US3844982A - Built detergent composition - Google Patents

Built detergent composition Download PDF

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Publication number
US3844982A
US3844982A US00142360A US14236071A US3844982A US 3844982 A US3844982 A US 3844982A US 00142360 A US00142360 A US 00142360A US 14236071 A US14236071 A US 14236071A US 3844982 A US3844982 A US 3844982A
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Prior art keywords
acid
sodium
detergent
benzene
water
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US00142360A
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D Connor
J Thompson
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Procter and Gamble Co
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Procter and Gamble Co
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Priority to BE759283D priority Critical patent/BE759283A/xx
Priority to AU22443/70A priority patent/AU2244370A/en
Priority to DE19702057354 priority patent/DE2057354A1/de
Priority to CA098830A priority patent/CA928603A/en
Priority to FR707042028A priority patent/FR2075875B1/fr
Priority to CH1739470A priority patent/CH547348A/xx
Priority to GB5582670A priority patent/GB1302788A/en
Priority to NL7017181A priority patent/NL7017181A/xx
Application filed by Procter and Gamble Co filed Critical Procter and Gamble Co
Priority to US00142360A priority patent/US3844982A/en
Priority to CA122,893,A priority patent/CA950788A/en
Priority to PH12860*UA priority patent/PH9244A/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
    • 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
    • C11D3/2082—Polycarboxylic 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
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/02—Anionic compounds
    • C11D1/12—Sulfonic acids or sulfuric acid esters; Salts thereof
    • C11D1/29—Sulfates of polyoxyalkylene ethers
    • 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
    • C11D1/37—Mixtures of compounds all of which are anionic
    • 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
    • C11D1/12—Sulfonic acids or sulfuric acid esters; Salts thereof
    • C11D1/14—Sulfonic acids or sulfuric acid esters; Salts thereof derived from aliphatic hydrocarbons or mono-alcohols

