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Publication numberUS3812044 A
Publication typeGrant
Publication dateMay 21, 1974
Filing dateDec 28, 1970
Priority dateDec 28, 1970
Also published asCA947611A1, DE2164872A1
Publication numberUS 3812044 A, US 3812044A, US-A-3812044, US3812044 A, US3812044A
InventorsD Connor, H Krummel
Original AssigneeProcter & Gamble
Export CitationBiBTeX, EndNote, RefMan
External Links: USPTO, USPTO Assignment, Espacenet
Detergent composition containing a polyfunctionally-substituted aromatic acid sequestering agent
US 3812044 A
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Description  (OCR text may contain errors)

United States Patent Ofice 3,812,044 Patented May 21, 1974 ABSTRACT OF THE DISCLOSURE A detergent composition is provided comprising a water-soluble organic synthetic detergent, and as a detergency aid, a sequestering agent which is a water-soluble salt of a polyfunctionally-substituted aromatic acid compound having the formula wherein at least two Rs are different functional groups of the type described.

BACKGROUND OF THE INVENTION Metal sequestering agents are frequently used as additives in detergent compositions of all types including household detergent compositions, e.g., laundry detergents and industrial compositions, e.g., hard-surface cleaning products. It is known, for instance, that when soaps are used in hard water, insoluble calcium and magnesium soaps are formed which detract considerably from the detergency objectives.

The surface-active and foaming properties of non-soap synthetic detergents are also adversely effected by the presence of hardness minerals, such as alkaline earth metals.

The precipitation of soap and inactivation of synthetic detergents by hardness constituents of water, especially calcuim and magnesium, is a cause of considerable wastefulness in the use of such detergent ingredients. Detergent ingredients thus reacted and rendered ineffective are not available to contribute their detergency properties.

Condensed polyphosphates such as sodium tripolyphosphate and sodium pyrophosphate and nitrogen-containing compounds'such as sodium nitrilotriacetate are common examples of known sequestering agents useful as ingredients in detergent compositions. As a consequence of the contribution by sequestering agents to overall improved cleaning results, such additives are referred to as builders. In one respect, the enhanced cleaning is due to decreased adsorption of detergents and allied materials on the fabrics being washed or treated.

The phosphorus-content and nitrogen-content of such compositions may have adverse environmental effects, such as accelerated eutrophication of lakes and streams.

Eutrophication is a natural process which is vital to sustaining the life of any body of water by enabling plant organisms to grow in the water and thus provide food for fish.

Accelerated" or excessive eutrophication, however, is of timely concern. Too much plant life in lakes tergent compositions are two such nutrients. These materials, however, by themselves do not cause excessive eutrophication. Other nutrients such as carbon must also be present. A combination of nutrients stimulates the growth of plant life in lakes and streams.

A primary object of the present invention is to pro vide phosphateand nitrate-free detergent compositions which are effective in water solutions over a wide range of concentrations and pHs inasmuch as the conditions under which laundry is done vary widely with the individual and the locality. Another object is to provide improved heavy-duty laundry detergent compositions containing, as builders, sequestering agents selected from the novel classes of compounds described herein.

DESCRIPTION OF THE INVENTION An improved detergent composition, according to the present invention, comprises a water-soluble organic synthetic detergent and, as a detergency aid, a sequestering agent which is a water-soluble salt of a polyfunctionally-substituted aromatic acid compound having the formula wherein each R represents --CH CH wherein X represents halogen;

wherein R represents SO H,

and wherein at least two R substituents on the aromatic nucleus are different functional groups.

Illustrative examples of the novel class of sequestering agents of this invention are:

l,3,5-trihydroxy-2,4,6-benzene trisulfonic acid 1,4-disulfo-2,3,5,6tetracarboxybenzene, 1,4-dihydroxy-2,3,5,6-tetracarboxybenzene, 1,3,5-trihydroxy-2,4,6-benzenetricarboxylic acid 1,3-disulfo-2,4,5,6-tetracarboxybenzene 1,3-dihydroxy-Z,4,5,6-tetracarboxybenzene 1,3,5-trist[carboxymethylether]-2,4,6-trisulfobenzene 1,3,5-tris[carboxymethylether]-2,4,6-tricarboxybenzene 1,3,5-tris [2-carboxyethylether] 2,4,6-trisulfobenzene 1,3,5-tris[Z-carboxyethylether]-2,4,6-tricarboxybenzene 1,3,5-trihydroxy-2,4,6-benzenetriacetic acid 1,3,5-trisulfo-2,4,6-benzenetriacetic acid 1,3,5-triacetal-2,4,6-trihydroxybenzene 2,3,4,5,6-pentacarboxybenzyl alcohol 2,4-disulfo-3,5,6-tricarboxybenzyl alcohol 4sulfo-2,3,5,6-tetracarboxybenzyl alcohol 1,4-methoxy-2,3,5,6-tetracarboxybenzene 1,4-bis(hydroxymethyl)-2,3,5,6-tetracarboxybenzene 1,3-dihydroxy-5- [carboxymethylether] benzene 1-carboxy-2-hydroxy-3,S-disulfobenzene 1,2,4,5-tetraakis[hydroxymethyl]-3-sulfobenzene 1-hydroxy-2,6-disulfo-4-carboxybenzene 1,3-dihydroxy-5-[acetylether1benzene 1-methy1-2,3,4,5,6-pentacarboxybenzene 2,3,4,5,6-pentacarboxybenzaldehyde 1-sulf0-2,3,4,5,6-pentacarboxybenzene 1,4 dimethyl-2,3,5,6-tetracarboxybenzene 1,3,5-trihydroxy-2,4,6-benzenetrimethylsulfonate 2,3,4,5,6-pentacarboxybenzylsulfuric acid 2,3,4,5,6-pentacarboxybenzylsulfonic acid 2,3,4,5,6pentacarboxybenzyl-carboxyrnethyl-ether 2,3,4,5,6-pentacarboxybenzyl-2-carboxyethyl-ether 1,3-disulfo-2,4,S-tricarboxybenzene 1-sulfo-2,3,5,6-tetracarboxybenzene 1,S-disulfo-Z,3,4-trihydroxybenzene 1,3,5-trihydroxy-2,4-disulfobenzene 1,3,5-trisulfo-Z,4-dihydroxybenzene 1-hydroxy-2,3,5,6-tetracarboxybenzene 2,4-dihydroxy-1,3,5-tricarboxybenzene 2,3,4-trihydroxy1,5-dicarboxybenzene 1,3,S-trihydroxy-Z,4-dicarboxybenzene 1,3,5-tris[carboxymethylether]-2,4-dicarboxybenzene 1,3,5-tris[2-carboxyethylether] -2,4-dicarboxybenzene 2,4-bis[carboxymethylether]-1,3,5-tricarboxybenzene 2,4-bis [2-carboxyethylether] l ,3 ,5 -tricarboxybenzene 2,3,5,6-tetracarboxybenzyl-carboxyrnethyl-ether 2,3,5,6-tetracarboxybenzyl-Z-carboxyethyl-ethe S-sulfo-1,2,4-tricarboxybenzene 4 2,3-dihydroxy-1,4-benzenediacetic acid l,3-dihydroxy-2,4-disulfobenzene 1,2-dihydroxy-3,5-disulfobenzene 2,4,6-tricarboxybenzyl-carboxymethyl-ether 1-sulfo-2,4,6-tricarboxybenzene 2,4,6-tricarboxybenzyl-2-carboxyethyl-ether 1-hydroxy-2,4-disulfo-6-carboxybenzene 1,3-disulfo-2,S-dicarboxybenzene l-hydroxy-2,4,6-tricarboxybenzene 1,3,5-trihydroxy-2-carboxybenzene 1,3,5-trisulfo-2-carboxybenzene 1,2,3-trihydroxy-5-carboxybenzene 1,3,5-trisulfo-Z-hydroxybenzene 1, 3 ,5 -tris [carboxyethylether] -2-carboxybenzene 1,3 ,5 -tris [2-carboxyethylether] -2-carboxybenzene 2- [2-carboxyethylether1-l, 3,5 -tricarboxybenzene 2-[carboxymethylether]-1,3,5-tricarboxybenzene 1,2-dihydroxy-3-sulfo-5-carboxybenzene 1-sulfo-2,4,5-tricarboxybenzene l,4-dihydroxy-2,S-disulfobenzene 2,4-disulfo-1,5-dihydroxybenzene l,4-dihydroxy-2,S-benzenediacetic acid 4,6-dicarboXy-1,3-dihydroxybenzene 1,4-bis [carboxymethylether] -2,5-dicarboxybenzene 1,4-bis [Z-carboxyethylether] -2,5-disulfobenzene 1,4-bis[carboxymethylether]-2,5-disulfobenzene 2,4,S-tricarboxybenzyl-carboxymethyl-ether 1-carboxy-2-hydroxy-4-sulfo-5-benzeneacetic acid 1,4-dihydroxy-2,S-dicarboxybenzene 1,3-dihydroxy-2-carboxybenzene 1-sulfo-2-hydroxy-S-carboxybenzene l,3-bis[carboxymethylether]-2-carboxybenzene 1,3-bis [2-carboxyethylether] -2-carboxybenzene 1,3-dihydroxybenzyl-carboxymethyl-ether 1,3-dihydroxybenzyl-Z-carboxyethyl-ether 1-hydroxy-4-sulfo-2-carboxybenzene 2,4-disulfo-l-hydroxybenzene 1- [carboxymethylether] -2,4-disulfobenzene 1- [2-carboxyethylether] -2,4-disulfobenzene 1-hydroxy-2-carboxybenzene l- [2-carboxyethylether] -2-carboxybenzene 1-[carboxymethylether]-2-carboxybenzene 1-hydroxy-4-benzenesulfonic acid l-hydroxy-Z-benzene sulfonic acid 1-[carboxyrnethylether]-4-benzene sulfonic acid 1-[2-carboxyethylether]-4-benzene sulfonic acid 1-[carboxymethylether]-2-benzene sulfonic acid 1-[2-carboxyethylether]-2-benzene sulfonic acid 1,5-dicarboXy-2,4-bis [carboxyformyl] benzene.

