US3159581A - Detergency composition - Google Patents

Detergency composition Download PDF

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Publication number
US3159581A
US3159581A US187327A US18732762A US3159581A US 3159581 A US3159581 A US 3159581A US 187327 A US187327 A US 187327A US 18732762 A US18732762 A US 18732762A US 3159581 A US3159581 A US 3159581A
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Prior art keywords
builder
detergent
sodium
water
ehdp
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Expired - Lifetime
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US187327A
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Francis L Diehl
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Procter and Gamble Co
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Procter and Gamble Co
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Priority to NL132418D priority Critical patent/NL132418C/xx
Application filed by Procter and Gamble Co filed Critical Procter and Gamble Co
Priority to US187327A priority patent/US3159581A/en
Priority to DK156563AA priority patent/DK111829B/da
Priority to DE19631467648 priority patent/DE1467648A1/de
Priority to FI0728/63A priority patent/FI41762B/fi
Priority to GB14689/63A priority patent/GB1035913A/en
Priority to FR931532A priority patent/FR1439824A/fr
Priority to AU51843/64A priority patent/AU294552B2/en
Priority to BE655988A priority patent/BE655988A/xx
Priority to NL6413483A priority patent/NL6413483A/xx
Application granted granted Critical
Publication of US3159581A publication Critical patent/US3159581A/en
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Expired - Lifetime legal-status Critical Current

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    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/36—Organic compounds containing phosphorus
    • C11D3/361—Phosphonates, phosphinates or phosphonites