Definitions

  • ABSTRACT I Built detergent compositions comprising an organic synthetic detergent and, asa detergency builder, the biodegradable water-soluble salts of a mixture of benzene pentacarboxylic acid and benzene hexacarboxylic acid in a proportion by weight of detergent to,
  • the water-soluble salts of benzene pentacarboxylic acid and benzene hexacarboxylic acid are present as a mixture in a ratio of from 1:10 to 2:1.
  • This invention relates to a detergent composition which contains an organic water-soluble synthetic detergent and a detergency builder.
  • Such compositions are generally referred to in the art as built detergent compositions.
  • the composition is characterized as a heavy duty composition intended primarily for laundering heavily soiled fabrics which ordinarily comprise a household laundry.
  • Detergent compositions which contain relatively lesser amounts of builder are light-duty compositions intended for lightly soiled fabrics and so-called fine fabrics and woolens.
  • polyphosphates are known to hydrolyze to pyrophosphates and orthophosphates.
  • Pyrophosphates have a tendency to form undesirable, insoluble precipitates with water hardness minerals such as calcium and magnesium which tend to deposit on fabrics.
  • they are similar to other well-known precipitating builders such as carbonates, soaps and mellitic acid.
  • This latter compound which is an-essential ingredient in this invention, is described in US. Pat. No. 2,264,103 issued to Nathaniel Beverly Tucker.
  • Mellitic acid (common nominer of benzene hexacarboxylic acid) does perform satisfactory at certain usage levels and water hardness contents.
  • built detergent formulations are commonly formulated to be used over a wide part of the country and, oftentimes, over a wide part of the world. Because of this fact, a very broad range of water hardness will be encountered which in itself dictates that a built detergent composition must be effective at both extremes of water hardness contents.
  • Detergent compositions containing a water-soluble salt of mellitic acid as the builder component perform satisfactorily from a nonprecipitating standpoint at normal usage levels in areas where the water hardness content of the water is relatively low. However. where the water is relatively hard, water-insoluble calcium and magnesium salts of mellitic acid are formed which, as stated above, precipitate onto the laundry.
  • the present invention relates to built detergent compositions, consisting essentially of: (a) an organic water-soluble synthetic detergent; and (b) as a detergency builder, the substantially biodegradable phosphorus-free water-soluble saltsof a mixture of benzene pentacarboxylic acid and benzene hexacarboxylic acid in. the proportion by weight of from l:l0 to 2 :1, respectively, and wherein the proportion by weight of the detergent to the detergency builder is from 5:1 -to 1:20.
  • the water-soluble cation of the polycarboxylic acids can be alkali metal such as sodium or potassium, ammonium or substituted ammonium such as tetraalkylammonium in which the alkyl group is methyl, ethyl, propyl, or isopropyl.
  • the preferred biodegradable builders are sodium or potassium salts of benzene penta-and hexacarboxylic acid.
  • Benzene pentacarboxylic acid having the formula C H OW and molecular weight of 298, has the following formula:
  • Benzene hexacarboxylic acid is commonly referred I to as mellitic acid.
  • Mellitic acid, C I- 50 molecular weight 342.1 has the following formula Thiscommercially available acid has colorless needles having a meltingpoint of 287C. which are soluble in water or alcohol. lts aluminum salt occurs in brown coal as honeystoneThis acid is further described together with properties and preparations on Page 2067 of Dictionary of Organic Compounds (Heilbron Oxford University Press, 1965), Volume 4, (.l-Phloi).
  • a mixture of the benzene pentaand hexacarboxylic acid salts when incorporated into a detergent composition results in a dc tergent composition that is satisfactorily useful in waters possessing a broad range of water hardness contents.
  • a detergent composition containing a mixture of the above mentioned polycarboxylate acid salts performs satisfactorily in relatively hard water, while another detergent composition containing the same totalamount of builder in the form of a benzene hexacarboxylic acid salt does not perform satisfactorily at the same useage level.
  • a benzene pentacarboxylic acid salt to the benzene hexacarboxylic acid salt significantly decreases the amount of precipitate that will form from a wash solution containing the same. It has been found that a mixture of benzene pentacarboxylic acid salt to benzene hexacarboxylic acid salt of from 1:10 to 2:1 ona weight basis provides a builder mixture that when formulated into a detergent composition at a level hereinafter disclosed is eminently satisfactory for a wide range of washing conditions. A ratio below 1:10 does provide some benefit but is not significant enough to be observed by most consumers.
  • a mixture ratio above 2: 1 is avoided in part because no added advantages accrue with respect to the prevention or modification of precipitates. Additionally, the benzene hexacarboxylic acid salt is a more effective cleaning component with respect to removing soil from laundry than is the benzene pentacarboxylic acid salt. Therefore, mixture ratios above 2:1 of the benzene pentato benzene hexacarboxylic acid salt adversely have an effect on the aforementioned cleaning power.
  • the aforementioned mixture ratio of 1:10 to 2:] possesses the best performance properties with respect to precipitates prevention and cleaning ability.
  • a mixture ratio of 1:5 to 1:1 on a weight basis is used in this invention.
  • organic water-soluble synthetic detergent compounds with which the biodegradable builder compounds ofthe present invention can be used include anionic, nonionic, zwitterionic, or ampholytic detergents or mixtures of such classes of detergents. Each of these classes is illustrated below.
  • Anionic Soap and Non-Soap Synthetic Detergents This class of detergents includes ordinary alkali metal soaps such as the sodium, potassium, ammonium and alkylolammonium salts of higher fatty acids containing from about 8 to about 24 carbon atoms and preferably from about to about carbon atoms. Suitable fatty acids can be obtained from natural sources such as, for instance, from plant oranimal esters (e.g., palm oil, co-
