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Publication numberUS3130165 A
Publication typeGrant
Publication dateApr 21, 1964
Filing dateAug 22, 1962
Priority dateAug 31, 1961
Also published asDE1227179B
Publication numberUS 3130165 A, US 3130165A, US-A-3130165, US3130165 A, US3130165A
InventorsPeter Brocklehurst
Original AssigneeProcter & Gamble
Export CitationBiBTeX, EndNote, RefMan
External Links: USPTO, USPTO Assignment, Espacenet
Inorganic peroxy-compounds containing organic activators
US 3130165 A
Abstract  available in
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Claims  available in
Description  (OCR text may contain errors)

United States Patent 3,130,165 Patented Apr. 21, 1964 "ice 3 130 165 phatic carboxylic acid. Permissible substituent groups on the henol in lude r INORGANIC PEROXY-bOMPOUNDS CONTAINING grouis. 6 ca boxyl groups and Sulphomc acid ORGANIC ACTIVATORS preferred esters Peter Brocklehurst, Fairway, Meadow Close, Harden, Chlmacet l h n 1 near Bingley, England, assignor to The Procter & Ganiy p e o ble Company, Cincinnati, Ohio, a corporation of Ohio No Drawing. Filed Aug. 22, 1962, Ser. No. 218,524 @rOCQCIhCl Claims priority, application Great Britain Aug. 31, 1961 4 Claims (CL 252 99) Chloracetyl phenol-4-potassium sulphonate The invention relates to detergent compositions con- 10 KSO3 C OCO'CH,Cl taining oxygen-yielding compounds, such as sodium perborate, which provide a simultaneous washing and stain chioraceiyiphenowCarboxyhc acid removing action.

Many detergent compositions contain an inorganic O peroxy-compound, such as sodium perborate ouodium percarbonate, to provide bleaching and stain-removing COOH properties. These compositions provide an excellent Y ga a bleaching effect at the boil but at a lower temperatures, 000311201 for example 58-80" C., the bleaching action is slower. This means that the detergent composition can be used HOOC OCOCHzCl for washing whites, for example white cotton or linen goods such as table-linen, bed-linen and shirts, at the boil, 5 mm with satisfactory stain removal. Such detergent compositions are also safe to use on coloured cotton goods Alpha Chloropmplonyl Sahcychc acid and goods of more delicate fabrics such as those con- OCOCHCLCU3 sisting of or containing rayon or artificial fibres, which are normally washed at lower temperatures, such as 50- 5 80 C., without the risk of damage to the colour or the fabric. It is customary for housewives to use detergent chloracetylsahcychc acid compositions for boiling whites and then to wash, at a lower temperature, a second load of coloureds in the QOCOCHZCI wash liquor previously used for Washing the whites.

In domestic washing machines it is often impracticable -L or inconvenient to boil the wash liquor and it is desirable, The a flamed ester is Particularly PTefflredtherefg e to provide a detergent composition has iS believed the esters of the invention Teilct effective bleaching and stain removing properties at the with hydrogen Peroxide in the washing Soiutioh temperatures conventionally used in domestic washing hydrogen Peroxide being Provided y the inorganic p y machines, vis. 50-80 c. At the same time, it is imcompound) to produce a P y chloroaliphatic acid portant that this low temperature bleaching effect should 40 which is highly reactive and which ProvideS an effective not persist so as to be present when the second load bieachihg action, but that the P Y chiofoaiiphatic of coloureds is washed, as it might have a deleterious acid is highly unstable 50 that the bleaching effect is ff t on h l d transient and does not perisist into the second load. In

Accordingly, it is an object of this invention to provide Spite of this rapid 1055 of activity, the Compositions of detergent compositions which have an accelerated bleachthe invention d0 nevertheless give eiiectivfi bleaching ing effect on the first load of clothes washed and no and Stain removal on the first ioadaccelerated bleaching effect on the second load of clothes The P y Compounds of this invention are those washed in the same wash liquor as the first load. having Oxygen bleaching Poweh The Customary ihof It is a further object of this invention to provide a g i W W- p are the alkali metal perborates, process for washing a load of white clothes and a load of PtiicaibhhttteS and mohopeisuiiates, Such as Sodium and coloured clothes in the same wash water whereby the white clothes are subjected to an accelerated bleaching effect and the coloured clothes are not subjected to said accelerated bleaching effect.

