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Publication numberUS3919107 A
Publication typeGrant
Publication dateNov 11, 1975
Filing dateMar 23, 1973
Priority dateMar 23, 1973
Publication numberUS 3919107 A, US 3919107A, US-A-3919107, US3919107 A, US3919107A
InventorsThompson James Edwin
Original AssigneeProcter & Gamble
Export CitationBiBTeX, EndNote, RefMan
External Links: USPTO, USPTO Assignment, Espacenet
Built detergent compositions containing dextrin esters of poly carboxylic acids
US 3919107 A
Abstract
Detergent compositions comprising a combination of certain water-soluble organic surface-active agents and, as detergent builders, certain water-soluble salts of dextrin polycarboxylates.
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AU 165 EX 0 R 3 9 9 l 9 9 1 0 7 United States Patent 1191 Thompson 1 BUILT DETERGENT COMPOSITIONS CONTAINING DEXTRIN ESTERS OF POLY CARBOXYLIC ACIDS [75] Inventor: James Edwin Thompson, Cincinnati.

Ohio

[73] Assignee: The Procter & Gamble Company, Cincinnati, Ohio [22.1 Filed: Mar. 23, 1973 1211 Appl. No.: 344,465

[52] US. Cl. 252/99; 252/89; 252/132; 252/135; 252/180; 252/532; 252/536; 252/551; 252/555; 260/233.5

1511 1111.01. c111) 1/08 [58] Field of Search 252/135, 95. 99

[56] References Cited UNITED STATES PATENTS 2.311.008 2/1943 Tucker 252/89 X 3.332.880 7/1967 Kessler et al. 252/161 3.494.786 2/1971) Nielsen 252/95 Prinmry Eruminer-Benjamin R. Padgett Assistant Ernminer-Christine M. Nucker Attorney, Agent, or Firm-George W. Allen; Jerry .1. Yetter; Jack D. Schaeffer [57] ABSTRACT Detergent compositions comprising a combination of certain water-soluble organic surface-active agents and, as detergent builders, certain water-soluble salts of dextrin polycarboxylates.

10 Claims, No Drawings BUILT DETERGENT COMPOSITIONS CONTAINING DEXTRIN ESTERS OF POLY CARBOXYLIC ACIDS BACKGROUND OF THE INVENTION Sequestering builders, particularly polyphosphates, have been used for several decades as builder salts in detergent compositions. Phosphate builders serve multiple purposes, the better known ones of which relate to their capability for softening water, and, hence protecting the surfactants, particularly the calcium-sensitive surfactants from being, partially or wholly, inactivated by water hardness. Known sequestering builders also contribute in a manner which can be termed as synergistic, to cleaning performance when combined with organic surface-active agents. As an example, sodium tripolyphosphates are most widely used in granular detergent compositions, whereas potassium pyrophosphates are preferred for use in liquid detergent compositions. That latter choice is in order because tripolyphosphates hydrolyze in liquid medium thereby forming a certain amount of orthophosphate which tends to adversely effect cleaning performance.

It has been reported that the presence of phosphates in streams and lakes allegedly contributes to what is called excessive eutrophication. Or, in other words, the presence of said phosphates in water apparently facilitates the uptake by algae and other water plants of nutrients present in water, thereby initiating an accelerated growth of said water plants. This increased growth speed requires more oxygen thereby creating an oxygen deficiency in water which, in turn, results in more difficult conditions or even impossibility for fish to live in said waters. It, therefore, has become desirable to substitute said polyphosphate builders, wholly or partially, by effective detergent builder salts which do not have the shortcomings of polyphosphates, i.e., which are likely to be eliminated from water, through natural purification steps including degradability and biodegradability, under naturally occurring conditions.