  • the fatty acids also can be synthetically prepared (e. g., by the oxidation of petroleum, or by hydrogenation or carbon monoxide by the Fischer-Tropsch process).
  • Resin acids are suitable such as rosin and those resin acids in tall oil.
  • Napthenic acids are also suitable.
  • 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. Particularly useful are the sodium and potassium salts of the mixtures of fatty acids derived from coconut oil and tallow, i.e., sodium or potassium tallow and coconut soap.
  • This class of detergents also includes water-soluble 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 sulfonic acid or sulfuric acid ester radical.
  • alkyl is the alkyl portion of higher acyl radicals.
  • this group of synthetic detergents which form a part of the preferred built detergent compositions of the present invention are the sodium or potassium 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 alkyl benzene sulfonates, in which the alkyl group contains from about 9 to about 15 carbon atoms, in straight chain or branched chain configuration, e.g. those of the type described in US. Pat. Nos.
  • C LAS linear straight chain alkyl benzene sulfonates in which the average of the alkyl groups is about 13 carbon atoms abbreviated hereinafter as C LAS); sodium alkyl glyceryl ether sulfonates, especially those ethers of higher alcohols derived from tallow and coconut oil; sodium coconut oil fatty acid monoglyceride sulfonates and sulfates; sodium or potassium salts of sulfuric acid esters of the reaction product of one mole of a higher fatty alcohol (e.g.
  • Anionic phosphate sulfactants are also useful in the present invention. These are surface active materials having substantial detergent capability in which the anionic solubilizing group connecting hydrophobic moieties is an oxy acid of phosphorus.
  • the more common solubilizing groups areSO H, -SO -,H, and CO H.
  • Alkyl phosphate esters such as (R-0) PO H and ROPO H in which R represents an alkyl chain containing from about .8 to about 20 carbon atoms are useful.
  • esters can be modified by including in the molecule from one to about alkylene oxide units, e.g., ethylene oxide units.
  • Formulae for these modified phosphate anionic detergents are it; which R represents an alkyl group containing from about 8 to carbon atoms, or an alkylphenyl group in which the alkyl group contains from about 8 to 20 carbon atoms, and M represents a soluble cation such as hydrogen, sodium, potassium, ammonium or substituted ammonium; and in which n is an integen from 1 to about 40.
  • Suitable anionic organic detergents particularly useful in this invention includes salts of 2-acyloxy-alkane-l-sulfonic acids. These salts have the formula (iJfIiRz where R, is alkyl of about 9 to about 23 carbon atoms (forming with the two carbon atoms an alkane group); R is alkyl of l to about 8 carbon atoms; and M is a saltforming radical.
  • the salt-forming radical M in the hereinbefore described structural formula is a water-solubilizing cation and can be, for example, an alkali metal cation (e.g. sodium, potassium, lithium), ammonium or substitutedammonium cation.
  • alkali metal cation e.g. sodium, potassium, lithium
  • substituted ammonium cations include methyl-, dimethyl-, and trimethylammonium cations and quaternary ammonium cations such as tetramethyl-ammonium and dimethyl piperdinium cations and those derived from alkylamines such as ethylamine, diethyl-amine, triethylamine, mixtures thereof, and the like.
  • Preferred B-acyloxy-alkane-l-sulfonate salts therein are the alkali metal salts of ,B-acetoxy-alkanel -sulfonic acids corresponding to the above formula wherein R is an alkyl of about l2 to about 16 carbon atoms, these salts being preferred from the standpoints of their excellent cleaning properties and ready availability.
  • a preferred class of anionic organic detergents are the B-alkyloxy alkane sulfonates. These compounds have the following formula:
  • R is a straight chain alkyl group having from 6 to 20 carbon atoms
  • R is a lower alkyl group having from 1 to 3 carbon atoms
  • M is a salt-forming radical hereinbefore described.
  • B-alkyloxy alkane sulfonates or alternatively 2-alkyloxy-alkane-l-sulfonates, utilizable herein to provide superior cleaning and whitening levels under household washing conditions include potassium B-methoxydecanesulfonate,
  • alkyl ether sulfates are alkyl ether sulfates. These materials have the formula RO(C H O),SO M wherein R is alkyl or alkenyl or about 10 to about 20 carbon atoms, x is l to 30, and M is a salt-forming cation defined hereinbefore.
  • the alkyl ether sulfates of the present invention are condensation products of ethylene oxide and monohydric alcohols having about 10 to about 20 carbon atoms.
  • R has 14 to 18 carbon atoms.
  • the alcohols can be derived from fats, e.g., coconut oil or tallow, or can be synthetic. Lauryl alcohol and straight chain alcohols derived from tallow are preferred herein. Such alcohols are reacted with l to 30, and especially 6, molar proportions of ethylene oxide and the resulting mixture ofmolecular species, having, for example, an average of 6 moles of ethylene oxide per mole of alcohol, is sulfated and neutralized.
  • alkyl ether sulfates of the present invention are sodium coconut alkyl ethylene glycol ether sulfate; lithium tallow alkyl triethylene glycol ether sulfate; and sodium tallow alkyl hexaoxyethylene sulfate.
  • alkali metal coconutand tallow-alkyl oxyethylene ether sulfates having an average of about I to about 10 oxyethylene moieties.
  • the alkyl ether sulfates of the present invention are known compounds and are described in Pat. No. 3,332,876 to Walker (July 25, 1967) incorporated herein by reference.
  • anionic non-soap synthetic detergents which come within the terms of the present invention are the reaction product of fatty acids esteritied with isethionic acid and neutralized with sodium hydroxide where, for example, the fatty acids are derived from coconut oil; sodium or potassium salts of fatty acid amide of methyl tauride in which the fatty acids, for example, are derived from coconut oil.
  • Other an ionic synthetic detergents of this variety are setforth in Pat. Nos. 2,486,921; 2,486,922; and 2,396,278.