The process by which these sequestering agents can be prepared form no part of this invention. The discovery upon which the present invention is based is the discovery that sequestering agents coming within the class defined above and the specific examples given are effective sequestering agents which, when used in conjunction with watersoluble organic synthetic detergents, serve to significantly enhance the cleaning action of such detergents.

Of the sequestering agents described herein optimum detergency building action is achieved with those in which the functional groups are positioned near each other as illustrated for example when functional groups are attached to adjacent carbon atoms on the aromatic nucleus.

For purposes of this invention and with reference specifically to the R substituents noted above, hydrogen, the lower alkyl groups such as methyl, ethyl, propyl, butyl, isobutyl, and the halogens and halogenated-alkyl groups are non-functional substituents.

The amount of sequestering agent required to aid in the detergency varies widely depending on many circum stances including the specific sequesterants properties, the detergent employed, the hardness content of the Water, the oil load and the nature of the substrate being washed or treated, and the like. In any event, an effective or sufiicient amount is used, and this implies that a sulficient amount of sequesterant is used to render the water suitable for its intended purpose. This may be judged by various means, such as soap titration, observation of the clarity of the solution, or by a practical trial of the softened water for its intended purpose. A complete softening, although sometimes desirable, is in many cases not necessary.

In preparing built laundry detergent compositions, the proportion by weight of the detergent to the sequestering agent is in the range of 20:1 to 1:20 and preferably :1 to 1:10. Within these ranges, compositions are represented which are lightly built or heavily built depending on the amount of sequestrant builder used.

The compositions of this invention are effective over the broad pH range of about 6 to 12, but optimum cleaning results are achieved with ordinary alkaline detergents in the range of 8 to 12 and preferably 9 to 11. The compositions can be formulated to provide a desired pH in the ranges by proper selection of appropriates salts. Thus, for example, preferred water-soluble salts for both the detergent and sequestering agent, are alkali metal salts such as sodium, potassium, lithium and ammonium or alkylsubstituted ammonium, e.g. triethanol ammonium. Sodium and potassium are preferred water-soluble cations.

Depending on the pH of the desired solution, the salts are partially or fully neutralized.

The detergent compositions can be prepared as solid (granular, tablet, powder) or liquid (aqueous or nonaqueous-based) physical forms.

Any water-soluble organic synthetic detergent can be used in conjunction with the novel class of sequestering builder agents of this invention and have its detergency properties improved. The detergents include anionic, nonionic, ampholytic, and zwitterionic surface-active agents, or mixtures of such materials. Each of these classes of detergents is illustrated by the following listed compounds:

A. 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 10 to about 20 carbon atoms. Suitable fatty acids can be obtained from natural sources such as, for instance, from plant or animal esters (e.g., palm oil, coconut oil, babassu oil, soybean oil, castor oil, tallow, whale and fish oils, grease, lard, and mixtures thereof). The fatty acids also can be synthetically prepared (e.g., by the oxidation of petroleum, or by hydrogenation of carbon monoxide by the Fischer-Tropsch process). Resin acids are suitable such as resin and those resin acids in tall oil. Naphthenic 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. (Included in the term alkyl is the alkyl portion of higher acyl radicals.) Examples of 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 United States Letters Patents Numbers 2,220,099 and 2,477,383

(especially valuable are 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., tallow or coconut oil alcohols) and about 1 to 6 moles of ethylene oxide; sodium or potassium salts of alkyl phenol ethylene oxide ether sulfate with about 1 to about 10 units of ethylene oxide per molecule and in which the alkyl radicals contain about 8 to about 12 carbon atoms.

Additional examples of 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 from coconut oil. Other anionic synthetic detergents of this variety are set forth in United States Letters Patents 2,486,921; 2,486,922; and 2,396,278.

Still other anionic synthetic detergents include the class designated as succinamates. This class includes such surface active agents as disodium N-octadecylsulfo succinamate; tetrasodium N-(1,2-dicarboxyethyl)-N-octadecylsulfo-succinamate; diamyl ester of sodium sulfosuccinic acid; dihexyl ester of sodium sulfosuccinic acid; dioctyl ester of sodium sulfosuccinic acid.

Anionic phosphate surfactants 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, of course, are --SO H, SO H, and CO H. Alkyl phosphate esters such as (R-O) PO H and ROPO H in which R represents an alkyl chain containing from about 8 to about 20 carbon atoms are useful.

These esters can be modified by including in the molecule from one to about 40 alkylene oxide units, e.g., ethylene oxide units. Formulae for these modified phosphate anionic detergents are o ta-oonzornomi -o-u in which R represents an alkyl group containing from about 8 to 20 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 integer from 1 to about 40.

A specific anionic detergent which has also been found excellent for use in the present invention is described more fully in the U.S. Pat. 3,332,880 of Phillip F. Pflaumer and Adriaan Kessler, issued July 25, 1967, titled Detergent Composition. This detergent comprises by Weight from about 30% to about 70% of Component A, from about 20% to about 70% of Component B, and from about 2% to about 15% of Component C, wherein:

(a) Said Component A is a mixture of double-bond positional isomers of water soluble salts of alkene-l sulfonic acids containing from about 10 to about 24 carbon atoms, said mixture of positional isomers including about 10% to about 25% of an alpha-beta unsaturated isomer, about 30% to about 70% of a beta-gamma unsaturated isomer, about 5% to about 25% of a gamma-delta unsaturated isomer, and about 5% to about 10% of a deltaepsilon unsaturated isomer;

(b) Said Component B is a mixture of water soluble salts of bifunctionally-substituted sulfur-containing saturated aliphatic compounds containing from about 10 to about 24 carbon atoms, the functional units being hydroxy and sulfonate radicals with the sulfonate radical always being on the terminal carbon and the hydroxyl radical being attached to a carbon atom at least two carbon atoms removed from the terminal carbon atom, at least 90% of the hydroxy radical substitutions being in the 3, 4, and positions; and

(c) Said Component C is a mixture comprising from about 30-95% water soluble salts of alkene disulfonates containing from about to about 24 carbon atoms, and from about 5% to about 70% water soluble salts of hydroxy disulfonates containing from about 10 to about 24 carbon atoms, said alkene disulfonates containing a sulfonate group attached to a terminal carbon atom and a second sulfonate group attached to an internal carbon atom not more than about six carbon atoms removed from said terminal carbon atom, the alkene double bond being distributed between the terminal carbon atom and about the seventh carbon atom, said hydroxy disulfonates being saturated aliphatic compounds having a sulfonate radical attached to a terminal carbon, a second sulfonate group attached to an internal carbon atom not more than about six carbon atoms removed from said terminal carbon atom, and a hydroxy group attached to a carbon atom which is not more than about four carbon atoms removed from the site of attachment of said second sulfonate group.

B. Nonionic synthetic detergents 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 partic'ular hydrophobic group can be readily adjusted to yield a water-soluble compound having the desired degree of balance between hydrophilic and hydrophobic elements.

For example, 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 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.

Other suitable nonionic synthetic detergents include:

(1) 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 S 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.

(2) Those derived from the condensation of ethylene oxide with the product resulting from the reaction of propylene oxide and ethylene diamine. For example, compounds containing from about 40% to about 80% polyoxyethylene by weight and having a molecular weight of from about 5,000 to about 11,000 resulting from the reaction of ethylene oxide groups with a hydrophobic base constituted of the reaction product of ethylene diamine and excess propylene oxide, said base having a 8 molecular weight of the order of 2,500 and 3,000, are satisfactory.

(3) The condensation product of aliphatic alcohols having from 8 to 22 carbon atoms, in either straight chain or branched chain configuration, with 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 10 to 14 carbon atoms.

(4) 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.

Other examples include dodecylphenol condensed with 12 moles of ethylene oxide per mole of phenol; dinonylphenol condensed with 15 moles of ethylene oxide per mole of phenol; dodecyl mercaptan condensed with 10 moles of ethylene oxide per mole of mercaptan; bis-(N- 2-hydroxyethyl) lauramide; nonyl phenol condensed with 20 moles of ethylene oxide per mole of nonyl phenol; myristyl alcohol condensed with 10 moles of ethylene oxide per mole of myristyl alcohol; lauramide condensed with 15 moles of ethylene oxide per mole of lauramide; and di-isooctylphenol condensed with 15 moles of ethylene oxide.

(5) A detergent having the formula -R R R N 0 (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 other 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 hydroxalkyl radicals containing from 1 to about 3 carbon atoms;

Specific examples of amine oxide detergents include:

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, dimethyloleylamine oxide, dimethyl- (2-hydroxydodecyl)amine oxide,

and the corresponding decyl, hexadecyl and octadecyl homologs of the above compounds.

(6) A detergent having the formula R R R P O (phosphine 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 of R and R are selected from the group consisting of alkyl radicals and hydroxyalkyl radicals containing from 1 to about 3 carbon atoms.

Specific examples of the 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.

(7) A detergent having the formula (sulfoxide detergent) wherein R is an alkyl l'afllC'dl containing from about 10 to about 28 carbon atoms, from 0 to about ether linkages and from 0 to about 2 hydroxyl substituents at least one moiety of R being an alkyl radical containing 0 ether linkages and containing from about to about 18 carbon atoms, and wherein R is an alkyl radical containing from 1 to 3 carbon atoms and from one to two hydroxyl groups: octadecyl methyl sulfoxide, dodecyl methyl sulfoxide, tetradecyl methyl sulfoxide, S-hydroxytridecyl methyl sulfoxide, B-methoxytridecyl methyl sulfoxide, 3-hydroxy-4-dodecoxybutyl methyl sulfoxide, octadecyl Z-hydroxyethyl sulfoxide. dodecylethyl sulfoxide.

