 2020-08-11 江苏久茂精密电子科技有限公司 一种电子产品外壳生产用酸洗剂及其制备方法

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Publication number Publication date
BE674561A (de) 1966-06-30
GB1049736A (en) 1966-11-30
DE1467652A1 (de) 1969-09-18
NL6511600A (de) 1967-03-07
BE674560A (de) 1966-06-30
GB1049732A (en) 1966-11-30
GB1049733A (en) 1966-11-30
GB1049735A (en) 1966-11-30
NL6511599A (de) 1967-03-07
FI41315B (de) 1969-06-30
GB1049734A (en) 1966-11-30

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