  • anionic, non-soap, synthetic detergents which come within the terms of the present invention, are the compounds which contain two anionic functional groups. These are referred to as dianionic detergents.
  • Suitable di-anionic detergents are the disulfonates, disulfates, or mixtures thereof which may be represented by the following formulae:
  • R is an acyclic aliphatic hydrocarbyl group having 15 to 20 carbon atoms and M is a water-solubilizing cation, for example, the C to disodium 1,2- alkyldisulfates, C to C dipotassium-l,2-alkyldisulfonates or disulfates, disodium l,9-hexadecyl sidulfates, C, to C disodium-l,2-alkyldisulfonates, disodium l,9stearydisulfates and 6,l0-octadecyldisulfates.
  • the aliphatic portion of the disulfates or disulfonates is generally substantially linear, desirable, among other reasons, because it imparts desirable biodegradable properties to the detergent compound.
  • the water-solubilizing cations include the customary cations known in the detergent art, i.e., the alkali metals, and the alkaline earth metals, as well as other metals in group "A, B, lllA, [VA and [VB of the Periodic Table except for Boron.
  • the preferred watersolubilizing cations are sodium or potassium.
  • anionic non-soap synthetic detergents which come within the terms of the present invention are the reaction product of fatty acids esterified with isethionic acid and neutralized with sodium hydroxide where, for example, the fatty acids are derived from coconut oil; sodium or potassium salts of fatty acid amide of methyl tauride in which the fatty acids, for example, are derived fron coconut oil.
  • Other anionic synthetic detergents of this variety are set forth in US. Pat. Nos. 2,486,921, 2,486,922; and 2,396,278.
  • succinamates include the class designated as succinamates.
  • This class includes such surface active agents as disodium N- octadecylsulfo succinamate; tetrasodium N-(l,2- dicarboxyethyl)-N-octadecyl-sulfo-succinamate; diamyl ester of sodium sulfosuccinic acid; dihexyl ester of sodium sulfosuccinic acid; dioxtyl ester of sodium sulfosuccinic acid.
  • olefin sulfonates having about 12 to about 24 carbon atoms.
  • olefin sulfonates is used herein to mean compounds which can be produced by the sulfonation of a-olefin by means of uncomplexed sulfur trioxide, followed by neutralization of the acid reaction mixture in conditions such that any sultones which have been formed in the reaction are hydrolyzed to give the corresponding hydroxy-alklanesulfonates.
  • the sulfur trioxide may be liquid or gaseous, and is usually, but not necessarily, diluted by inert diluents, for example by liquid SO chlorinated hydrocarbon, etc., when used in the liquid form, or by air, nitrogen, gaseous S0 etc., when used in the gaseous form.
  • inert diluents for example by liquid SO chlorinated hydrocarbon, etc., when used in the liquid form, or by air, nitrogen, gaseous S0 etc., when used in the gaseous form.
  • the a-olefins from which the olefin sulfonates are derived are mono-olefins having 12 to 24 carbon atoms, preferably 14 to 16 carbon atoms. Preferably, they are straight chain olefins.
  • suitable l-olefins include l-dodecene; l-tetradecene; l-hexadecene; loctadecene; l-eicosene and l-tetracosene.
  • the olefin sulfonates can contain minor amounts of other materials, such as alkene disulfonates depending upon the reaction conditions, proportions of reactants, the nature of the starting olefins and impurities in the olefin stock and side reaction during the sulfonation process.
  • Nonionic 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 water-soluble 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.
  • Pluronic These compounds are formed by condensing ethylene oxide with 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 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 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 5 to 25 moles of ethylene oxide per mole of alkyl phenol.
  • the alkyl substituent in such compounds may be derived from polymerized propylene, diisobutylene, octene, or
  • nonene for example.
  • ethylene oxide e.g., a coconut alcohol-ethylene oxide condensate having from 5 to 30 moles of ethylene oxide per mole of coconut alcohol, the coconut alcohol fraction having from l to 14 carbon atoms.
  • Nonionic detergents include nonyl phenol condensed with either about 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 moles of ethylene oxide per mole of alcohol and the condensation product of about 15 moles of ethylene oxide with one mole of tridecanol.
  • a detergent having the formula R'R R N O (amine oxide detergent) wherein R is an alkyl group containing from about 10 to about 28 carbon atoms, from 0 to about 2 hydroxy groups and from 0 to about 5 ether linkages, there being at least one moiety of R which is an alkyl group containing from about 10 to about 18 carbon atoms and 0 ether linkages, and each R and R" are selected from the group consisting of alkyl radicals and hydroxyalkyl radicals containing from 1 to about 3 carbon atoms;
  • amine oxide detergents include: dimethyldodecylamine oxide, dimethyltetradecylamine oxide, ethylmethyltetradecylamine oxide, cetyldimethylamine oxide, dimethylstearylamine oxide, cetylethylpropylamine oxide, diethyldodecylamine oxide, diethyltetradecylamine oxide, dipropyldodecylamine oxide, bis-(Z-hydroxyethyl)dodecylamine oxide, bis- (2-hydroxyethyl )-3-dodecoxyl -hydroxypropylamine oxide, (2-hydroxypropyl)methyltetradecylamine oxide, dimethyloleyamine oxide, dimethyl-(2- hydroxydodecyl)amine oxide, and the corresponding decyl, hexadecyl and octadecyl homologs of the above compounds.
  • a detergent having the formula R R R"P O phosphine oxide detergent
  • R is an alkyl group containing from about 10 to about 28 carbon atoms, from 0 to about 2 hydroxy groups and from 0 to about 5 ether linkages, there being at least one moiety of R which is an alkyl group containing from about 10 to about 18 carbon atoms and 0 ether linkages, and each of R and R are selected from the group consisting of alkyl radicals and hydroxyalkyl radicals containing from 1 to about 3 carbon atoms.
  • phosphine oxide detergents include: dimethyldodecylphosphine oxide, dimethyltetradecylphosphine oxide, ethylmethyltetradecylphosphine oxide, cetyldimethylphosphine oxide, dimethylstearylphosphine oxide, cetylethylpropylphosphine oxide, diethyldodecylphosphine oxide, diethyltetradecylphosphine oxide, dipropyldodecylphosphine oxide, bis- (hydroxymethyl )dodecylphosphine oxide, bis-( 2- hydroxyethyl )-dodecylphosphine oxide, (2- hydroxypropyl )methyltetradecylphosphine oxide,