Definitions

  • This invention relates to detergent compositions, and more particularly detergent compositions containing socalled builder materials that serve to enhance the cleaning capacity of detergent compounds.
  • water-soluble inorganic alkaline builder salts which are used alone or in combination.
  • alkali metal carbonates borates, phosphates, polyphosphates, bicarbonates and silicates.
  • organic builder compounds known heretofore and which also can be used alone and in. combination are alkali metal, ammonium or substituted ammonium aminopolycarboxylates, e.g., sodium'and potassium ethylenediaminetetraacetate, sodium and potassium N-(2- hydroxyethyl)-ethylenediaminetriacetate, sodium and potassium nitrilotriacetate and sodium, potassium and tri- United States Patent v sess builder properties to an exceptional degree.
  • alkali metal, ammonium or substituted ammonium aminopolycarboxylates e.g., sodium'and potassium ethylenediaminetetraacetate, sodium and potassium N-(2- hydroxyethyl)-ethylenediaminetriacetate, sodium and potassium nitrilotriacetate and sodium, potassium and tri- United States Patent v sess builder properties to an exceptional degree.
  • watersoluble salts of ethane-bhydroxy-l,l-diphosphonate pos- can be used to build detergent compositions containing a broad range of known detergent active materials. For instance, these compounds can build detergent compositions containing as active ingredients anionic, nonionic, ampholytic and zwitterionic detergent compounds.
  • FIGURE 1 is a graph showing washing grades obtained as a function of the molar concentration of two builder materials as hereinafter more fully described.
  • the water-soluble builder salts of this invention are derivatives of ethane -l-hydroxy-l,l-diphosphonic acid which has the following molecular formula CHSU a 2h hydrogens are replaced by sodium.
  • the salt comethanolammonium N (2 hydroxyethyl)-nitrilodiacetate.
  • Alkali metal salts of phytic acid, e.g.,' sodium phytate are also suitable asorganic builders.
  • the tetrasodium salt, the trisodium salt and mixtures thereof are the preferred forms.
  • Mixtures of the tetrasodium and trisodium salts give a pH in water solution from about 9.5 to 11.5.
  • Each of the lesser neutralized forms such as monosodium and disodium derivatives or the free acid have comparable builder capacity to the trisodium and tetrasodium salt forms'provided that additional alkali is added to adjust the pH of the washing solution to about 9 to about 12.
  • the standard alkaline materials can be used for this purpose, such as alkali metal silicates, phosphates, borates and carbonates.
  • Free alkali materials such as sodium and potassium hydroxides can also be used.
  • EHDP novel builder compound
  • compositions consisting essentially of a synthetic non-soap detergent surfactant compound and as a builder, a watersoluble salt of ethane-l-hydroxy-l,l-diphosphonate, such as the sodium or potassium salts, the ratio by weight of the builder to the detergent surfactant compound being in the range of about 1:2 to about 10:1, said composition providing in solution a pH of about 9 to 12.
  • the preferred ratio of diphosphonate builder to said detergent surfactant compound is in the range of about 1:1 to about 5:1 and the optimum pH range is 9.5 to 11.5.
  • EHDP-built compositions forms a highly soluble compound in water whereas the ST? complex forms a sodium salt which is substantially less soluble and tends to precipitate out on the articles being washed.
  • the insoluble complex which precipitates out on the articles firmly adheres to such articles.
  • the precipate is ex posed to an excess of hardness imparting ingredients which proceed to react with the precipitated complex salt and transform it to an even more insoluble adherent form.
  • the washing process can be complicated by the complex forming properties of an STP built detergent composition where the active STP builder is consumed and bound up in an insoluble complex.
  • EHDP when used as a detergency builder is bound up in a solubiliz ed form which allows it to participate in and carry on the many other builder functns.
  • Anionic synthetic detergents This class of synthetic detergents can be broadly described as the watersoluble salts, particularly the alkali metal salts of organic sulfuric reaction products having in their 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.
  • alkyl is the alkyl portion of higher acyl radicals.
  • the synthetic detergents which form a part of the preferred compositions of the present invention are the sodium alkyl sulfates, especially those obtained by sulfating the higher alcohols (C C carbon atoms) produced by reducing the glycerides of tallow or coconut oil; sodium or potassium alkylbenzenesulfonates, in which the alkyl group contains from about 9 to about 15 carbon atoms, especially those of the types described in United States Letters Patent Numbers 2,220,099, and 2,477,383; sodium alkylglycerylethersulfonates, especially those ethers of the higher alcohols derived from tallow and coconut oil; sodium coconut oil fatty acid monoglyceride sulfates and sulfonates; sodium or potassium salts of sulfuric acid esters of the reaction product of one mole of a higher fatty alcohol (e.g., tallow or
  • Nonionic synthetic detergents This class of synthetic detergents may be broadly defined as compounds aliphatic or alkyl aromatic in nature which do not ionize in water solution.
  • 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 with an 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 1200 to 2500.
  • 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 product is retained up to the point where polyoxyethylene content is about 50% of the total weight of the condensation product.
  • nonionic synthetic detergents include:
  • the polyethylene oxide condensates of alkylphenols, e.g., the condensation products of alkylphenols or dialkylphenols wherein the alkyl group contains 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 10 to 25 moles of ethylene oxide per mole of alkylphenol.
  • alkyl substituent in such compounds may be derived from polymerized propylene, diisobutylene, n-octene, or
  • Those derived from the condensation of ethylene oxide with the product resulting from the reaction of propylene oxide and ethylenediamine For example, compounds containing from about 40% to about polyoxyethylene by weight and having a molecular weight of from about 5000 to about 11,000 resulting from the (3)
  • R R R N O Long chain tertiary amine oxides corresponding to the following general formula, R R R N O, wherein R is an alkyl radical of from about 8 to 18 carbon atoms, and R and R are each methyl or ethyl radicals.
  • the arrow in the formula is a conventionalrepresentation of a semi-polar bond.
  • amine oxides suitable for use in this invention include dimethyldodecylarnine oxide, dimethyloctylamine oxide, dimethyldecylamine oxide, dimethyltetradecylamine oxide, dimethylhexadecylamine oxide.
  • Long chain tertiary phosphine oxides correspond ing to the following general formula RRR"P O wherein R is an alkyl, alkenyl or monohydroxyalkyl radical ranging from 10 to 18 carbon atoms in chain length and R and R are each alkyl or monohydroxyalkyl groups containing from 1 to 3' carbon atoms.
  • RRR"P O wherein R is an alkyl, alkenyl or monohydroxyalkyl radical ranging from 10 to 18 carbon atoms in chain length and 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.