C. Ampholytic synthetic detergents Ampholytic synthetic detergents can be broadly described as derivatives of aliphatic or aliphatic derivatives of heterocyclic secondary and tertiary amines, in which the aliphatic radical may be straight chain or branched and wherein one of the aliphatic substituents contains from about 8 to 18 carbon atoms and at least one contains an anionic water-solubilizing group, e.g., carboxyl, sulfo, sulfato, phosphate, or phosphono. Examples of compounds falling within this definition are sodium 3-(dodecylamino)-propionate,

sodium 3-(dodecylamino)propane-l-sulfonate,

sodium 2-(dodecylamino)ethyl sulfate,

sodium 2-(dimethylamino)octadecanoate,

disodium 3-(N-carboxymethyl-dodecylamino)-propanel-sulfonate,

disodium 2-(oleylamino)ethyl phosphate,

disodium 3-(N-methylhexadecylamino)propyl-l-phosphonate,

disodium octadecyl-iminodiacetate,

sodium l-carboxymethyl-Z-undecylimidazole,

disodium 2-[N-(2-hydroxyethyl)octadecylamino] ethyl phosphate, and

sodium N,N-bis-(2-hydroxyethyl)-2sulfato-3-dodecoxypropylamine.

D. Zwitterionic synthetic detergents 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 watersolubilizing 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-hydroxypropane-l-sulfonate,

3- (N,N-dimethyl-N-hexadecylammonio) -propane-1- sulfonate,

2-(N,N-dimethyl-N-dodecylammonio)acetate,

2- (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 pro pylphosphonate,

3- (P,P-dimethyl-P-dodecylphosphonio -propane-1- sulfonate,

2- (S-methyl-S-tert.hexadecyl-sulfonio ethane-l-sulfonate,

3- (S-methyl-S-dodecylsulfonio propionate,

sodium 2- (N,N-dimethyl-N-dodecylammonio) ethyl phosphonate,

4- S -methyl-S-tetradecylsulfonio butyrate,

1- Z-hydroxyethyl) -2-un decylimmidazoliuml-acetate,

2- (trimethylammonio octadecanoate, and

3- (N,N-bis 2-hydroxyethyl -N-octadecylammonio -2- hydroxypropanel-sulfonate.

Some of these detergents are described in the following US. Patents: 2,129,264; 2,178,353; 2,774,786; 2,813,898; and 2,828,332.

An especially useful class of detergents which represent a preferred embodiment of the present invention when and in conjunction with the sequestering agents described above are those identified herein as calcium insensitive detergents. The term calcium insensitive is a functional descriptive term used to designate a class of detergents whose detergency performance properties are not as adversely effected by water hardness minerals as, for instance, soap. Besides having an inordinately high resistance to precipitation or inactivation by hard water mineral ions, these detergents are efiicient in soil-removal and soil-dispersal in concentration of about 0.05% in water and, in addition, are soluble in water to at least a concentration of 0.05% at a temperature of about F. to about F.

Such materials include water-soluble (sodium or potassium) salts of sulfonated fatty acid esters of fl-acyloxyalkane-l-sulfonic acids; p-alkyloxyalkane sulfonates; alkyl polyethylene sulfates or olefin sulfonates.

These calcium insensitive classes of detergents which represent a preferred embodiment of this invention are described more specifically below.

Anionic organic detergents which are calcium insensitive in the terms described above include alkali metal, ammonium and substituted-ammonium salts of esters of an a-sulfonated fatty acid in which the esters contain about 15 to about 25 carbon atoms. These detergent compounds have the following structure:

wherein R is alkyl or alkenyl of about 10 to about 20 carbon atoms (forming with the two carbon atoms a fatty acid group); R is alkyl of 1 to about 10 carbon atoms; and M is a salt-forming 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. Specific examples of substituted ammonium cations include methyl-, dimethyl-, and trimethyl-ammonium cations and quaternary ammonium cations such as tetramethyl-ammonium and dimethyl piperidinium cations and those derived from alkylamines such as ethylamine, diethylamine, triethylamine, mixtures thereof, and the like.

Specific examples of this class of compounds include the sodium and potassium salts of esters where R; is selected from methyl, ethyl, propyl, butyl, hexyl and octyl groups and the fatty acid group (R plus the two carbon atoms in the structure above) is selected from lauric, myristic, palmitic, stearic, palmitoleic, oleic, linoleic acids and mixtures thereof. A preferred ester material herein is the sodium salt of the methyl ester of u-sulfonated tallow fatty acid, the term tallow indicating a carbon chain distribution approximately as follows: C -2.5%, C 28%, O -23%, palmitoleic-2%, oleic41.5%,

and linoleic3% (the first three fatty acids listed are saturated).

Other examples of suitable salts of a-sulfonated fatty esters utilizable herein include the ammonium and tetramethylammonium salts of the hexyl, octyl, ethyl, and butyl esters of u-sulfonated tridecanoic acid; the potassium and sodium salts of the ethyl, butyl, hexyl, octyl, and decyl esters of a-sulfonated pentadecanoic acid; and the sodium and potassium salts of butyl, hexyl, octyl, and decyl esters of a-sulfonated heptadecanoic acid; and the lithium and ammonium salts of butyl, hexyl, octyl, and decyl esters of u-sulfonated nonadecanoic acid.

The salts of a-sulfonated fatty acid esters of the present invention are known compounds and are described in US. Pat. 3,223,645, issued Dec. 14, 1965 to Kalberg, this patent being hereby incorporated by reference.

Another specific class of suitable calcium insensitive anionic organic detergents includes salts of 2-acyloxy-alkane-l-sulfonic acids. These salts have the formula where R is alkyl of about 9 to about 23 carbon atoms (forming with the two carbon atoms an alkaline group); R is alkyl of 1 to about 8 carbon atoms; and M is a saltforming radical hereinbefore described.

Specific examples of jS-acyloxy-alkane-l-sulfonates, or alternatively 2-acyloxy alkane 1 sulfonates, utilizable herein to provide excellent cleaning levels under households washing conditions include the sodium salt of 2-acetoxy-tridecane-l-sulfonic acid; the potassium salt of 2-propionyloxy-tetradecanel-sulfonic acid; the lithium salt of Z-butanoyloxy-tetradecane-l-sulfonic acid; the sodium salt of 2-pentanoyloxy-pentadecane-l-sulfonic acid; the ammonium salt of 2-hexanoyloxy-hexadecane-1- sulfonic acid; the sodium salt of 2-acetoxy-hexadecane-lsulfonic acid; the dimethylammonium salt of 2-heptanoy1- oxy tridecane l sulfonic acid; the potassium salt of -2-octanoyloxy-tetradecane-l-sulfonic acid; the dimethylpiperdinium salt of 2-nonanoyloxy-tetradecane-l-sulfonic acid; the sodium salt of 2-acetoxy-heptadecane-l-sulfonic acid; the lithium salt of 2-acetoxy-octadecane-l-sulfonic acid; the dimethylamine salt of 2-acetoxyoctadecane-1- sulfonic acid; the potassium salt of 2-acetoxy-nonadecanel-sulfonic acid; the sodium salt of 2-acetoxy-uncosane-1 sulfonic acid; the sodium salt of 2-propionyloxy-docosanel-sulfonic acid; and isomers thereof.

Preferred fl-acyloxy-alkane-l-sulfonate salts herein are the alkali metal salts of B-acetoxy-alkane-l-sulfonic acids corresponding to the above formula wherein R is an alkyl of about 14 to about 18 carbon atoms, these salts being preferred from the standpoints of the excellent cleaning properties and ready availability.

Typical examples of the above described fi-acetoxy alkanesulfonates are described in the literature: Belgian Pat. 650,323 issued July 9, 1963, discloses the preparation of certain Z-acyloxy alkanesulfonic acids. Similarly, U.S. Pats. 2,094,451 issued Sept. 28, 1937, to Guenther et al. and 2,086,215 issued July 6, 1937 to DeGroote disclose certain salts of fi-acetoxy alkanesulfonic acids. These references are hereby incorporated by reference.

Other synthetic anionic detergents useful herein are alkyl ether sulfates. These materials have the formula RO(C H O),,SO M wherein R is alkyl or alkenyl of about 10 to about 20 carbon atoms, x is 1 to 30, and M is a salt-forming cation defined hereinbefore.

The alkyl ether sulfates calcium insensitive detergents of the present invention are condensation products of ethylene oxide and monohydride alcohols having about 10 to about 20 carbon atoms. Preferably, 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 1 to 30, and especially 3 to 6, molar proportions of ethylene oxide and the resulting mixture of molecular species, having, for example,.an average of 3 to 6 moles of ethylene oxide per mole of alcohol, is sulfated and neutralized.

Specific examples of alkyl ether sulfates of the present invention are sodium coconut alkyl ethylene glycol ether sulfate; lithium tallow alkyl triethylene glycol ether sulfate; sodium tallow alkyl hexaoxyethylene sulfate; and ammonium tetradecyl octaoxyethylene sulfate.

Preferred herein for reasons of excellent cleaning properties and ready availability are the alkali metal coconutand tallow-alkyl oxyethylene ether sulfates having an average of about 1 to about 10 oxyethylene moieties. The alkyl ether sulfates of the present invention are known compounds and are described in U.S. Pat. 3,332,876 to Walker (July 25, 1967) incorporated herein by reference.

A preferred class of calcium insensitive anionic organic detergents are the fl-alkyloxy alkane sulfonates. These compounds have the following formula:

where R is a straight chain alkyl group having from 10 to 20 carbon atoms, R is a lower alkyl group having from 1 to 3 carbon atoms, and M is a salt-forming radical hereinbefore described.