U.S. Pat. No. 2,311,008, Tucker, discloses water-soluble salts of aliphatic polycarboxylic acids containing, per molecule, three or more carboxyl groups, as well as ether groupings. These salts can advantageously be used for water-softening; they can be prepared by etherifying polyhydroxy substances such as starch, glucose, gums and the like, or polyhydr'ic alcohols such as glycerol, sorbitol, mannitol, xylitol. US. Pat. No. 3,634,392, Lyness, discloses carboxymethylated derivatives of diand tri-saccharide compounds as detergent builders. It is known, however, that the prior art carbohydrate derivatives, although possessing detergency characteristics in combination with surface-active agents, are not well suitable for being used because of their deficient bioegradability characteristics.

It is a main object of this invention to provide detergent compositions which are substantially free of phosphorus-containing builder salts.

It is another object of this invention to provide detergent compositions, capable of effective cleaning performance, containing water-soluble builder salts which are readily biodegradable and, therefore, will not disturb ecological conditions.

It is still another object of this invention to provide detergent compositions containing surface-active agents and biodegradable water-soluble detergent 2 builder salts, namely, low molecular weight carbohydrates esters.

It is a further object of this invention to provide built detergent compositions whereby the builder component is degradable and biodegradable under naturally j occurring conditions, and, accordingly will not contribute to environmental nuisances.

By utilizing certain detergent builder ingredients, i I

made from low molecular weight carbohydrates and i polycarboxylic acids, in combination with organic sur-' 3 face-active agents, these above-described objectives 5 can be attained and built detergent compositions formulated which are substantially free of phosphoruscontaining builder salts. Said compositions, especially the detergent builder component, are biodegradable and thus can be degraded under naturally occurring conditions, i.e., they do not have, with respect to ecological conditions, the shortcomings of polyphosphates and the like detergent builder ingredients known in the art.

SUMMARY OF THE INVENTION I i H OY n wherein n is an integer from about 20 to about 120; Y is selected from the group consisting of hydrogen and polycarboxylic moieties; the degree of substitution 1 (DS) is in the range from about 0.2 to 3; whereby the j weight ratio of said organic surface active agents to said builders is in the range from about 20:1 to about 1: l5.

DETAILED DESCRIPTION OF THE INVENTION Detergent compositions of this invention comprise (l) a water-soluble salt of an organic surface-active agent; and (2) a detergent builder derived from a low molecular weight carbohydrate esterified with polycarboxylic acids. Each of these components is discussed in detail hereinafter.

Unless indicated to the contrary, the indications used hereinafter stand for percent by weight.

The instant detergent compositions comprise from about 5% to about 95%, preferably from about 20% to about of a water-soluble organic surface-active agent selected from the group consisting of anionic,

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 eight to about 24 carbon atoms and preferably from about l 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 rosin and those resin acids in tall oil. Napthenic acids are also suitable. Sodium and potassium soaps can be made by direct saponification of the fats and oils or by the neutralization of the free fatty acids which are prepared in a separate manufacturing process. Particularly useful are the sodium and potassium salts of the mixtures of fatty acids derived from coconut oil and tallow, i.e., sodium or potassium tallow and coconut soap.

This class of detergents also includes water-soluble salts, particularly the alkali metal salts of organic sulfuric reaction products having in their molecular structure an alkyl radical containing from about eight 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 nine to about carbon atoms, in straight chain or branched chain configuration, e.g., those of the type described in US. Pat. Nos. 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 alkyl phenol ethylene oxide ether sulfate with about one to about l0 units of ethylene oxide per molecule and in which the alkyl radicals contain about eight to about 12 carbon atoms.

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 oxyacid of phosphorus. The more common solubilizing groups, of course, are SO,H, SO H,

and CO,H. Alkyl phosphate esters such as (RO),.

- P0, and ROPO H, in which R represents an alkyl chain containing from about eight to about carbon atoms are useful.

4 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 in which R represents an alkyl group containing from about eight to 20 carbon atoms, or an alkylphenyl group in which the alkyl group contains from about eight 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 I to about 40.