  • dimethyloleylphosphine oxide and dimethyl-(2- hydroxydodecyl)phosphine oxide and the corresponding decyl, hexadecyl, and octadecyl homologs of the above compounds.
  • disodium octadecyl-iminodiazetate sodium 1- carboxymethyl-2-undecyl-imidazole, and sodium N,N- bis(2-hydroxyethyl)-2-sulfato3-dodecoxypropylamine.
  • Zwitterionic synthetic detergents can be broadly described as derivatives of aliphatic quaternary ammonium and phosphonium or tertiary sulfonium compounds, in which the cationic atom may be part of a heterocyclic ring, and in which the aliphatic radical may be straight chain or branched, and wherein one of the aliphatic substituents contains from about 3 to 18 carbon atoms, and at least one aliphatic substituent contains an anionic water-solubilizing group, e.g., carboxy, sulfo, sulfato, phosphato, or phosphono.
  • anionic water-solubilizing group e.g., carboxy, sulfo, sulfato, phosphato, or phosphono.
  • Examples of compounds falling within this definition are 3- (N,N-dimethyl-N-hexadecyl-ammonio)-2- hydroxypropanel -sulfonate, 3-( N,N-dimethyl-N- hexadecylammonio )-propanel -sulfonate, 2-( N,N- dimethyl-N-dodecylammino)acetate, 3-(N,N-dimethyl N-dodecylammonio)propionate, 2-(N,N-dimethyl-N- octadecylammonio)-ethyl sulfate, 2-(trimethylammonio)ethyl dodecylphosphonate, ethyl 3-(N,N- dimethyl-N-dodecylammonio)propylphosphonate, 3- (P,P-dimethyl-P-dodecylphosphonio )-propanel sulfonate
  • a detergent composition prepared according to the present invention contains as essential ingredients (a) a detergent ingredient and (b) a builder ingredient.
  • a composition can contain a single detergent compound and the biodegradable builder mixture of benzene pentaand hexacarboxylic acid salts.
  • the detergent ingredient consists of composition of detergent compounds selected from the foregoing classes.
  • the active ingredient can consist of a mixture of two or more anionic detergents; or a mixture of an anionic detergent and a nonionic detergent; or, by way of another example, the active detergent can be a ternary mixture of two anionic detergents and a zwitterionic detergent.
  • the present invention can find useful application by practicing a partial replacement of the biodegradable benzene pentaand hexacarboxylic acid salt mixture for traditional, commonly used detergency builders.
  • the portion of the complete detergent formulation that functions as a builder can likewise be composed of a mixture of builder compounds.
  • the substantially biodegradable builder compounds described herein can be mixed together with other water-soluble inorganic alkaline builder salts such as sodium tripolyphosphate or potassium pyrophosphate or water-soluble organic builder salts such as watersoluble salts of nitrilotriacetic acid, ethylenediaminetetraacetic acid, ethane-l-hydroxy-l, 1- diphosphonic acid.
  • the builder component of a complete formulation can consist of ternary mixtures of these several types of builder compounds. In this way, it is possible to obtain a balance between the mixture of the biodegradable salts of benzene pentaand hexacarboxylic acid and such builders as sodium tripolyphosphate and the like.
  • Water-soluble inorganic alkaline builder salts which can be used in this invention in combination with the mixture of the biodegradable salts of benzene pentaand hexacarboxylic acid are alkali metal carbonates,
  • borates phosphates, polyphosphates, bicarbonates and silicates.
  • Ammonium and substituted ammonium salts of these materials can also be used.
  • suitable salts are sodium tripolyphosphate, sodium carbonate, sodium tetraborate, sodium and potassium pyrophosphate, sodium and ammonium bicarbonate, potassium tripolyphosphate, sodium hexametaphosphate, sodium sesquicarbonate, sodium orthophosphate and potassium bicarbonate.
  • organic alkaline detergency builder salts are: (1 Water-soluble aminopolycarboxylates, e.g., sodium and potassium ethylenediaminetetraacetates, nitrilotriacetates and N-(2-hydroxyethyl)- nitrilodiacetates; (2) Water-soluble salts of phytic acid, e.g., sodium and potassium phytates See Pat. No.
  • Water-soluble, polyphosphonates including specifically, sodium, potassium and lithium salts of ethane-l-hydroxy-l,l-diphosphonic acid, sodium, potassium and lithium salts of methylene diphosphonic acid, sodium, potassium and lithium salts of ethylene diphosphonic acid, and sodium, potassium and lithium salts of ethane-1 ,1 ,2-triphosphonic acid.
  • a detergent builder material comprising a water-soluble salt of a polymeric aliphatic polycarboxylic acid having the following structural relationships as to the position of the carboxylate groups and possessing the following prescribed physical characteristics: (a) a minimum molecular weight of about 350 calculated as to the acid form; (b) an equivalent weight of about to about calculated as to acid form; (c) at least 45 mole percent of the monomeric species having at least 2 carboxyl radicals separated from each other by not more than 2 carbon atoms; (d) the site of attachment of the polymer chain of any carboxyl-containing radical being separated by not more than 3 carbon atoms along the polymer chain from the site of attachment of the next carboxylcontaining radical.
  • Mixtures of organic and/or inorganic builders can be used in combination with the builder mixture of the present invention and are generally desirable.
  • One such auxiliary mixture of builders is disclosed In Pat. No. 3,392,121, e.g., ternary mixtures of sodium tripolyphosphate, sodium nitrilotriacetate and trisodium ethane- 1 -hydroxy-l ,l-diphosphonate.
  • the above described builders can also be utilized singly in this invention.
  • compositions in which the proportion by weight of detergent to builder mixture is in the range of 2:1 to 1:10.
  • An illustrative and preferred embodiment is a biodegradable built detergent composition consisting essentially of (A) a detergent selected from alkali metal straightchain alkyl benzene sulfonate, the alkyl group having from 8 to 24 carbon atoms, preferably 8 to 18, and an alkali metal olefin sulfonate having 8 to 24 carbon atoms, preferably 8 to 18, and (B) as a detergency builder, the biodegradable phosphorus-free watersoluble alkali metal salts of the benzene pentaand hexacarboxylic acid mixture, the proportion by weight of said detergent to said builder mixture being in the range of 5:1 to 1:20, and preferably2:l to 1:10.