  • suitable phosphine oxides are:
  • anionic, nonionic, ampholytic and zwitterionic detergent surfactants mentioned above can be used singly or in combination in the practice of the present invention.
  • the above examples are merely specific illustrations of the numerous detergents which can find application within the scope of thisinvention.
  • Granular detergent compositions according to one embodiment of this invention can contain the EHDP builder and the detergent active in the ratio of about'lzZ to about 10: 1.
  • the preferred ratio of builder to active is about 1:1 to aboutSzl.
  • Another embodiment of this invention is a liquid detergent composition also containing the EHDPbuilder and the detergent active in the ratio of about 1:2 to about about 1:2 to about 3:1.
  • a'sample'built detergent composition' of this invention can consist essentially of EHDP and a detergent surfactant in: the ratios above described and the balance beinga vehiclemediurn, for example, water, a, g V "water-alcohol mixture, nonionic. surfactant compounds, 7'0 a
  • F minor amounts to inhibit soil redeposition.
  • a tarnish inhibitor such as benzotriazole or ethylenethiourea may also be added in amounts up to about 2%.
  • Fluorescers, perfume and color while not essential in the compositions of the invention may be added in amounts up to about 1%.
  • An alkaline material or alkali such as sodium hydroxide or potassium hydroxide can be added in minor amounts as supplementary pH adjusters. There might also be mentioned as suitable additives moisture, brightening agents, sodium sulfate, and sodium carbonate.
  • Corrosion inhibitors generally are also added.
  • Soluble silicates are highly effective inhibitors and can be added to certain formulas of this invention at levels of from about 3% to about 8%.
  • Alkali metal, preferably potassium or sodium, silicates having a weight ratio of SiO M O of from 1.0:1 to 28:1 will be used. M in this ratio refers to sodium and potassium.
  • a sodium silicate having a ratio of SiO :Na O of about 1.6:1 to 2.45:1 is especially pre ferred for economy and effectiveness.
  • a hydrotropic agent may at times be found desirable.
  • Suitable hydrotropes are water-soluble alkali metal salts of toluenesulfonate, benzenesulfomate, and xylenesulfonate.
  • the preferred hydrotropes are the potassium or sodium toluenesulfonatcs.
  • the hydrotrope salt may be added, if desired, at levels of to about 12%. While a hydrotrope will not ordinarily be found necessary, it can be added if so desired for any reason such as to produce a product which retains its homogeneity at a low temperature.
  • compositions will serve to illustrate this facet of the invention.
  • gent formulation according to this invention has the following composition, in which the percentages are by weight.
  • sodium dodecylbenzenesulfonate (dodecyl group derived from tetrapropylene) 2.0% potassium toluenesulfonate 47.0% trisodium ethane-l-hydroxy-l,l-diphosphonate 6.0% sodium silicate (ratio siO zNa O of 2:1)
  • a granular detergent composition was prepared having Condensation products of ethylene oxide with a hydrophobic oase formed by the condensation of propylene oxide avitlz propylene glycol and having molecular weights of approximately 3000 and 8000 respectively.
  • Washing performance characteristics of this composition are exceptionally good from the point of view of general cleaning and whiteness maintenance performance.
  • sodium dodecylbenzenesulfonate (dodecyl group derived from tetrapropylene) 2.0% potassium toluenesulfonate .5 trichlorocarbanilide (as a bacteriostat) 30.0% trisodium ethane-1-hydr0x -1,1-diphosphonate 6.0% sodium silicate (ratio SiO :Na O of 2:1)
  • An effective cool water built granular composition according to this invention has the following composition:
  • the test employed was conducted in the following manner. White dress shirts, cotton T-shirts and other fabrics were distributed among various individuals. Each dress shirt and T-shirt was worn for one normal working day under uniform conditions and the other articles were used for their generally intended purposes. The soiled clothes and fabrics were then washed in an automatic agitating type washer, for a period of ten minutes, with detergent solutions at F. temperature. The wash water was at a pH of 10 and had a hardness of 7 grains per gallon.
  • the detergent composition employed during the tests consisted of 20% sodium tallow alkyl sulfate asthe detergent active, (the alkyl chain length distribution of tallow alkyl sulfate was approximately 66% C 30% C and 4% others), 50% sodium tripolyphosphate or a molar equivalent of EHDP, 6% sodium silicate and 24% sodium sulfate. On a total basis of 100%, a molar equivalent of 50% sodium tripolyphosphate is 37.0% EI-IDP (as trisodium salt). In this instancewhen EHDP was employed,
  • FIGURE 1 The concentrations of FIGURE 1" are millimoles of EHDP or STP per liter of wash water. concentration of the builder detergent in solution was varied from about 033% to .050% of STPiand..024% to 037% of EHDP (as trisodiumsalt) to provide the molar concentration of builder in the wash water set of'the builder materials.
  • An improved cleansing and laundering composition consisting essentially of a water-soluble trisodium salt of ethane-l-hydroxy-l,l-diphosphonate as a builder and. an organic water-soluble non-soap synthetic detergent surfactant having pronounced detergent power selected from the group consisting of anionic, nonionic, zwitterionic, ampholyrtic detergent surfactants, and mixtures thereof, the ratio, by weight, of said disph'osphonate builder to said detergent surfactant being in the range of about 1:2 to about 10:1, said composition providing in aqueous solution a pH between about 9 and about 12.
  • the ratio of said diphosphonate builder to said detergent active being in the range of about 1:2 to about ;10:1, said composition providing in aqueous solution a pH between about 9.and about 12.
  • An improved cleansing and laundering composition consisting essentially of awater-soluble trisodium salt of ethane-l-hydroxy-1,1-diphosphonateas a builder and as a detergent active.
  • an anionic Water-solublealkali metal salt Yof an organic sulfuric reaction product having in its jmolccular structure an alkyl radical having 8 to '22 carbon atoms and'a radical selecte d from the group consisting of Itwill benoted from FIGURE 1 that this snperiority i of *the .EHDP formulation was l, consistently maintained sulfonicacid and sulfuric acid/ester radicals, the ratio of said diphosphonate builder to said detergentfactive being inthe range of 5 about.-1. 2 to about 10:1,. said.
  • composition providing in aqueous solution a pH between References Cited in the file of this patent abOutg UNITED STATES PATENTS 6.
  • anionic detergent active is selected from 2,491,920 Emsberger 1949 the group consisting of alkali metal alkyl sulfates in 5 which the alkyl substituent contains from about 8 to 18 FOREIGN PATENTS carbon atoms, alkali metal alkylbenzenesulfonates in 1,010,965 Germany May 8, 1956 which the alkyl group contains from about 9 to about 15 1,072,346 Germany Dec.
  • alkali metal alkylglycerylethersulfo- 1,082,235 Germany May 25, 1960 mates in which the alkyl is derived from the higher alcohols 10 1 107,207 Germany May 25, 19 1 obtained from tallow and coconut oil.