Another class of suitable anionic organic detergents particularly useful in this invention includes salts of 2- acyloxy-alkane-lsulfonic acids. These salts have the formula where R is alkyl of about nine to about 23 carbon atoms (forming with the two carbon atoms an alkane group); R is alkyl of one to about eight 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 substituted-ammonium cation. Specific examples of substituted ammonium cations include methyl-, dimethyl-, and trimethylammonium cations and quaternary ammonium cations such as tetramethyl-ammonium and dimethyl piperdinium cations and those derived from alkylamines such as ethylamine, diethylamine, triethylamine, mixtures thereof, and the like.

Specific examples of beta-acyloxy-alkane-l-sulfon ates, or alternatively 2-acyloxy-alkane-l-sulfonates, utilizable herein to provide superior cleaning levels under substantially neutral washing conditions include the sodium salt of Z-acetoxy-tridecane-l-sulfonic acid; the potassium salt of 2-propionyloxy-tetradecanel -sulfonic acid; the lithium salt of 2-butanoyloxy-tetradecane-lsulfonic acid; the sodium salt of Z-pentanoyloxypentadecane-l-sulfonic acid; the sodium salt of 2- acetoxy-hexadecane-l-sulfonic acid; the potassium salt of 2-octanoyloxy-tetradecane-l-sulfonic acid; the sodium salt of 2-acetoxy-heptadecane-l-sulfonic acid; the lithium salt of Z-acetoxy-octadecane-l-sulfonic acid; the potassium salt of 2-acetoxy-nonadecane-lsulfonic acid; the sodium salt of 2-acetoxy-uncosane-lsulfonic acid; the sodium salt of 2-propionyloxy-docd sane-l-sulfonic acid; the isomers thereof.

Preferred beta-acyloxy-alkane-l-sulfonate salts therein are the alkali metal salts of beta-acetoxyalkanel -sulfonic acids corresponding to the above for mula wherein R, is an alkyl of about 12 to about 16 carbon atoms, these salts being preferred from the standpoints of their excellent cleaning properties and ready where R is a straight chain alkyl group having from six to 20 carbon atoms, R is a lower alkyl group having from one to three carbon atoms, and M is a salt-forming radical hereinbefore described.

Specific examples of beta-alkyloxy alkane sulfonates or alternatively 2-alkyloxy-alkane-l-sulfonates, utilizable herein to provide superior cleaning and whitening levels under household washing conditions include:

potassium beta-methoxydecanesulfonate,

sodium beta-methoxy-tridecanesulfonate,

potassium beta-ethoxytetradecylsulfonate,

sodium beta-isopropoxyhexadecylsulfonate,

lithium beta-tert-butoxytetradecylsulfonate,

sodium beta-methoxyoctadecylsulfonate, and

ammonium beta-n-propoxydodecylsulfonate.

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 US. Nos. 2,486,921; 2,486,922; and 2,396,278.

Additional examples of anionic, non-soap, synthetic detergents, which come within the terms of the present invention, are the compounds which contain two anionic functional groups. These are referred to as dianionic detergents. Suitable di-anionic detergents are the disulfonates, disulfates, or mixtures thereof which may be represented by the following formulae:

3)z z 4)z z 6 3) 0 2 where R is an acyclic aliphatic hydrocarbyl group having to carbon atoms and M is a water-solubilizing cation, for example, the C to C disodium 1,2-alkyldisulfates, C to C dipotassium-l,2-alkyldisulfonates or disulfates, disodium l,9-hexadecyl disulfates, C to C disodium-l,2-alkyldisulfonates, disodium 1,9- stearyldisulfates and 6,l0-octadecyldisulfates.

6 The aliphatic portion of the disulfates or disulfonates is generally substantially linear, desirable, among other reasons, because it imparts desirable biodegradable 1 properties to the detergent compound.

The water-solubilizing cations include the customary 1 cations known in the detergent art, ie., the alkali metals, and the alkaline earth metals, as well as other metals in group [1A, [1B, "A, [VA and NE of the Periodic Table except for Boron. The preferred water-solubiliz-.

ing cations are sodium or potassium. These dianionic detergents are more fully described in Brit. Pat. specification No. l,l5l,392.