  • the preferred detergents are sodium B-methoxy hexadecane sulfonate, sodium salt of the sulfonation product of the condensation product of one mole of tallow alcohol with three moles of ethylene oxide, sodium dodecyl benzene sulfonate, sodium tridecyl benzene sulfonate, and sodium dodecene-l-sulfonate, sodium tetradecene-l-sulfonate, and sodium hexadecene-lsulfonate.
  • Sodium salt is the preferred salt of the benzene pentaand hexacarboxylic acids.
  • the built detergent compositions of the present invention can be formulated and prepared into any of the several commercially desirable solid and liquid forms including, for example, granules, flakes, tablets, and water-based and alcohol-based liquid detergents, and the like.
  • a special embodiment of this invention is a built liquid detergent composition containing a detergent and a builder mixture is the by weight ratio (detergent to builder mixture) of 2:1 to about 1:5; preferably 2:1 to about 1:3. Potassium salts are especially useful in liquid formulations due to the increased solubility characteristics of potassium over sodium.
  • the built detergent compositions of the present invention perform at their maximum level in a washing solution which has a pH in the range of from about 8 to about 12. Within this broad range, it is preferred to operate at a pH of from about 8.5 to 11.
  • the detergent and the builder mixture can be neutralized to a degree sufficient to insure that this pH prevails in any washing solution. If desired, other alkaline materials can be added to the complete formulation to provide for any pH adjustments desired.
  • a preferred embodiment is to have the detergent composition whether in solid or liquid form provide a pH in the aforementioned ranges at the usual recommended usage levels.
  • a water-soluble sodium carboxymethyl cellulose can be added in minor amounts to inhibit soil redeposition.
  • Tarnish inhibitors such as benzotriazole or ethylenethiourea can also be added in amounts up to about 3 percent.
  • an alkaline material or alkali such as sodium or potassium hydroxide can be added as supplementary pH adjusters.
  • Other usual additives include sodium sulfate, sodium carbonate, water, and the like.
  • Corrosion inhibitors are also frequently used.
  • Watersoluble silicates are highly effective corrosion inhibi tors and can be added if desired at levels of from about 3 to about 8 percent by weight of the total composition.
  • Alkali metal, preferably potassium and sodium silicates are preferred having a weight ratio of SiO :M O of from about 1.0:1 to 2.8: 1. (M refers to sodium or potassium).
  • Sodium silicate having a ratio of SiO :Na O of from about 1.621 to 2.45:1 is especially preferred.
  • a hydrotrope is desirable.
  • Suitable hydrotropes are water-soluble alkali metal salts of toluenesulfonate, benzenesulfonate, and xylenesulfonate.
  • Preferred hydrotropes are potassium or sodium toluenesulfonates.
  • the hydrotrope salt may be added at levels up to about 12 percent. While a hydrotrope will not ordinarily be found necessary, it can be added, if so desired, for any reason such as to function as a solubilizing agent and to produce a product which retains its homogeneity at a low temperature.
  • compositions in which the precentages are by weight, will serve to illustrate, but not limit, the invention.
  • Each of the compositions in the following Examples give in solution a pH within the desired range of from about 8 to about 12.
  • a granular built detergent composition according to this invention has the following formulation:
  • the straight chain dodecyl benzene sodium sulfonate in the preceding composition can be replaced on an equal weight basis by either branched chain sodium dodecyl benzene sulfonate, sodium tallow alkyl sulfate, sodium coconut oil alkyl sulfate, sodium olefin sulfonate as described in the specification derived from alpha olefins having an average of 14 carbon atoms in the molecule, or a mixture of straight chain dodecyl benzene sodium sulfonate and sodium tallow alkyl sulfate on an equal weight basis.
  • the sodium salts of the builders can be added as the salt or they can be present as the free acid neutralized in situ to the salt form.
  • the effectiveness of the mixture of sodium salts of the benzene pentaand hexacarboxylic acids builder was demonstrated by a detergency test referred to as a fabric softness/deposition test. This test generally involves a procedure of washing laundry with the detergent composition to be tested.
  • the laundry pieces are washed, rinsed, graded, and the cycle is repeated several times. Grading of fabric deposition is made on a scale of to 5 where 0 represents no visual precipitate deposit. Softness is also reflected in this grading in that the deposit of precipitates on the laundry samples will adversely affect its feel.
  • a commercially available automatic washer was filled with 16 gallons of water having a temperature of 100F and hardness of 14 grains. One and one-fourth cups of the above detergent composition was next added. The contents of the washer was agitated for 30 seconds to dissolve the detergent composition. Thereafter, 2 pounds of ordinary soiled laundry plus a dark colored cotton wash cloth were added and washed for 6 minutes. The ordinary soiled laundry in addition to the wash cloth was used in this example as a source of soil and in order to give a full load. For purposes of this example, the originally soiled laundry was not evaluated at the end of the wash cycles. After a cold rinse, the originally soiled laundry and wash cloth were spun. removed, and line dried.
  • compositions of this invention are:
  • EXAMPLE F Pcntasodium salt of benzene pentacarboxylic acid 5.07: Hexasodium salt of benzene hexacarboxylic acid 50.07: Sodium tallow soap 5.5% Sodium silicate (siO- zNa O ratio 2.0) l6.0'7r Sodium sulfate l3.5'71 Water EXAMPLE G Pentasodium salt of benzene pentacarboxylic acid 2.0% Hcxasodium salt of benzene hexacarboxylic acid 10.09: TE;,S (as in Example C) 60.0% Sodium Silicate (SiO-,:Na O ratio 2.0) 8.0% Sodium sulfate 10.0% Water 10.0%
  • a built detergent composition consisting essentially of:
  • an organic water-soluble synthetic detergent selected from the group consisting of anionic, nonthe detergency builder is from 5:1 to 1:20.