Specific examples of ,EZ-alkoxy alkane sulfonates or alternatively 2 alkoxy-alkane 1 sulfones, utilizable herein to provide superior cleaning and whitening levels under household washing conditions include potassium fl-ethoxytetradecylsulfonate, sodium p-methoxy-tridecanesulfonate, potassium ,B-ethoxytetradecylsulfonate, sodium p-isopropoxyhexadecylsulfonate, lithium fi-t-butoxytetradecylsulfonate, sodium B-methoxyoctadecylsulfonate, and ammonium fl-n-propoxydodecylsulfonate.

Other suitable anionic detergents utilizable herein are olefin sulfonates having about 12 to about 24 carbon atoms. The term olefin sulfonates is used herein to mean compounds which are produced by the sulfonation of u-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-alkanesulfonates. The sulfur trioxide may be liquid or gaseous, and is usually, but not necessarily, diluted by inert diluents, for example by liquid S0 chlorinated hydrocarbon, etc., when used in the liquid form, or by air, nitrogen, gaseous 50;, etc., when used in the gaseous form.

The m-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. Examples of suitable l-olefins include l-dodecene; l-tetradecene; l-hexadecene; l-octadecene; l-eicosene and l-tetracosene.

In addition to the true alkene sulfonates and a proportion of hydroxy-alkanesulfonates, 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 reactions during the sulfonation.

Calcium insensitive ampholytic synthetic detergents utilizable herein have the formula wherein R is alkyl of about 8 to about 18 carbon atoms, R is alkyl of 1 to about 3 carbon atoms or is hydrogen, R is alkylene of 1 to about 4 carbon atoms, Z is carboxy,

sulfonate, or sulfate, and M is a salt-forming cation. Examples of compounds falling within this'definition are sodium 3-dodecylaminopropionate; sodium 3-dodecylaminopropane sulfonate; N-alkyltaurines such as the ones prepared by reacting dodecylamine with sodium isethionate according to the teaching of U.S. Pat. 3,658,072; sodium salts of N-higher alkyl aspartic acids such as those produced according to the teaching of U.S. Pat. 2,438,- 091; and the products sold under the trade name Miranol and described in U.S. Pat. 2,528,378.

Calcium insensitive zwitterionic synthetic detergents in which the aliphatic radicals can be straight chain or branched, and wherein one of the aliphatic substituents contains from about 8 to 18 carbon atoms and one contains an anionic water solubilizing group, e.g., carboxy, sulfonate or sulfate. A general formula for these compounds is:

wherein R contains an alkyl, alkenyl, or hydroxyalkyl radical of from about 8 to about 18 carbon atoms having from to about 10 ethylene oxide moieties and from 0 to 1 glyceryl moiety; Y is selected from the group consisting of nitrogen and sulfur atoms; R is an alkyl or monohydroxy alkyl group containing 1 to about 3 carbon atoms; x is 1 when Y is a sulfur atom and 2 when Y is a nitrogen atom, R is an alkylene or hydroxy alkylene of from 1 to about 4 carbon atoms and Z is a radical selected from the group consisting of carboxylate, sulfonate, sulfate, phosphonate, and phosphate groups.

Examples include:

4- [N,N-di Z-hydroxyethyl -N-octadecylammonio] butanel-carboxylate;

5- [S-3 -hydroxypropyl-S-hexadecylsulfonio] -3- hydroxypentane-l-sulfate;

3- [P,P-diethyl-P-3,6,9-trioxatetracosanephosphonio] 2-hydroxyprop anel-phosphate;

3- [N,N- dipropyl-N-3-do decoxy-2-hydroxypropylammonio] -propane-1-phosphonate;

3- (N,N-dimethyl-N-hexadecylammonio) propane-1- sulfonate,

3- (N,N-dimethyl-N-hexadecylammonio) -2-hydroxypropanel-sulfonate,

4- [N,N-di 2-hydroxyethyl) -N- (2-hydroxydodecyl) ammonio]-butane-1-carboxylate,

3 [S-ethyl-S- (3-dodecoxy-2-hydroxypropyl sulfonio]- propanel-pho sphate,

3- [P,P-dimethyl-P-dodecylpho sphonio] -propane- 1- phosphonate, and

3- [N,N-di( 3-hydroxypropyl) -N-hexadecylammonio] 2-hydroxyp entanel-sulfonate.

Examples of compounds falling within this definition are 3 (-N,N-dimethyl-N-hexadecylammonio)propane-1- sulfonate and 3 (N,N-dirnethyl-N-tridecylammonio)-2- hydroxypropane-l-sulfonate which are especially preferred for their excellent cool water detergency characteristics.

The alkyl groups contained in said detergent surfactants can be straight or branched, preferably straight, and saturated or unsaturated as desired.

In a finished detergent formulation, there can be present other materials which make the product more effective or more aesthetically attractive. The following are mentioned only by way of example. A water-soluble sodium carboxymethyl cellulose can be added in minor amounts to inhibit soil redeposition or for other reasons. Tarnish inhibitors such as benzotriazole or ethylenethiourea can also be added in amounts up to about 3%. Fluorescers, enzymes, and brighteners, perfumes, coloring agents, while not per se essential in the compositions of this invention, can be added in minor amounts. As already mentioned, 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. Water-soluble silicates are highly effective corrosion inhibitors and can be added if desired'at levels of from about 3% to about 8% 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.

In the embodiment of this invention which provides for a built liquid detergent, a hydrotropic agent may be found desirable. Suitable hydrotropes are water-soluble alkali metal salts of toluenesulfonate, benzenesulfonate, and xylene sulfonate. Preferred hydrotropes are potassium or sodium toluenesulfonates. The hydrotrope may be added, if desired, at levels of from 0% up 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 function as a solubilizing agent and to produce a product which retains its homogeneity at a low temperature.

EXAMPLE An effective granular laundry detergent composition according to this invention has the following formulation.

The sequestering agent in the preceding example can be replaced with an equal weight proportion of sodium- 1,3,5-trihydroxy-2,4,6-benzene tricarboxylate, or sodium- 1,3,5-trihydroxy-2,4,6-benzene triacetate and an effective composition is obtained.

SEQUESTRATION EVALUATION PROCEDURE The sequestering properties of the novel class of sequestrants of this invention are demonstrated with the following procedure.

The evaluations are run in 200 ml. beakers at 23 i3 C. with a magnetic stirrer. 50 ml. 14 gram/ gal. (calculated as Caflo CaCl solution is poured into the breaker. The requisite amount of sequestering agent (builder) sample to give a final solution concentration of 0.06%, 0.03%, or 0.02%, is weighed or pipetted into the beaker. The sample is brought to pH 7 with KOH or HCl as needed. Distilled water is added to give a total volume of :3 ml. Fine adjustment is made to pH 7.00:0.05 with a Corning Model 12 meter and Corning Model 476022 glass electrode. At this point the calcium ion electrode is plugged in place of the pH electrode and the calcium ion activity is measured. The expanded scales either 0 to +100 or 0 to 100 millivolts, as necessary, are used. All readings are made with slow stirring. The resultant millivolt reading is converted into grains/ gal. using a standardization curve. This amount represents residual hardness. The standards, 100, 10, 7, 5, 3, 1, 0.5 and 0.1 grains/gal. (as CaCO CaCl at pH 7.00 are linear with potential down to 1 grain/gal. and by 0.1 grain/gal. (1.7 10- molar) the practical limit of measurement has been reached. Day-today variation in potential readings is appreciable above 1 grain/gaL; it amounts to :3 millivolts or i10%. Below 1 grain/gal. error grows rapidly; however, precise statements of error limits are meaningless. A day-to-day variation in the behavior of even good calcium electrodes is to be expected below 1 grain/ gal. At times, linearity will extend almost to 0.1 grain/ gal. and then the best error limits will obtain. A further clue to superb calcium electrode performance is the rate at which it comes to its final potential.

15 At best, this will be on the order of a second; about 10 seconds is the usual time. In summary, readings to within 10% can always be made down to 1 grain/gal. With a superb electrode, this can be extended to 0.1 grain/ gal.

This procedure was used in the examples given below in which sequestering properties are given.

As noted above, the synthesis methods for preparing the sequestering agents represent no part of this invention. While any known reactions can be used, the following examples are given to illustrate successful preparative methods. The sequestration values are given with several of the following examples.

EXAMPLE I Preparation of Na -1,3,5-trihydroxy-2,4,G-benzene trisulfonate Two hundred grams of 1,3,5-trihydroxy benzene dihydrate were added to a stirred four-neck flask cooled by an ice bath to C. Two kilograms of chlorosulfonic acid were then carefully added over a period of twenty-five minutes. After standing for an hour, the reaction mass was filtered through a fritted glass funnel and washed with 6 liters of dichloromethane. This acid batch was then added to a second similar batch and allowed to stand in a desiccator over sulfuric acid for two days at reduced pressure. Part of the dried solid was suspended in dichloromethane and neutralized with 50% NaOH/H O. After the solvent was pulled off by heating at 30 C. under reduced pressure, the product, Na -1,3,5-trihydroxy-2,4,6-benzene trisulfonate, was freeze dried.

A calcium electrode test yielded the following results:

[011*] grain/gal. pH (residual) Weight sequestrant:

A calcium electrode test was then performed on this product with thef ollowing results:

One hundred grams of Na -1,3,5-trihydroxy-2,4,6-benzene trisulfonate, as from the first example, 600 mls. of distilled water, 100 grams of sodium acetate and a few drops of acetic acid are added to a stirred reaction vessel. To this, 100 grams of bromine, is added dropwise. This mixture is agitated and held at 0 C. for two hours. The precipitate, 1,3,5 trihydroxy 2,4,6 tribromobenzene, is then filtered out and freeze dried. Thirty grams of this dried material are slurried into 200 mls. of ethyl ether. Fifty mls. of this slurry, grams of magnesium turnings, and 200 mls. of ethyl ether are charged into a three-neck reaction vessel and heated to reflux. After adding one gram of iodine crystals, the remainder of the slurry is added slowly. An additional gram of iodine crystals is added when about half of the slurry has been added to the reaction mass. The mixture is agitated at reflux for six hours then allowed to stand for two days. After separatout all residual magnesium turnings, the remaining material is placed in an agitated reaction flask and 2 pounds of Dry Ice are added slowly. The slurry is then filtered and the 1,3,5-trihydroxy-2,4,6-benzene tricarboxylic acid is neutralized with 10% NaOH to yield Na -1,3,5-trihydroxy-2,4,6-benzene tricarboxylate. In the calcium electrode test described above, this compound has demonstrable sequestering properties.