It has now been found that the customary inorganic peroxy-compounds, such as sodium perborate and sod'nim percarbonate, can be activated so as to have effective b eac ing and stain-Femoving properties at washing machine temperatures (5080 C.) such activation being transient in nature and not persisting into the second load so that a second load of coloureds can be washed in the same wash liquor with no risk of damage to the colours. This is achieved by incorporating in a detergent composition containing suc l wmpnundsxer- W e n inven ion provides a detergent composition comprising a soap and/or a synthetic detergent, an inorganic peroxy compound, and an ester of a phenol or substituted phenol with an alpha-chlorinated lower aliphatic carboxylic acid, such as chloracetic acid or alpha chlorpropionic acid, the esters containing no ester group of any acid other than an alpha chlorinated lower alipotassium perborates and sodium and potassium percarbonates or complex salts such as KHSO -K SO 2KHSO The proportions of soap or synthetic detergent and olf inorganic peroxy compound in the compositions can be those customarily used in conventional detergent bleaching compositions. For example, compositions containing 5 to 50%, by weight, of soap or synthetic detergent and 3 to 20%, by weight, of sodium perborate are suitable. The proportion of the ester in the compositions can vary from about 0.05 mole of ester per atom of available oxygen to about 2 moles of ester per atom of available oxygen. A proportion of one mole of ester per atom of available oxygen is highly effective.

Examples of suitable detergents include:

(1) Ordinary alkali metal soaps such as the sodium and potassium salts of the higher fatty acids of naturally occurring plant or animal esters (e.g., palm oil, coconut oil, habassu oil, soybean oil, castor oil, tallow, whale and fish oils, grease and lard, and mixtures thereof) or of synthetically produced fatty acids (e.g., by the oxidation of petroleum, or by hydrogenation of carbon monoxide by the Fischer-Tropsch process), of resin acid (e.g. rosin and those resin acids in tall oil) and/or of naphthenic acids. 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. These soaps are normally hydrogenated, at least slightly, for better keeping qualities.

(2) Synthetic organic detergents characterized by their high solubility in water, their resistance to precipitation by the constitutents of hard water and their surface active and effective detergent properties, including:

(a) Anionic synthetic detergents (excluding true soaps): This class of synthetic detergents can be broadly described as the water-soluble salts, particularly the alkali metal salts, of organic sulfuric reaction product having in the molecular structure an alkyl radical containing from about 8 to about 22 carbon atoms and a radical selected from the group consisting of sulfonic acid and sulfuric acid ester radicals. Important examples of the synthetic detergents which form a part of the preferred compositions of the present invention are the sodium or potassium alkyl sulfates, especially those obtained by sulfating the higher alcohols 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 carbon atoms, especially those of the types described in United States Letters Patent Numbers 2,220,099 and 2,477,383; sodium alkyl glyceryl ether sulfonates, especially those ethers of the higher alcohols derived from tallow and coconut oil; sodium coconut oil fatty acid monoglyceride sulfates and sulfonates; sodium or potassium salts of sulfuric acid esters of the reaction product of one mole of a higher fatty alcohol (e.g., tallow or coconut oil alcohols) and about three moles of ethylene oxide; sodium or potassium salts of alkyl phenol ethylene oxide ether sulfate with about four units of ethylene oxide per molecule and in which the alkyl radicals contain about 9 carbon atoms; 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 a methyl taurine in which the fatty acids, for example, are derived from coconut oil; and others known in the art, a number being specifically set forth in United States Letters Patent Numbers 2,486,921, 2,486,922 and 2,396,278.