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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)
  • Health & Medical Sciences (AREA)
  • Emergency Medicine (AREA)
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US00142360A 1969-11-24 1971-05-11 Built detergent composition Expired - Lifetime US3844982A (en)

Priority Applications (11)

Application Number Priority Date Filing Date Title
BE759283D BE759283A (fr) 1969-11-24 Composition detergente avec adjuvant, notamment biodegradable
AU22443/70A AU2244370A (en) 1969-11-24 1970-11-19 Built detergent composition
DE19702057354 DE2057354A1 (de) 1969-11-24 1970-11-21 Gerueststoffhaltige Wasch- und Reinigungsmittelmischung
CA098830A CA928603A (en) 1969-11-24 1970-11-23 Built detergent composition
FR707042028A FR2075875B1 (ja) 1969-11-24 1970-11-23
GB5582670A GB1302788A (ja) 1969-11-24 1970-11-24
CH1739470A CH547348A (de) 1969-11-24 1970-11-24 Gerueststoffhaltiges, phosphorfreies wasch- und reinigungsmittel.
NL7017181A NL7017181A (ja) 1969-11-24 1970-11-24
US00142360A US3844982A (en) 1969-11-24 1971-05-11 Built detergent composition
CA122,893,A CA950788A (en) 1969-11-24 1971-09-15 Built detergent composition
PH12860*UA PH9244A (en) 1969-11-24 1971-09-22 Built detergent composition