EXAMPLE III Preparation of Na -2,4,6-trisulfo phenol Twenty-five grams of chemically pure phenol were dissolved in 600 ml. of dichloromethane in a three-neck 2000 ml. reaction vessel. To this 200 grams of chlorosulfonic acid were added. The reaction mass was heated until the solvent had evaporated and them aterial reached 140 C. This temperature was held for 30 minutes. The sample was then cooled in a Dry Ice/acetone bath and neutralized with 380 grams of a 21% NaOH aqueous solution. The product, Na -3,4,6-trisulfo phenol, was filtered and washed with distilled water, then dried at C. in an oven.

A calcium electrode test was then performed on this product with the following results:

[Ca1+] grain/gal. pH (residual) Weight sequestrant:

EXAMPLE IV Preparation of Na (l,5-disulfo-2,3,4-trihydroxy benzene) Thirty-five gram of 1,2,3-trihydroxy benzene were added with 300 ml. of dichloromethane to a stirred 2000 ml. reaction vessel. The vessel was held in an ice bath at 0 C. 175 grams of chlorosulfonic acid were added dropwise to this over a period of twenty minutes. The sample was neutralized with 200 grams of a 25% NaOH aqueous solution. The resulting product, Na 1,5-disulfo-2,-3,4'-trihydroxy benzene), was filtered and dried in an oven at 0 A calcium electrode test was performed on this salt and on the starting material, 1,3,5-t1'ihydroxy benzene, with the following results:

Forty grams of sodium salicylate and 500 ml. of dichloromethane were added to a stirred 3000 ml. reaction flask cooled by an ice bath to 0 C. To this, 175 grams of chlorosulfonic acid were added slowly. After standing at 0 C. for 30 minutes, the material was neutralized with grams of a 28% NaOH aqueous solution. The resulting product, Na -1-carboxy-2-hydroxy-3,S-disulfobenzene, was filtered and dried in an oven at 110 C.

A calcium electrode test was performed andyeilded the following results:

Residual pH [Ca grain/gal.

Weigfit sequestrant:

17 EXAMPLE VI Preparation of Na -1-hydroxy-2,6-disulfo-4-carboxybenzene Into a three liter stirred reaction flask, 15 grams of phydroxy benzoic acid, 20 grams phosphorous pentoxide, and 300 mls. of chloroform were added. To this, 300 grams of 30% oleum were added slowly. This reaction mass was heated to 100 C. and held there while being agitated for 30 minutes. The reaction vessel was then placed in an ice bath to cool the mixture to C. 300 grams of concentrated hydrochloric acid were added. The precipitate was filtered out and neutralized with 80 grams of 50% NaOH/H O. The Na -l-hydroxy-2,6-disulfo-4- carboxybenzene was dried for two days in an oven at 105 C.

The results of a calcium electrode test performed on this sample are as follows:

Residual pH [Ca grain/gal.

Wei%ht sequestrant:

EXAMPLE VII Preparation of Na -1,3,5-trisulfo-2,4-dihydroxy benzene Residual pH [Ca grain/gal.

Weight sequestrant:

EXAMPLE VIII Preparation of Na -1,3-dihydroxy-4,6-disulfobenzene Ten grams of resorcinol and /2 pint of carbon disulfide were added to a stirred reaction flask being held in an ice/ water bath. Fifty grams of chlorosulfonic acid were added slowly. The mixture was allowed to react for one hour while being stirred continuously. The sample was then neutralized with 35 grams of 50% NaOH/H O.

Calcium electrode test results for this, Na -1,3-dihydroxy-4,6-disulfobenzene, are as follows:

tff; 7

EXAMPLE IX Preparation of Na -1,2,3,5-trihydroxy-2,4-disulfobenzene Ten grams of 1,3,5-trihylroxy benzene dihydrate and 200 mls. of chloroform were added to a stirred reaction vessel being held at 0 C. 110 grams of chlorosulfonic acid were added dropwise to this. This mixture was heated to 110 C. and allowed to react at this temperature for one hour. This reaction mass was then neutralized with 80 grams of 50 NaOH/H O. The Na -1,3,5-trihydroxy-2,4- disulfobenzene was dried at 100 C.

Calcium electrode test results are as follows:

Residual pH [Ca grain/gal.

We1%ht sequestrant:

l0 EXAMPLE X Preparation of 1,3,5-trihydr0xy-2,4,6-triacetyl benzene Three moles of carbon sulfoxide in an ethereal solution are added to three moles of methylmagnesium iodide at C. The reaction mass is permitted to react for four hours. 1,3,S-trihydroxy-2,4,6-triacetylbenzene is isolated in ten percent yield.

sequestering properties are demonstrated by the calcium electrode test described herein above.

EXAMPLE XI Preparation of Na -l-sulfo-2-methyl-4,S-dicarboxybenzene P ad} (residual) Weight sequestrant:

EXAMPLE XII Preparation of Na -2,3-dihydroxy-1,4 benzene diacetate Ten grams of 2,3-dihydroxy-1,4-benzene diacetic acid were neutralized with ten grams of 50% NaOH/H O. The product was dried in an oven at 110 C.

Calcium electrode test results for Na -2,3-dihydroxy- 1,4-benzene diacetate are as follows:

pH [03*] (residual) EXAMPLE XIII Preparation of 1,3-dihydroxy-5 [acetyl ether] benzene One mole of 1,3,5-trihydroxy benzene is added to one mole of acetylchloride. The mixture is permitted to react at 30 C. for 24 hours. From the reaction mass, 1,3-dihydroxy-S-[acetyl ether] benzene is separated.

sequestering properties are demonstrated by the calcium electrode test described herein.

EXAMPLE XIV Preparation of 1,3-dihydroxy-5-[carboxymethyl ether] benzene One mole of 1,3,5-trihydroxy benzene is added to one mole of chloroacetic acid. The mixture is permitted to' react for 24 hours at 30 C. From this reaction mass, 1,3-

dihydroxy-S-[carboxymethyl ether] benzene is isolated.

sequestering properties are demonstrated by the calcium electrode test described herein.

19 EXAMPLE XV Preparation of Na-1,2,4,5-tetraakis[hydroxymethyl1-3- sulfobenzene EXAMPLE XVI A calcium electrode evaluation with 2,3,4-trihydroxy- 1,5-disulfobenzene yielded the following results:

[Ca+] grain/gal. pH (residual) Weig)ht sequestrant: 7 0135 "'i' 0.03 2. 7 0.06 7 4 0.06 10 O. 25

EXAMPLE XVII A calcium electrode evaluation with 1-sulfo-2, 3,5,6- tetracarboxybenzene yielded the following results:

[Ca grain/gal. DH (residual) Weight sequestrant: 7 "'2' 5 10 4. 5 7 3. 6 10 2. 95

EXAMPLE XVIII A calcium electrode evaluation with l-sulfo-2,4,6-tricarboxybenzene yielded the following results:

[Ca grain/gal. DH (residual) Weight sequestrant:

EXAMPLE XIX A calcium electrode evaluation with 1-hydroxy-2,4-disulfobenzene yielded the following results:

A calcium electrode evaluation with 1,3,5-trihydroxy-2 carboxybenzene yielded the following results:

[Ca+] rain/ al. DH (res idual) Weight sequestrant:

20 EXAMPLE XXI A calcium electrode evaluation with 1,2,3-trihydroxy-5- carboxybenzene yielded the following results:

[0v] grain/gal. pH (residual) WeigJht sequestrant: 7 "'5' 4. 5 10 2. 8 7 1. 1 10 0. 6

EXAMPLE XXII A calcium electrode evaluation with Na(1-hydroxy-2- EXAMPLE XXIII A calcium electrode evaluation with 1,4-dihydroxy-2,5- disulfobenzene yielded the following results:

[ /gal.

pH (residual) Weight sequestrant:

EXAMPLE XXIV A calcium electrode evaluation with 1-hydroxy-2,4,6- tricarboxybenzene yielded the following results:

[Ca grain/gal.

pH (residual) Wei%ht sequestrant:

In many industrial, institutional and household processses and products, a small amount of a metal ion contamination present in water can adversely affect color, stability, appearance, quality and saleability of a product or the efficiency of a process. The role of a sequestering agent in overcoming such adverse affects of metal ions is fairly well recognized and appreciated. Accordingly, another embodiment of the present invention is to provide a process for treating aqueous solutions containing polyvalent metal ions by adding to the solution an efiective amount of at least one of the novel class of sequestering agents described and illustrated above. Ordinarily, this amount ranges from .25 p.-p.m. to 10,000 p.p.m of the aqueous solution. This embodiment of the present invention is based on the discovery of the sequestering properties of the sequestering agents described herein.

As indicated above, the manner of synthesizing the sequestering agents of this invention form no part of this invention. lAny suitable reaction can be used. Thus, for example, sulfonations are effected by reaction of the arcmatic-based material with in such solvents as HCl, H 80 $0 or H O. Carboxy groups are formed by adding previously carboxylated materials to aromatics by oxidation of methyls or chloromethyls with H 0 potassium dichromate, potassium permanganate, or nitric acid. Phenolic OH groups are added by means of alkali fusion of aromatics or by means of acidification of hydroperoxides of isopropyl aromatics Alcoholic OH groups are added by reacting chloromethyl aromatics with aqueous NaOH or KOH. These procedures and the others used are adapted as needed so as to obtain the desired end product. The aforementioned processes are more fully described in Organic Chemistry by R. T. Morrison and R. N. Boyd, published by Allyn and Bacon, Inc. in 1962.