(b) Nonionic synthetic detergents: This class of 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.

For examples, a well known class of nonionic syn thetic detergents is made available on the market under the trade name of Pluronic. These compounds are formed by condensing ethylene oxide with an hydrophobic base formed by the condensation of propylene oxide with propylene glycol. The hydrophobic portion of the molecule which, of course, exhibits water insolubility has a molecular weight of from about 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 products 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:

(i) 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 10 to 25 moles of ethylene oxide per mole of alkyl phenol. The alkyl substituent in such compounds may be derived from polymerized propylene, diisobutylene, octane, or nonane, for example.

(ii) Those derived from the condensation of ethylene oxide with the product resulting from the reaction of propylene oxide and ethylene diamineproducts which may be varied in composition depending upon the balance between the hydrophobic and hydrophilic elements which is desired. For examples, compounds containing from about 40% to about polyoxyethylene by weight and having a molecular weight of from about 5000 to about 11,000, resulting from the 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 molecular weight of the order of 2500 to 3000, are satisfactory.

(iii) The condensation product of aliphatic alcohols having from 8 to 18 carbon atoms, in either straight chain or branched chain configuration, with ethylene oxide, e.g., a coconut alcohol ethylene oxide condensate having from 10 to 30 moles of ethylene oxide per mole of coconut alcohol, the coconut alcohol fraction having from 10 to 14 carbon atoms.

(iiii) Trialkyl phosphine oxides wherein one alkyl group ranges from 10 to 18 carbon atoms and two alkyl groups range from 1 to 3 carbon atoms; the alkyl groups can contain hydroxy substituents; a specific example is tetra decyl dimethyl phosphine oxide.

(0) Zwitterionic detergents such as betaine and betainelike detergents wherein the molecule contains both basic and acidic groups which form an inner salt giving the molecule both cationic and anionic hydrophilic groups over a broad range of wash water pH values. Some common examples of these detergents are described in U.S. Patents 2,082,275; 2,702,279; and 2,255,082.

(d) Amphoteric and ampholytic detergents which can be either cationic or anionic depending upon the pH of the system and which are represented by detergents such as dodecyl-beta-alanine, Nalkyltaurines such as the one prepared by reacting dodecylamine with sodium isethionate according to the teaching of U.S. 2,658,072, N-higher alkylaspartic acids such as those produced according to the teaching of U.S. 2,438,091, and the products sold under the trade name Miranol" and described in U.S. 2,528,378.

The compositions can also contain conventional in gredients such as builder salts (e.g., pyrophosphates, tripolyphosphates, carbonates, acid pyrophosphates, phosphates, and silicates of alkali metals; nitrilo triacetic acid and ethylene diaminetetraacetic acid and alkali metal salts thereof; and sodium and potassium phytates); antiredeposition agents such as sodium carboxymethyl cellulose; suds builders such as ammonia amides, N-alkyl amides, and alkanolamides of fatty acids (e.g., coconut monoethanolamide and lauroyl and myristoyl glycerol amides, ethanol amides and isopropanol amides); optical bleaching agents; colour; and perfume. For heavy-duty laundering, the compositions of this invention preferably contain about 20% to about 60% sodium tripolyphosphate.

Example A spray dried detergent composition was prepared, containing the following (all figures are parts by weight):

Sodium dodecyl benzene sulphonate, the dodecyl being derived from tetrapropylene 20 Sodium tripolyphosphate 35 Sodium silicate solids (ratio SiO :Na- .O=2:l) 5

Monoethanolamide of coconut fatty acids 2.5 Sodium carboxymethyl cellulose 1.0 Sodium sulphate 27.5 Moisture 10 80 parts by weight of this detergent powder were mixed with 8 parts by weight of sodium perborate and 12 parts by weight of chloracetyl salicylic acid.

A two-inch square piece of tea-stained cloth was washed for minutes at 50 C. in a solution of 2.4 gms. of the above mixture in 400 ml. of distilled water. After rinsing in distilled water and drying and ironing the stain removal as measured on the Eel reflectometer was equivalent to an increase in reflectance of 30%.