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-octadecyl-sulfo-succinamate; diamyl ester of sodium sulfosuccinic acid; dioctyl ester of sodium sulfosuccinic acid.

Preferred anionic surface-active agents for use in the compositions of the instant invention include alkyl ether sulfates and olefin sulfonates." Said detergents are preferably used in an amount from about 20% to about The preferred alkyl ether sulfates have the formula wherein R is alkyl or alkenyl of about l0 to about ,20 carbon atoms, x is l to 30, and M is a salt-forming cat- Especially preferred are those alkyl ether sulfates wherein R has from about 14 to about 18 carbon atoms and wherein x has an average value of about 1 to about 6. Specific examples of especially preferred species are: sodium coconut alkyl ethylene glycol ether sulfate; sodium tallow alkyl trioxyethylene ether sulfate; sodium tallow alkyl pentaoxyethylene sulfate; ammonium tetradecyl pentaoxyethylene sulfate and ammonium lauryl hexaoxyethylene sulfate.

Especially preferred alkyl ether sulfate components have an average (arithmetic mean) carbon chain length within the range of from about 12 to 16 carbon atoms,

preferably from about 14 to 15 carbon atoms; and an average (arithmetic mean) degree of ethoxylation of from about 1 to 4 moles of ethylene oxide, preferably from about 2 to 3 moles of ethylene oxide.

Such mixtures comprise from about 0.05% to 5% by weight of mixture of C compounds, from about 55% to 70% by weight of mixture of C1445 compounds, from about 25% to 40% by weight of mixture of C compounds and from about 0.1% to 5% by weight of mixture of C1849 compounds. In addition, such preferred alkyl ether sulfate mixtures comprise from about 15% to 25% by weight of mixture of compounds having a degree of ethoxylation of 0, from about 50% to 65% by weight of mixture of compounds having a degree of 5 sawe. 1

gredients can be produced by sulfonation of a-olefrns by means of uncomplexed sulfurdioxide followed by July 25, 1967, enclosed herein by reference.

' Said a-olefin sulfonates can be represented either by individual species or by mixtures containing structurally difierent sulfonation products, Preferred mixtures are disclosed by Kessler, et al.; one such mixture consists essentially of from about 30% to about 70% by weight of a Component A, from about 20% to about 70% by weight of a Component B, and from about 2% to about 15% of a Component C, wherein a. said Component A is a mixture of double-bond positional isomers of water-soluble salts of alkene-lsulfonic acids containing from about 20 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 gamma-delta unsaturated isomer, and about 5% to about of a delta-epsilon unsaturated isomer;

b. said Component B is a mixture of water-soluble salts of bifunctionally-substituted sulfur-containing saturated aliphatic compounds containing from about 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 atoms, at least 90% of the hydroxy radical substitutions being in 3, 4, and 5 positions; and

c. said Component C is a mixture comprising from about 30-95% water-soluble salts of alkene disulfonates containing from about 20 to about 24 carbon atoms, and from about 5% to about 70% water-soluble salts of hydroxy disulfonates containing from about 20 to about 24 carbon atoms, said alkene disulfonates containing a sulfonic 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 TABLE I MlXTURE CHARACTERISTlC ALKYL ETHER SULFATE MIXTURE Average carbon chain 1 11 111 IV Length (No. C Atoms) 14.86 14.68 14.86 14.88 12-13 carbon atoms (wt. 4% 1% 1% 3% 14-15 carbon atoms (wt. 55% 65% 65% 57% 16-17 carbon atoms (wt. 35% 33% 33% 38% 18-19 carbon atoms (wt. 6% 1% 1% 2% Average degree of ethoxylation (No. Moles E0) 1.98 2.25 2.25 3.0 0 moles ethylene oxide (wt. 15% 21% 22.9% 18% 1-4 moles ethylene oxide (wt. 63% 59% 65% 55% 5-8 moles ethylene oxide (wt. 21% 17% 12% 22% 9+ moles ethylene oxide (wt. 1% 3% 0.1% 5% Salt K Na Na Na The preferred olefm sulfonates utilizable herein have from about 12 to about 24 carbon atoms. Said in- 20 from said terminal carbon atom, the alkene double bond being distributed between the terminal carbon atom and about the seventh carbon atoms, 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.