In addition, 3,6-dihydroxybenzene-l,2,4,5-tetracarboxylic acid and related compounds can be prepared by the procedure described in detail in J. U. Nef Annalen der Chemie 237, l-35 (1887).

A similar synthetic route is described in H. van Pechmann tfi Ludwig Wolmann, Berichte der Deutschen Chema ischen Gesellschaft 30, 2569-7l (1898).

Other sequestering agents which come within the novel class of the sequestering agents of this invention such as phenol-2,4,6-trisulfonic acid can be prepared according to the procedure described in Senhofer, Ann 170, 110.

A suitable reaction synthesis for the preparation of 1,3,5-trihydroxy-2,4,6-benzene trisulfonic acid is described in Pollak, Gebauer-Ffilnegg Monats helfe ftlr Chemie 47, 544-552.

The foregoing description and examples describe and illustrate certain operable hard preferred embodiments of the present invention. It is not intended that the invention should be so limited since variations and modifications thereof will be obvious to those skilled in the art, all of which are within the spirit and scope of this invention.

What is claimed is:

1. A detergent composition consisting essentially of a water-soluble organic synthetic detergent selected from the group consisting of anionic, nonionic, ampholytic and zwitterionic surface active agents and mixtures thereof, and as a detergency aid a sequestering agent which is a water-soluble salt selected from the group consisting 22 of alkali metal salts and ammonium salts of a polyfunctionally-substituted aromatic compound having the formula HO OH OOH and wherein the proportion by weight of the organic synthetic detergent to the sequestering agent is in the range of 20:1 to 1:20.

2. A detergent composition of claim 1 wherein the sequestering agent is the trisodium salt of 1,3,5-trihydroxy-2,4,6-benzene tricarboxylic acid.

References Cited UNITED STATES PATENTS 2,264,103 11/1941 Tucker 210-23 3,692,684 9/1972 Hentschel 252-89 OTHER REFERENCES Martell et al.: Chem. of the Metal Chelate Compounds, Chap. 4 (Influence of the Structure of the Chelating Agent); copyright 1952 (3rd printing), Prentice-Hall, Inc., N.I., p. 13 6.

LEON D. ROSDOL, Primary Examiner P. E. WILLIS, Assistant Examiner U.S. C. X.R.

"ten STATES PATENT omcs Q CERTIFICATE OF CORRECTION Patent 2 m9 (1414 Dated May 21. 1974 Inventor) Daniel 5. Connor & Harrv Karl Krummel It is certified that error appears in the above-identified patent and that said Letters Patent are hereby corrected as shown below:

Col. 4, line 14, delete "1,3, S-tris[carboxyethylether] -2- carboxybenzene" and insert therefor -l, 3,5-tris[carboxymethyl ether] -2carboxybenzene Col. 4, line 72, delete "oil" and insert therefor soil Col. 5, line 18, delete "appropriates" and insert therefor appropriate Col. 8, line 40 after detergents include: insert dimethyldodecylamine oxide Col. 9, line 36, delete "carboxyl" and insert therefor carboxy Col. 9, line 73, delete "2" and insert therefor 3 Col. 11, line 26, delete "alkaline" and insert therefor alkane Col. 11, line 71, delete "monohydride" and insert therefor monohydric Col. 12, line 30, delete "sulfones" and insert therefor sulfonates Col. 12, line 33, delete "ethoxytetradecylsulfonate" and insert therefor methoxydecanesulfonate Col. 14, line 48, delete "breaker" I and insert therefor L beaker I Y, J

Po-ww UNlTED STATES PATENT OFFICE it I Page 2 CERTIFICATE OF CORRECTION Patent NO. 3 2 Dated Mali}. 1974.

fl fls) Daniel S. Connor & Harry Karl Krummel g 2 It is certified that error appears in the above-identified patent and that said Letters Patent are hereby corrected as shown below:

Col. 15, line 22 delete "fritted" and insert therefor --ritted Col. 15, line 41, delete "thef ollowing" and insert therefor the following Col. 16, line 11, delete "them aterial" and insert therefor the material Col. 16, line 21, delete caf and insert therefor Col. 17, line 66, 4 delete "Na l,2,3.,5-" and insert therefor Na -l,3,5

Col. 17, line 74, delete "50" and insert therefor 50% Col. 18, line 12, delete "sulfoxide" and. insert therefor suboxide Col. 18, line 51, insert "Weight sequestrantz" over first column of figures Col. 21, line 24, delete "hard" and insert therefor and Signed'and sealed this 12th day of November 1974.

(SEAL) Attest:

MCCOY I -I.- GIBSON JR. C. MARSHALL DANN Attesting Officer Commissioner of Patents