A second two inch square piece of the same tea-stained cloth was then washed in the solution and rinsed, dried and ironed as described above. The stain removal was equivalent to an increase in reflectance of only 17%.

A test on wash liquor after the first piece of cloth had been washed and before the second piece has been added showed that it gave no titratable liberation of iodine when added to acidified potassium iodide. This indicates that the liquor no longer had any activated bleaching action.

In a similar experiment in which the chloracetyl salicylic acid was replaced by sodium sulphate the stain removal as measured on the Eel rellectometer was equivalent to an increase in reflectance of 16% on the first load and 16% on the second.

When, in the above example, equivalent amounts of chloracetyl phenol, chloracetyl phenol-4-potassium sul fonate, chloroacetylphenol-3-carboxylic acid, 3,4,5-tri- (chloroacetyl) gallic acid, or alpha chloropropionyl salicylic acid are substituted for the chloracetyl salicylic acid, substantially equivalent results are obtained.

When, in the above example, equivalent amounts of sodium or potassium percarbonates and monopersulfates are substituted for the sodium perborate, substantially equivalent results are obtained.

Similarly, when other detergent materials are used containing sodium or potassium, coconut or tallow soap; the alkali metal, ammonium, and substituted ammonium salts of coconut or tallow alkyl sulfates; sodium coconut or tallow alkyl glyceryl ether sulfonates; and alkali metal salts of the sulfuric acid ester of the reaction product of one mole of coconut or tallow alcohols and three moles of ethylene oxide are substituted in equivalent amounts by weight for the sodium alkyl benzene sulfonate of this example, substantially equivalent results in improved bleaching activity are obtained. Also, the substitution of other builders such as alkali metal pyrophosphates, phosphates, phytates, etc., for the sodium tripolyphosphate, or the elimination of builders altogether does not aflect the performance of the bleaching system. Furthermore, the substitution of coconut fatty acid ammonia amide, isopropanol amide, or glycerol amide for the ethanol amide of this example, or the elimination of suds builders altogether does not affect the performance of the bleaching system.

What we claim is:

1. A household laundry detergent composition com prising (A) from 5 to of an organic detergent selected from the group consisting of (l) alkali metal soaps of higher fatty acids, (2) anionic non-soap synthetic detergents, (3) nonionic synthetic detergents, (4) zwitterionic synthetic detergents, and (5) amphoteric synthetic detergents; (B) from 33-20% by weight of inorganic peroxy-compound selected from the group consisting of sodium and potassium perborates, percarbonates and monopersulfates; and (C) from about 0.5 to about 2.0 moles per mole of available oxygen in said peroxy-compound of an ester of a phenol selected from the group consisting of phenol and substituted phenols containing at least one substituent group selected from the group consisting of carboxyl groups and sulphonic acid groups and an alpha-chlorinated lower aliphatic acid selected from the group consisting of acetic and propionic acids.

2. The detergent composition of claim 1 in which the ester is selected from the group consisting of chloracetyl phenol; chloracetyl phenol-4-potassium sulphonate; chloracetyl phenol-3-carboxylic acid; 3,4,5-tri(chloracetyl) gallic acid; alpha chloropropionyl salicyclic acid; and chloracetyl salicyclic acid.

3. The detergent composition of claim 1 in which the ester is chloracetyl salicyclic acid.

4. The detergent composition according to claim 1 wherein there is one mole of ester per atom of available oxygen.

References Cited in the file of this patent UNITED STATES PATENTS 2,975,139 Kauifman et a1. Mar. 14, 1961 3,003,910 Dithmar Oct. 10, 1961 FOREIGN PATENTS 836,988 Great Britain June 9, 1960 OTHER REFERENCES Reactions in the Salicyclic Acid Series by Kagan et al., J. Amer. Chem. Soc. vol. 81 (1959) pages 1986- 91.