Especially preferred for use in the instant compositions are 3-, 4-, and S-hydroxy allcyl sulfonates and mixtures thereof. Specific examples of said hydroxy-sulfonates include sodium salts of sodium 3-hydroxy-n-decy1- 1 -sulfonate,

sodium 3-hydroxy-n-dodecyl- 1 -su1fonate,

sodium 3-hydroxy-n-tetradecy1- 1 -su1fonate,

sodium 3-hydroxy-n-hexadecy1-1-su1fonate,

sodium 3-hydroxy-n-octadecyll -sulfonate,

sodium 3-hydroxy-n-eicosy1- 1 -sulfonate,

sodium 3-hydroxy-n-docosyl- 1 -su1fonate,

sodium 3-hydroxy-n-tetracosyl- 1 -su1fonate,

sodium 4-hydroxy-n-decy1- l -su1fonate,

sodium 4-hydroxy-n-dodecy1- l -sulfonate,

sodium 4-hydroxy-n-tetradecy1- l -su1fonate,

sodium 4-hydroxy-n-hexadecyl- 1 -sulfonate,

sodium 4-hydroxy-n-o ctadecyl- 1 -su1fonate,

sodium 4-hydroxy-n-eicosy1- 1 -su1fonate,

sodium 4-hydroxy-n-docosyl- 1 -su1fonate,

sodium 4-hydroxy-n-tetracosyl-l-sulfonate,

sodium S-hydroxy-n-d ecyl- 1 -sulfonate,

sodium S-hydroxy-n-dodecyl- 1 -sulfonate,

sodium S-hydroxy-n-tetradecyl- 1 -sulfonate,

sodium 5-hydroxy-n-h exadecyl- 1 -su1fonate sodium 5-hydroxy-noctadecyll-sulfonate,

sodium S-hydroxy-n-eicosyl- 1 -su1fonate,

sodium S-hydroxy-n-docosyl-l-sulfonate, and

sodium S-hydroxy-n-tetracosyll -su1fonate.

Among these preferred species the 4-hydroxy substituent is preferred, e.g., for use in combination with 3- hydroxyand/or 5-hydroxy-compounds. This means that in a binary system of the 4-substituent in combination with the 3- and 5- substituents or either one of these alone, the 4-substituent is present in an amount of at least 50% of the mixture of 4 and 3 and/or S-substituents.

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 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 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 1,500 to 1,800. 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 six 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 to 25 moles of ethlylene 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 molecular weight of the order of 2,500 and 3,000, are satisfactory.

3. The condensation product of aliphatic alcohols having from eight 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 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-Z-hydroxyethyl) lauramide; nonyl 10 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-iso-octylphenol; condensed with 15 moles of ethylene oxide.

5. A detergent having the formula R,R R N O@ v (amine oxide detergent) wherein R is an alkyl group? containing from about 10 to about 28 carbon atoms, j from zero to about two hydroxy groups and from zero i to about five ether linkages, there being at least one diethyltetradecylamine oxide, dipropyldodecylamine oxide, bis-(2-hydroxyethyl)dodecylamine oxide, bis- (Z-hydroxyethyl )-3-dodecoxyl -hydroxypropylamine oxide, (2-hydroxypropyl)methyltetradecylamine oxide, dimethyloleylamine oxide, dimethyl-( 2-hydrox ydodecyl)amine oxide, and the corresponding decyl, hexadecyl and octadecyl homologs of the above compounds.