Referenced by
Citing PatentFiling datePublication dateApplicantTitle
US3933672 *Jul 23, 1973Jan 20, 1976The Procter & Gamble CompanySilica and silicone
US3985669 *Jun 17, 1974Oct 12, 1976The Procter & Gamble CompanyDetergent compositions
US4021376 *Jul 13, 1973May 3, 1977Lever Brothers CompanyDetergent compositions with nonphosphate builders containing two or more carboxyl groups
US4058472 *Jun 28, 1976Nov 15, 1977Texaco Inc.Alkali metal or ammonium sulfonated catechol
US4071476 *Sep 30, 1976Jan 31, 1978Texaco Inc.Detergent builders and composition containing the same
US4133779 *Mar 23, 1976Jan 9, 1979The Procter & Gamble CompanyDetergent composition containing semi-polar nonionic detergent and alkaline earth metal anionic detergent
US4274975 *Aug 20, 1979Jun 23, 1981The Procter & Gamble CompanyAbrasive, aluminosilicate ion exchange water softener, surfactant
US4605509 *Mar 11, 1974Aug 12, 1986The Procter & Gamble CompanyDetergent compositions containing sodium aluminosilicate builders
US4613448 *Mar 29, 1979Sep 23, 1986The Colgate-Palmolive Co.Tetrahydroxysuccinic acid as builder
US4913828 *Jun 10, 1987Apr 3, 1990The Procter & Gamble CompanyConditioning agents and compositions containing same
US4915854 *Oct 15, 1987Apr 10, 1990The Procter & Gamble CompanyIon-pair complex conditioning agent and compositions containing same
US4950424 *Apr 13, 1989Aug 21, 1990Lever Brothers CompanyNon-aqueous liquid detergent compositions containing di-sulphonic acids as deflocculants
US5019280 *Feb 8, 1989May 28, 1991The Procter & Gamble CompanyIon-pair complex conditioning agent with benzene sulfonate/alkyl benzene sulfonate anionic component and compositions containing same
US5073274 *Apr 30, 1990Dec 17, 1991The Procter & Gamble Co.Liquid detergent containing conditioning agent and high levels of alkyl sulfate/alkyl ethoxylated sulfate
US5202050 *Sep 19, 1990Apr 13, 1993The Procter & Gamble CompanyMethod for cleaning hard-surfaces using a composition containing organic solvent and polycarboxylated chelating agent
US5905065 *Jun 27, 1996May 18, 1999The Procter & Gamble CompanyCarpet cleaning compositions and method for cleaning carpets
US5928384 *Oct 31, 1995Jul 27, 1999The Procter & Gamble CompanyMethod of cleaning carpets
US6417424Jun 17, 1997Jul 9, 2002The Procter & Gamble CompanyBreathable absorbent articles having odor control
US6566320Oct 18, 2000May 20, 2003The Procter & Gamble CompanyStability
US6569826Oct 18, 2000May 27, 2003The Procter & Gamble CompanyA chromophoric 1-(p-hydroxyphenoxycarbonyl)-3,8-dimethyl-5-isopropyl-azulene compound; bleach stabilizer; washing fabrics
US6617300Aug 30, 2001Sep 9, 2003Procter & Gamble CompanyGranular bleach activators having improved solubility profiles
US6630435Jun 27, 2000Oct 7, 2003Procter & GamblePreformed monoperoxycarboxylic acid, tertiary alkyl amine oxide and anionic hydrotrope or surfactant; laundry and hard surfaces; odorless; colorfastness; less damaging; chlorine free
US6991747Mar 11, 2003Jan 31, 2006Procter & Gamble CompanyComplexing with chromogens; preservative for fuel, food
US7264845Apr 29, 2004Sep 4, 2007The Procter & Gamble CompanyRepeatedly applying to at least parts of said lavatory bowl surface a solution comprising less than 30 ppm of a surface modifying polymer
US7445644Oct 27, 2006Nov 4, 2008The Procter & Gamble CompanyTo remove clay and plant-derived polyphenolic compound soils; cleaning in laundry and dishwash
US7585376Oct 27, 2006Sep 8, 2009The Procter & Gamble CompanyComposition containing an esterified substituted benzene sulfonate
US7645731Jan 8, 2009Jan 12, 2010Ecolab Inc.for preventing calcium, magnesium and iron precipitation and for removing soils; selected from tiron aminocarboxylate, 4-methycatechol aminocarboxylate and 3-methoxy catechol aminocarboxylate as chelating agent; NaOH, NaCO3 or sodium silicate alkali material, a surfactant; biodegradable
US7842655Apr 23, 2009Nov 30, 2010The Procter & Gamble Companycomprising hypohalite bleach, trimethoxy benzoic acid, pigment and/or dye (copper phthalocyanine), alkali metal salt of silicate, and alkali metal periodate; storage stability
US7910536May 8, 2009Mar 22, 2011The Procter & Gamble CompanyBleaching composition comprising an alkoxylated benzoic acid
US8053402Jan 14, 2010Nov 8, 2011The Procter & Gamble CompanyBleaching compositions containing perfume microcapsules and a stabilizing agent
US8192552Feb 20, 2009Jun 5, 2012Rhodia ChimieDetergent composition comprising a block copolymer
US8198503Nov 18, 2008Jun 12, 2012The Procter & Gamble CompanyDisposable absorbent articles comprising odor controlling materials
US8252736Sep 3, 2009Aug 28, 2012The Procter & Gamble CompanyCleaning composition
US8343906Dec 13, 2010Jan 1, 2013The Procter & Gamble CompanyAlkaline liquid hand dish washing detergent composition
US8343907Aug 12, 2009Jan 1, 2013The Procter & Gamble CompanyParticulate bleaching composition comprising enzymes
US8440602Dec 20, 2010May 14, 2013The Procter & Gamble CompanyLiquid cleaning and/or cleansing composition comprising a divinyl benzene cross-linked styrene polymer
US8440603Jun 19, 2012May 14, 2013The Procter & Gamble CompanyLiquid cleaning and/or cleansing composition comprising a polylactic acid biodegradable abrasive
US8440604Sep 28, 2009May 14, 2013The Procter & Gamble CompanyLiquid hard surface cleaning composition
US8445422Sep 20, 2011May 21, 2013The Procter & Gamble CompanyLiquid cleaning composition
US8470759Jun 19, 2012Jun 25, 2013The Procter & Gamble CompanyLiquid cleaning and/or cleansing composition comprising a polyhydroxy-alkanoate biodegradable abrasive
US8546316Sep 20, 2011Oct 1, 2013The Procter & Gamble CompanyLiquid detergent composition with natural abrasive particles
US8546317Jul 9, 2010Oct 1, 2013The Procter & Gamble CompanyHard surface cleaning composition
US8551932Sep 28, 2009Oct 8, 2013The Procter & Gamble CompanyLiquid hard surface cleaning composition
US8558051Jul 15, 2008Oct 15, 2013The Procter & Gamble CompanyDisposable absorbent article having odor control system
US8563496Dec 10, 2010Oct 22, 2013The Procter & Gamble CompanyLiquid acidic hard surface cleaning composition
US8569223Sep 28, 2009Oct 29, 2013The Procter & Gamble CompanyLiquid hard surface cleaning composition
US8629095Apr 20, 2011Jan 14, 2014The Procter & Gamble CompanyLiquid cleaning and/or cleansing composition comprising polyurethane foam abrasive particles
US8680036Dec 20, 2010Mar 25, 2014The Procter & Gamble CompanyLiquid cleaning composition comprising color-stable polyurethane abrasive particles
US8703685Jun 19, 2012Apr 22, 2014The Procter & Gamble CompanyLiquid cleaning and/or cleansing composition comprising polylactic acid abrasives
US8754027May 9, 2013Jun 17, 2014Basf SeQuaternized polyethulenimines with a high ethoxylation degree
US8759270Jun 14, 2012Jun 24, 2014The Procter & Gamble CompanyLiquid detergent composition with abrasive particles
EP0693549A1Jul 19, 1994Jan 24, 1996THE PROCTER & GAMBLE COMPANYSolid bleach activator compositions
EP0751213A1 *Mar 4, 1996Jan 2, 1997THE PROCTER & GAMBLE COMPANYCarpet cleaning compositions and method for cleaning carpets
EP0751214A1Jun 30, 1995Jan 2, 1997THE PROCTER & GAMBLE COMPANYStable peroxygen bleach-containing compositions
EP0752469A1Jul 5, 1995Jan 8, 1997THE PROCTER & GAMBLE COMPANYLaundry pre-treatment with improved fabric/colour safety
EP0776966A1Dec 2, 1995Jun 4, 1997THE PROCTER & GAMBLE COMPANYLiquid bleaching compositions packaged in spray-type dispenser and a process for pretreating fabrics therewith
EP0779357A1Dec 16, 1995Jun 18, 1997THE PROCTER & GAMBLE COMPANYStable emulsions comprising a hydrophobic liquid ingredient
EP0791362A2Nov 13, 1996Aug 27, 1997THE PROCTER & GAMBLE COMPANYDisinfecting compositions and processes for disinfecting surfaces
EP0839462A1Oct 29, 1996May 6, 1998THE PROCTER & GAMBLE COMPANYBreathable perspiration pads having odour control
EP0839900A1Oct 31, 1996May 6, 1998THE PROCTER & GAMBLE COMPANYCarpet cleaning compositions and method for cleaning carpets
EP0839903A1Oct 31, 1996May 6, 1998THE PROCTER & GAMBLE COMPANYLiquid aqueous bleaching compositions and pretreatment process
EP0842604A1Nov 13, 1996May 20, 1998THE PROCTER & GAMBLE COMPANYSprayable disinfecting compositions and processes for disinfecting surfaces therewith
EP0842605A1Nov 13, 1996May 20, 1998THE PROCTER & GAMBLE COMPANYSprayable disinfecting compositions and processes for disinfecting surfaces therewith
EP0842606A1Nov 13, 1996May 20, 1998THE PROCTER & GAMBLE COMPANYDisinfecting microemulsions
EP0844302A1Nov 22, 1996May 27, 1998THE PROCTER & GAMBLE COMPANYLaundry bleaching compositions
EP0978247A1Aug 3, 1998Feb 9, 2000THE PROCTER & GAMBLE COMPANYStacked wet wipes having anti evaporation layers
EP1023863A1Jan 29, 1999Aug 2, 2000THE PROCTER & GAMBLE COMPANYPerforated sheet of material
EP1157672A1May 23, 2000Nov 28, 2001THE PROCTER & GAMBLE COMPANYLiquid and odour absorbent structure for inanimate places such as refrigerators
EP1835016A1Mar 17, 2006Sep 19, 2007The Procter and Gamble CompanyProcess of bleaching fabric
EP1845152A1Apr 14, 2006Oct 17, 2007The Procter and Gamble CompanyProcess of cleaning a hard surface with zwitterionic copolymer
EP1964543A1Feb 28, 2008Sep 3, 2008Takasago International CorporationPreservative compositions
EP2025742A1Apr 29, 2008Feb 18, 2009The Procter and Gamble CompanyLiquid acidic hard surface cleaning composition
EP2031048A1Dec 4, 2007Mar 4, 2009The Procter and Gamble CompanyLiquid acidic hard surface cleaning composition
EP2039749A1Sep 10, 2008Mar 25, 2009The Procter & Gamble CompanyProcess of treating inclined hard surface
EP2053119A1Oct 14, 2008Apr 29, 2009The Procter and Gamble CompanyFabric softening compositions having improved stability upon storage
EP2075324A1Dec 27, 2007Jul 1, 2009The Procter and Gamble CompanyLiquid acidic hard surface cleaning composition
EP2075325A1Nov 13, 2008Jul 1, 2009The Procter & Gamble CompanyLiquid acidic hard surface cleaning composition
EP2112218A1Apr 25, 2008Oct 28, 2009The Procter and Gamble CompanyColored bleaching composition
EP2135931A1Jun 16, 2008Dec 23, 2009The Procter and Gamble CompanyUse of soil release polymer in fabric treatment compositions
EP2157162A1Aug 13, 2008Feb 24, 2010The Procter and Gamble CompanyParticulate bleaching composition comprising enzymes
EP2166073A1Sep 23, 2008Mar 24, 2010The Procter & Gamble CompanyCleaning composition