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  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Wood Science & Technology (AREA)
  • Organic Chemistry (AREA)
  • Detergent Compositions (AREA)
US187327A 1962-04-13 1962-04-13 Detergency composition Expired - Lifetime US3159581A (en)

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Application Number Priority Date Filing Date Title
NL132418D NL132418C (en)) 1962-04-13
US187327A US3159581A (en) 1962-04-13 1962-04-13 Detergency composition
DK156563AA DK111829B (da) 1962-04-13 1963-04-04 Rense- og vaskemiddel.
FI0728/63A FI41762B (en)) 1962-04-13 1963-04-11
DE19631467648 DE1467648A1 (de) 1962-04-13 1963-04-11 Wasch- und Reinigungsmittel
GB14689/63A GB1035913A (en) 1962-04-13 1963-04-11 Detergent composition
FR931532A FR1439824A (fr) 1962-04-13 1963-04-12 Compositions détergentes à supports particulièrement efficaces
AU51843/64A AU294552B2 (en) 1962-04-13 1964-11-18 Detergent composition
BE655988A BE655988A (en)) 1962-04-13 1964-11-19
NL6413483A NL6413483A (en)) 1962-04-13 1964-11-19

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Cited By (88)

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US3351558A (en) * 1966-09-06 1967-11-07 Procter & Gamble Detergent composition containing organic phosphonate corrosion inhibitors
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BE655988A (en)) 1965-05-19
GB1035913A (en) 1966-07-13
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AU294552B2 (en) 1969-09-29
FR1439824A (fr) 1966-05-27

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