Chemical Abstracts, volume 54, March-April 1960, page 4445f.

Patent Citations
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Referenced by
Citing PatentFiling datePublication dateApplicantTitle
US3255116 *Oct 16, 1964Jun 7, 1966Procter & GambleSulfoximine-containing detergent compositions
US3338839 *Dec 28, 1964Aug 29, 1967Fmc CorpActivating of peroxygen compounds
US3671439 *Jul 22, 1969Jun 20, 1972American Home ProdOxygen bleach-activator systems stabilized with puffed borax
US3969257 *Jul 24, 1973Jul 13, 1976Colgate-Palmolive CompanyWashing and bleaching composition containing bleach, activator and a nitrilotricarboxylic acid compound
US4120809 *May 5, 1976Oct 17, 1978Colgate-Palmolive CompanyWashing and bleaching with composition containing bleach activator and a nitrilotricarboxylic acid compound
US4283301 *Jul 2, 1980Aug 11, 1981The Procter & Gamble CompanyComprising a peroxy bleach, activator
US4367156 *Aug 10, 1981Jan 4, 1983The Procter & Gamble CompanyBleaching process and compositions
US4483778 *Dec 22, 1983Nov 20, 1984The Procter & Gamble CompanyPeroxygen bleach activators and bleaching compositions
US4486327 *Dec 22, 1983Dec 4, 1984The Procter & Gamble CompanyBodies containing stabilized bleach activators
US4539130 *Oct 30, 1984Sep 3, 1985The Procter & Gamble CompanySulfonate and carboxylic acid esters, anhydrides and imide derivatives
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US4853143 *Mar 16, 1988Aug 1, 1989The Procter & Gamble CompanyBleach activator compositions containing an antioxidant
US4859800 *Apr 30, 1987Aug 22, 1989The Clorox CompanyPhenoxyacetate peracid precursors
US4956117 *May 19, 1989Sep 11, 1990The Clorox CompanyBleaches
US4964870 *Jun 8, 1989Oct 23, 1990The Clorox CompanyAnd hydrogen peroxide
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US5049305 *Jun 25, 1990Sep 17, 1991Zielske Alfred GBleach
US5130045 *Jun 5, 1990Jul 14, 1992The Clorox CompanyContaining quaternary amonium salt
US5182045 *Mar 29, 1989Jan 26, 1993The Clorox CompanyLate peracid precursors
US5234616 *Jan 16, 1992Aug 10, 1993The Clorox CompanyMethod of laundering clothes using a delayed onset active oxygen bleach composition
US5391812 *Sep 25, 1992Feb 21, 1995The Clorox CompanyPolyglycolate peracid precursors
US5545748 *Oct 18, 1994Aug 13, 1996The Clorox CompanyPolyglycolate peracid precursors
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US7067467 *Dec 19, 2002Jun 27, 2006Unilever Home & Personal Care Usa Division Of Conopco, Inc.Useful for bleaching various surfaces, especially in laundry cleaning
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EP0150532A1Dec 12, 1984Aug 7, 1985THE PROCTER & GAMBLE COMPANYPeroxygen bleach activators and bleaching compositions
EP0283252A1 *Mar 16, 1988Sep 21, 1988Procter & Gamble LimitedBleaching compositions
EP0320219A1 *Dec 7, 1988Jun 14, 1989Procter & Gamble LimitedDetergent compositions
EP0402047A1 *May 31, 1990Dec 12, 1990E.I. Du Pont De Nemours And CompanyImproved process for preparing phenyl esters of substituted acids
Classifications
U.S. Classification510/312, 510/376, 510/505, 510/495, 510/504
International ClassificationC11D9/04, C11D9/44, C11D3/39, C11D9/28, C11D3/24
Cooperative ClassificationC11D3/39, C11D3/3915, C11D3/391, C11D9/28, C11D9/446, C11D3/24
European ClassificationC11D3/39, C11D9/44F, C11D9/28, C11D3/39B2D5, C11D3/39B2D4, C11D3/24