EP2166075A1Sep 23, 2008Mar 24, 2010The Procter and Gamble CompanyCleaning composition
EP2166076A1Sep 23, 2008Mar 24, 2010The Procter & Gamble CompanyCleaning composition
EP2206766A1Dec 23, 2008Jul 14, 2010The Procter and Gamble CompanyLiquid acidic hard surface cleaning composition
EP2264136A1Jun 19, 2009Dec 22, 2010The Procter and Gamble CompanyLiquid hand dishwashing detergent composition
EP2264138A1Jun 19, 2009Dec 22, 2010The Procter and Gamble CompanyLiquid hand dishwashing detergent composition
EP2270124A1Jun 30, 2009Jan 5, 2011The Procter and Gamble CompanyBleaching compositions comprising a perfume delivery system
EP2272942A1Jul 8, 2009Jan 12, 2011The Procter and Gamble CompanyHard surface cleaning composition
EP2336282A1Dec 17, 2009Jun 22, 2011The Procter and Gamble CompanyLiquid acidic hard surface cleaning composition
EP2338962A1Dec 20, 2010Jun 29, 2011The Procter and Gamble CompanyLiquid cleaning and/or cleansing composition
EP2338963A1Dec 20, 2010Jun 29, 2011The Procter and Gamble CompanyLiquid cleaning and/or cleansing composition
EP2338964A2Dec 20, 2010Jun 29, 2011The Procter and Gamble CompanyLiquid cleaning and/or cleansing composition
EP2338965A1Dec 20, 2010Jun 29, 2011The Procter and Gamble CompanyLiquid cleaning and/or cleansing composition
EP2338966A1Dec 20, 2010Jun 29, 2011The Procter and Gamble CompanyLiquid cleaning and/or cleansing composition
EP2431452A1Sep 20, 2011Mar 21, 2012The Procter and Gamble CompanyLiquid cleaning composition
EP2431453A1Sep 20, 2011Mar 21, 2012The Procter and Gamble CompanyLiquid cleaning and/or cleansing composition
EP2431454A1Sep 20, 2011Mar 21, 2012The Procter and Gamble CompanyLiquid cleaning and/or cleansing composition
EP2431455A1Sep 20, 2011Mar 21, 2012The Procter and Gamble CompanyLiquid cleaning and/or cleansing composition
EP2520641A1Jun 30, 2006Nov 7, 2012The Procter and Gamble CompanyLow phosphate automatic dishwashing detergent composition
EP2537916A1Jun 29, 2010Dec 26, 2012The Procter and Gamble CompanyBleaching compositions comprising a perfume delivery system
EP2573156A1Sep 20, 2011Mar 27, 2013The Procter and Gamble CompanyLiquid cleaning composition
EP2586855A1Dec 23, 2008May 1, 2013The Procter and Gamble CompanyLiquid acidic hard surface cleaning composition
EP2631286A1Feb 23, 2012Aug 28, 2013The Procter and Gamble CompanyLiquid cleaning composition
EP2719752A1Oct 15, 2012Apr 16, 2014The Procter and Gamble CompanyLiquid detergent composition with abrasive particles
EP2727991A1Oct 30, 2012May 7, 2014The Procter and Gamble CompanyCleaning and disinfecting liquid hand dishwashing detergent compositions
WO1996025478A1Feb 6, 1996Aug 22, 1996Gerard Marcel BaillelyDetergent composition comprising an amylase enzyme and a nonionic polysaccharide ether
WO1997042282A1May 3, 1996Nov 13, 1997Procter & GambleDetergent compositions comprising polyamine polymers with improved soil dispersancy
WO1997046190A1 *May 23, 1997Dec 11, 1997Alessandro GagliardiniAbsorbent articles having an odour control system comprising a chelating agent
WO2000029311A1Nov 16, 1999May 25, 2000Melissa Dee AquinoOdor-neutralizing and liquid-absorbing trash bags
WO2001021499A1Sep 22, 1999Mar 29, 2001Citra Wijaya NgA hand-held liquid container
WO2001023274A1Sep 29, 2000Apr 5, 2001Foley Peter RobertDetergent package with means to mask amine malodours
WO2002000527A1Jun 19, 2001Jan 3, 2002Procter & GamblePop-up wipe dispensing system
WO2006123102A1May 10, 2006Nov 23, 2006Reckitt Benckiser NvAqueous cleaning compositions
WO2008039353A2Sep 20, 2007Apr 3, 2008Danisco Us Inc Genencor DivEnzymatic treatment of textiles using a pectate lyase from bacillus subtilis
WO2010075120A1Dec 16, 2009Jul 1, 2010The Procter & Gamble CompanyLiquid acidic hard surface cleaning composition
WO2010083124A1Jan 11, 2010Jul 22, 2010The Procter & Gamble CompanyBleaching compositions containing perfume microcapsules
WO2010083125A1Jan 11, 2010Jul 22, 2010The Procter & Gamble CompanyBleaching compositions containing perfume microcapsules
WO2010088112A1Jan 20, 2010Aug 5, 2010The Procter & Gamble CompanyLaundry multi-compartment pouch composition
WO2010094924A1Feb 19, 2010Aug 26, 2010Reckitt Benckiser N.V.Percarbonate containing detergent product
WO2010100028A2Feb 17, 2010Sep 10, 2010Huntsman Advanced Materials (Switzerland) GmbhEnzymatic textile bleach-whitening methods
WO2010101659A1Mar 5, 2010Sep 10, 2010Gowan Co.Plant treatment compositions and methods for their use
WO2010147916A1Jun 15, 2010Dec 23, 2010The Procter & Gamble CompanyLiquid hand dishwashing detergent composition
WO2010147933A1Jun 15, 2010Dec 23, 2010The Procter & Gamble CompanyLiquid hand dishwashing detergent composition
WO2011002759A2Jun 29, 2010Jan 6, 2011The Procter & Gamble CompanyBleaching compositions comprising a perfume delivery system
WO2011075466A1Dec 14, 2010Jun 23, 2011The Procter & Gamble CompanyLiquid acidic hard surface cleaning composition
WO2011084569A1Dec 16, 2010Jul 14, 2011The Procter & Gamble CompanyDishwashing detergent composition having a malodor control component and methods of cleaning dishware
WO2011084577A1Dec 16, 2010Jul 14, 2011The Procter & Gamble CompanyHard surface cleaning composition having a malodor control component and methods of cleaning hard surfaces
WO2011087733A1Dec 20, 2010Jul 21, 2011The Procter & Gamble CompanyLiquid cleaning and/or cleansing composition
WO2011087735A1Dec 20, 2010Jul 21, 2011The Procter & Gamble CompanyLiquid cleaning and/or cleansing composition
WO2011087736A1Dec 20, 2010Jul 21, 2011The Procter & Gamble CompanyLiquid cleaning and/or cleansing composition
WO2011087739A1Dec 20, 2010Jul 21, 2011The Procter & Gamble CompanyLiquid cleaning and/or cleansing composition
WO2011087744A2Dec 20, 2010Jul 21, 2011The Procter & Gamble CompanyLiquid cleaning and/or cleansing composition
WO2011087748A1Dec 20, 2010Jul 21, 2011The Procter & Gamble CompanyLiquid cleaning and/or cleansing composition
WO2011087754A1Dec 20, 2010Jul 21, 2011The Procter & Gamble CompanyAn alkaline liquid hand dish washing detergent composition
WO2011100667A1Feb 14, 2011Aug 18, 2011Ls9, Inc.Surfactant and cleaning compositions comprising microbially produced branched fatty alcohols
WO2011133438A1Apr 18, 2011Oct 27, 2011The Procter & Gamble CompanyLiquid cleaning and/or cleansing composition
WO2011133508A1Apr 19, 2011Oct 27, 2011The Procter & Gamble CompanyLiquid cleaning and/or cleansing composition
WO2011163457A1Jun 23, 2011Dec 29, 2011The Procter & Gamble CompanyProduct for pre-treatment and laundering of stained fabric
WO2012001078A1Jun 29, 2011Jan 5, 2012Hindustan Unilever LimitedPackaged fabric cleaning compositions
WO2012001079A1Jun 29, 2011Jan 5, 2012Hindustan Unilever LimitedPackaged fabric cleaning compositions
WO2012025736A2Aug 12, 2011Mar 1, 2012Reckitt & Colman (Overseas) LimitedDetergent product
WO2012027325A1Aug 23, 2011Mar 1, 2012Gowan Comercio Internacional E Servicos LimitadaPlant treatment compositions and methods for their use
WO2012040136A1Sep 20, 2011Mar 29, 2012The Procter & Gamble CompanyLiquid cleaning composition
WO2012040141A1Sep 20, 2011Mar 29, 2012The Procter & Gamble CompanyLiquid cleaning composition
WO2012040142A1Sep 20, 2011Mar 29, 2012The Procter & Gamble CompanyLiquid cleaning composition
WO2012040143A1Sep 20, 2011Mar 29, 2012The Procter & Gamble CompanyLiquid cleaning composition
WO2012138727A1Apr 4, 2012Oct 11, 2012The Procter & Gamble CompanyHome care article
WO2012140413A1Apr 5, 2012Oct 18, 2012Reckitt & Colman (Overseas) LimitedCoated fabric care agent
WO2012140421A1Apr 12, 2012Oct 18, 2012Reckitt & Colman (Overseas) LimitedNovel composite
WO2012177615A1Jun 19, 2012Dec 27, 2012The Procter & Gamble CompanyLiquid cleaning and/or cleansing composition
WO2012177617A1Jun 19, 2012Dec 27, 2012The Procter & Gamble CompanyLiquid cleaning and/or cleansing composition
WO2012177628A1Jun 19, 2012Dec 27, 2012The Procter & Gamble CompanyLiquid cleaning and/or cleansing composition
WO2012177676A1Jun 20, 2012Dec 27, 2012The Procter & Gamble CompanyLiquid cleaning and/or cleansing composition
WO2012177709A1Jun 20, 2012Dec 27, 2012The Procter & Gamble CompanyProduct for pre-treatment and laundering of stained fabric
WO2013016030A1Jul 13, 2012Jan 31, 2013The Procter & Gamble CompanyMultiphase liquid detergent composition
WO2013016031A1Jul 13, 2012Jan 31, 2013The Procter & Gamble CompanyMultiphase liquid detergent composition
WO2013043622A1Sep 19, 2012Mar 28, 2013The Procter & Gamble CompanyLiquid cleaning composition
WO2013070559A1Nov 6, 2012May 16, 2013The Procter & Gamble CompanySurface treatment compositions including shielding salts
WO2013070560A1Nov 6, 2012May 16, 2013The Procter & Gamble CompanySurface treatment compositions including shielding salts
WO2013086251A1Dec 7, 2012Jun 13, 2013The Procter & Gamble CompanyMethod of providing fast drying and/or delivering shine on hard surfaces
WO2013126535A1Feb 21, 2013Aug 29, 2013The Procter & Gamble CompanyLiquid cleaning composition with abrasive powder from olive kernels
WO2013167401A1Apr 26, 2013Nov 14, 2013Basf SeQuaternized polyethylenimines with a high ethoxylation degree
WO2013167467A1May 2, 2013Nov 14, 2013Basf SeQuaternized polyethylenimines with a high quaternization degree
WO2013170001A1May 9, 2013Nov 14, 2013The Procter & Gamble CompanyLiquid detergent composition for improved shine
WO2013170002A1May 9, 2013Nov 14, 2013The Procter & Gamble CompanyLiquid detergent composition for improved shine
WO2013187917A1Jun 19, 2012Dec 19, 2013The Procter & Gamble CompanyLiquid cleaning and/or cleansing composition
WO2014018309A1Jul 16, 2013Jan 30, 2014The Procter & Gamble CompanyLow ph liquid cleaning compositions with enzymes
WO2014070643A1Oct 28, 2013May 8, 2014The Procter & Gamble CompanyCleaning and disinfecting liquid hand dishwashing detergent compositions
Classifications
U.S. Classification510/477, 510/489, 510/361, 510/495, 510/357
International ClassificationC07C309/58, C07C59/52, C11D3/16, C07C309/42, C07C49/825, C11D3/00, C07C45/00, C07C45/49, C07C59/70, C07C65/05, C11D3/20
Cooperative ClassificationC07C49/825, C07C45/004, C07C59/52, C07C309/58, C07C65/05, C07C309/00, C07C309/42, C07C59/70, C11D3/2086, C07C45/49
European ClassificationC07C309/00, C07C45/49, C07C45/00G, C07C309/42, C07C65/05, C07C49/825, C07C59/52, C07C59/70, C07C309/58, C11D3/20E5