6. A detergent having the formula t l r P (sulfoxide detergent) wherein R, is an alkyl radical containing from about 10 to about 28 carbon atoms, from zero to about five ether linkages and from zero to about two hydroxyl substituents at least one moiety of 3 R being an alkyl radical containing zero ether linkages f and containing from about 10 to about 18 carbon. atoms, and wherein R is an alkyl radical containing from one to three carbon atoms and from one to two 1 hydroxyl groups: octadecyl methyl sulfoxide, dodecyl methyl sulfoxide, tetradecyl methyl sulfoxide, 3- hydroxytridecyl methyl sulfoxide, 3-methoxytridecyl i methyl sulfoxide, 3-hydroxy-4-dodecoxybutyl methyl sulfoxide, octadecyl 2-hydroxyethyl sulfoxide, dodecylethyl sulfoxide. Of all the above-described types of nonionic surfactants, preferred nonionic surfactants include the condensation product of nonyl phenol with about 9.5 moles of ethylene oxide per mole of nonyl phenol, thecondensation product of coconut fatty alcohol with about 6 moles of ethylene oxide per mole of coconut fatty alcohol, the condensation product of tallow fatty alcohol with about l 1 moles of ethylene oxide per mole of tallow fatty alcohol and the condensation product of: a secondary fatty alcohol containing about 15 carbon: atoms with about 9 moles of ethylene oxide per mole of fatty alcohol.

C. Ampholytic Synthetic Detergents Ampholytic synthetic detergents can be broadly described as derivatives of aliphatic or aliphatic deriva tives of heterocyclic secondary and tertiary amines, in which the aliphatic radical may be straight chain or branched and wherein one of the aliphatic substituents 1 contains from about eight to 18 carbon atoms and at least one contains an anionic water-solubilizing group, e.g., carboxy, sulfo, sulfato. Examples of compounds falling within this definition are sodium 3- (dodecylamino)-propionate, sodium 3- (dodecylamino)propanel -sulfonate, sodium 2- (dodecylamino)ethyl sulfate, sodium 2-(dime- 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 three to 18 carbon atoms, and at least one aliphatic substituent contains an anionic water-solubilizing group, e.g., carboxy, sulfo, sulfato, phosphato, or phosphono. Examples of compounds falling within this definition are 3- (N,N-dimethyl-N-hexadecyl-ammonio)-2-hydroxypropane- 1 -sulfonate, 3-( N ,N-dimethyl-N-hexadecylammonio )-prop ane- 1 -sulfonat'e, 2-(N,N-dimethy1-N- dodecylammonio)acetate, 3-(N,N-dimethyl N- dodecylammonio)propionate, 2-(N,N-dimethyl-N- octadecylammonio)-ethyl sulfate, Z-(trimethylammonio)ethyl dodecylphosphonate, ethyl 3-(N,N- dimethyl-N-dodecylammonio)-propylphosphonate, 3- (P,P-dimethyl-P-dodecylphosphonio)-propane- 1 -sulfonate, 2-(S-methyl-S-tert.hexadecyl-sulfonio)ethanel-sulfonate, 3-(S-methyl-S-dodecylsulfonio)propionate, sodium 2-(N,N-dimethyl-N-dodecylammonio)e- ,thylphosphonate, 4-(S-methyl-S-tetradecylsulfonio)butyrate, l 2-hydroxyethy1)-2-undecylimidazoliuml-acetate, 2-(trimethylammonio)octadecanoate, and

, 3-( N,N-bis-( 2-hydroxyethyl )-N-octadecylammonio)-2- hydroxypropane-l-sulfonate. Some of these detergents are described in the following U.S. Patents: U.S. Pat. Nos. 2,129,264; 2,178,353; 2,774,786; 2,813,898; and 2,828,332.

Of all the above-described types of zwitterionic surfactants, preferred compounds include 3(N,N-dimethyl-N-alkylammonio)-propane-l-sulfonate and 3(N,N- dirnethyl-N-alkylammonio )-2-hydroxypropanel -sulfonate wherein in both compounds the alkyl group averages 14.8 carbon atoms in length; 3(N,N-dimethyl-N- hexadecylammonio)-propane-l-sulfonate; 3(N,N- dimethyl-N-hexadecylammonio)-2-hydroxypropane-lsulfonate; 3-(N-dodecylbenzyl-N,N-dimethylamrnonio)-propane- 1 -su1fonate; (N-dodecylbenzyl-N,N-dimethylammonio)acetate; 3-(N-dodecylbenzyl-N,N-dimethylammonio)propionate; 6-(N-dodecy1benzyl-N,N-

dirnethylammonio)hexanoate; and (N,N-dimethyl-N- 3 hexadecylammonio)acetate.