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US87961269A 1969-11-24 1969-11-24
US00142360A US3844982A (en) 1969-11-24 1971-05-11 Built detergent composition

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US3844982A true US3844982A (en) 1974-10-29

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US00142360A Expired - Lifetime US3844982A (en) 1969-11-24 1971-05-11 Built detergent composition

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US (1) US3844982A (ja)
AU (1) AU2244370A (ja)
BE (1) BE759283A (ja)
CA (2) CA928603A (ja)
CH (1) CH547348A (ja)
DE (1) DE2057354A1 (ja)
FR (1) FR2075875B1 (ja)
GB (1) GB1302788A (ja)
NL (1) NL7017181A (ja)
PH (1) PH9244A (ja)

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3915879A (en) * 1973-04-10 1975-10-28 Lever Brothers Ltd Detergent compositions
US3951826A (en) * 1972-07-25 1976-04-20 Colgate-Palmolive Company All purpose liquid detergent
US3951877A (en) * 1972-07-17 1976-04-20 Lion Fat & Oil Co., Ltd. Heavy-duty granular detergent composition with sodium citrate builder
US4013577A (en) * 1972-04-14 1977-03-22 Colgate-Palmolive Company Heavy duty dry biodegradable detergent composition
US4021376A (en) * 1972-05-17 1977-05-03 Lever Brothers Company Detergent compositions with nonphosphate builders containing two or more carboxyl groups
US4071476A (en) * 1974-01-28 1978-01-31 Texaco Inc. Detergent builders and composition containing the same
US4476929A (en) * 1982-09-29 1984-10-16 Phillips Petroleum Company Sulfoxide cosurfactants in enhanced oil recovery processes

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2556364B1 (fr) * 1983-12-10 1989-10-27 Sandoz Sa Compositions detergentes liquides exemptes de phosphate

Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2264103A (en) * 1936-06-06 1941-11-25 Procter & Gamble Process and product for softening hard water
US2311008A (en) * 1939-06-12 1943-02-16 Procter & Gamble Process and composition for softening hard water
US3308067A (en) * 1963-04-01 1967-03-07 Procter & Gamble Polyelectrolyte builders and detergent compositions
US3368978A (en) * 1964-12-28 1968-02-13 Monsanto Co Builder compositions and detergent compositions using same
US3459670A (en) * 1966-07-01 1969-08-05 Monsanto Co Builders for synthetic detergents
US3463734A (en) * 1966-06-16 1969-08-26 Monsanto Co Builders for synthetic detergents
US3692684A (en) * 1969-10-01 1972-09-19 Valter Sven Erwin Hentschel Detergent

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2264103A (en) * 1936-06-06 1941-11-25 Procter & Gamble Process and product for softening hard water
US2311008A (en) * 1939-06-12 1943-02-16 Procter & Gamble Process and composition for softening hard water
US3308067A (en) * 1963-04-01 1967-03-07 Procter & Gamble Polyelectrolyte builders and detergent compositions
US3368978A (en) * 1964-12-28 1968-02-13 Monsanto Co Builder compositions and detergent compositions using same
US3463734A (en) * 1966-06-16 1969-08-26 Monsanto Co Builders for synthetic detergents
US3459670A (en) * 1966-07-01 1969-08-05 Monsanto Co Builders for synthetic detergents
US3692684A (en) * 1969-10-01 1972-09-19 Valter Sven Erwin Hentschel Detergent

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4013577A (en) * 1972-04-14 1977-03-22 Colgate-Palmolive Company Heavy duty dry biodegradable detergent composition
US4021376A (en) * 1972-05-17 1977-05-03 Lever Brothers Company Detergent compositions with nonphosphate builders containing two or more carboxyl groups
US3951877A (en) * 1972-07-17 1976-04-20 Lion Fat & Oil Co., Ltd. Heavy-duty granular detergent composition with sodium citrate builder
US3951826A (en) * 1972-07-25 1976-04-20 Colgate-Palmolive Company All purpose liquid detergent
US3915879A (en) * 1973-04-10 1975-10-28 Lever Brothers Ltd Detergent compositions
US4071476A (en) * 1974-01-28 1978-01-31 Texaco Inc. Detergent builders and composition containing the same
US4476929A (en) * 1982-09-29 1984-10-16 Phillips Petroleum Company Sulfoxide cosurfactants in enhanced oil recovery processes

Also Published As

Publication number Publication date
AU2244370A (en) 1972-05-25
PH9244A (en) 1975-07-30
DE2057354A1 (de) 1971-05-27
FR2075875A1 (ja) 1971-10-15
NL7017181A (ja) 1971-05-26
CA950788A (en) 1974-07-09
FR2075875B1 (ja) 1973-02-02
BE759283A (fr) 1971-05-24
CA928603A (en) 1973-06-19
CH547348A (de) 1974-03-29
GB1302788A (ja) 1973-01-10

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