Another essential ingredient for use in the instant compositions m a water-soluble biodegradable detergent builder salt. Said builder has the general formula:

cmov

H (Iro H 1 H \l c wherein n is an integer from about 20 to about Y is selected from the group consisting of hydrogen and polycarboxylic acids; the degree of substitution is in the range from about 0.2 to 3. The weight ratio of said builders to the organic surface-actives, as already referred to hereinbefore, is in the range from about 15:1 to about 1:20, preferably from 8:1 to 1:12. The builder is used in an amount from about 5% to about 95%, preferably from about 20% to about 70%.

The essential builder component is an ester of polysaccharides and polycarboxylic acids.

The polysaccharides suitable for use have a degree of polymerization of about 20 to about 120, preferably of about 20 to about 80, and is commonly known as dextrin. Dextrins are derived from more highly polymerized branched and linear polysaccharides such as starch and glycogen. These raw materials are hydrolyzed to dextrin thereby using any technique suitable for that purpose.

By way of example, dextrin can be produced from dryroasted starch by various degradation-recombinations. The species known as white dextrin is, for example, prepared by hydrolytic breakdown of starch in the presence of moisture and high acidity at a temperature of about C. Yellow dextrin is prepared from starch at temperatures from about 150 to 200C under conditions of moderate acidity and low moisture (as compared to the conditions for preparing white dextrins). Species prepared by molecular rearrangement and repolymerization are, also, well-known and may serve as raw material for the essential builder ingredient.

Starch and glycogen are the commonest food reserve materials of the plant animal kingdom, respectively. Starch is a mixture of two main polysaccharide components, namely, a linear species called amylose and a highly branched species called amylopectin. Glycogen is constituted of a single polysaccharide species with a similar, but more highly branched structure than amylopectin.

In general, starches contain, depending upon their origin, up to 30% of amylose and up to 98% of amylopectin.

Amylose contains linear chains of l 4' a-D- glycopyranose having a degree of polymerization of about 1,000 to about 6,000. Amylopectin has a molecular weight in the range from 10 to 10 million. It has a branched structure whereby the chains having 1 4 a- D-glycopyranose bonds are branched through 1 6 linkages. Glycogen is essentially similar to amylopectin except that the degree of branching is somewhat greater. For more details, see POLYSACCHARIDES, by Gerald O. Aspinall, Pergarnmon Press, New York, 1st Edition, 1970, incorporated herein by reference.

Polycarboxylic acids suitable for the dextrin esterification include aromatic and aliphatic polycarboxylic acids. Examples of preferred aromatic species include mellitic acid, benzene pentacarboxylic acid, benzene wherein R is selected from:

Cl-l COOH; CH CH COOH;

cloon (icon coon coon and R is selected from:

CH COOH; CH CH COOH;

cn -cn, coon coon coon coon coon: coon; c =c coon coon and CH CH whereby R and R form a closed ring structure in the event said radicals are selected from:

CIOOH (ITOOH COOH COOH Specific examples of polyethercarboxylic acids include oxydiacetic acid having the formula:

/ CH ,COOH

oxydisuccinic acid having the formula:

coon coon cn cn, cn cn,

coon coon carboxy methyl oxysuccinic acid having the formula:

coon coon cn-cn, cn,-coon furan tetracarboxylic acid having the formula:

and tetrahydrofuran tetracarboxylic acid having the formula:

coon poon C OOH COOH The degree of substitution (with respect to the hydroxyl functions of the dextrin) is in the range from ents of the instant compositions at normal usage concentration, for example, in laundry solutions containing from about 0.05% to about 1% of detergent compositions of the instant invention. The biodegradable builders for use in the instant compositions can be prepared using techniques known in the art. As an example, dextrin succinate was prepared as described hereinafter.

PREPARATION OF DEXTRIN SUCCINATE Dextrin (50.0 g., 0.3 mole) was placed in a 2-liter, three-necked flask along with 1 liter of pyridine. The flask was equipped with a magnetic stirrer, Dean-Stark trap, thermometer, and an argon inlet.

The above mixture was refluxed for 1 hour while -l00 ml. of distillate was collected (this removes excess moisture). The reactants were then cooled to 60-70C and succinic anhydride (120 g., 12 moles) was added all at once. The reaction mixture was then heated at C overnight.

Most of the pyridine was then stripped from the dextrin reaction mixture; thereafter the residue was cooled in an ice bath and acidified to pH 2-3 with hydrochloric acid. A sticky mass fon'ned which was hard to stir.

The supernatant was decanted and the residue was washed three times with water. The residue was dissolved in acetone and ether was added until a thick, molasses-like solid precipitated. The supernatant was decanted and the remaining solvent was removed on a flash evaporator. This was repeated until a crystalline product was obtained. The product was then vacuum dried to give 81 g. of dextrin succinate.

The protonated succinates can be converted to the TABLE II Average Degree of Polymerization Polycarboxylic Average Degree of of Dextrin (n) Acid Moiety Substitution (DS) 50 Succinic acid 2.0 30 Maleic acid 2.0

TABLE lI-continued Average Degree of Polymerization Average Degree of Polycarboxylic carboxylic acid The preferred builder ingredients listed above have a degree of esterification (DE) of about 1, i.e., one of the esterifiable carboxylic moieties per mole of polyacid reacts, on the average, with one hydroxyl group of the dextrin.

The free (non-esterified) carboxylic radicals can be neutralized partially or wholly whereby the choice of the neutralizing cation, to a certain extent, determines the water solubility. Suitable cations can be represented by sodium, potassium, lithium, amines and alka- .nolamines such as triethanolamine, diethanolamine and monoethanolamine.

1n the foregoing, the essential ingredients which are comprised in the detergent formulations of this invention are described in great detail. However, in the finished detergent formulations of this invention, there are usually added other optional detergent composition ingredients which make the product more effective and more attractive. So, for example, organic and inorganic peroxy bleach compounds can be incorporated in these compositions in an amount from about 5% to about 40%.

.'lhe peroxy bleach compound can be represented by all usual inorganic and organic ingredients which are known to be satisfactory for being incorporated for that purpose in detergent compositions. Examples of inorganic peroxy bleach compounds are the alkaline metal salts of perborates, percarbonates, persilicates, persulfates, and perphosphates. As is well known, the perborates can have different degrees of hydration. Although frequently the tetrahydrate form is used, it is for certain purposes desirable to incorporate the perborates having a lower degree of hydration water, for example, 1 mole, 2 moles, or 3 moles. Organic peroxy bleach agents may be used as well. The like ingredients can be incorporated as such, i.e., they have been prepared previously or they may be prepared in situ through the addition of, for example, any peroxy bleach agents suitable for being used in combination with an organic peroxy-bleach activator.

Specific examples of the organic peroxy-bleach compounds are the water-soluble salts of monoand diperoxy acids such as perazelaic acid, monoperoxyphthalic acid, diperoxy-terephthalic acid, 4- chlorodiperoxyphthalic acid. Preferred aromatic peracids include the water-soluble salts of diperisophthalic acid, m-chloroperbenzoic acid and p-nitroperbenzoic acid.

In the event the peroxy bleach compound is to be prepared in situ, then its precursors, i.e., the peroxy bleach agent and peroxygen activators are to be added separately to the detergent composition. The peroxygen bleach can be represented by all oxyen bleaching agents which are commonly used in detergent technology, i.e., organic and inorganic species, as mentioned hereinbefore. The activating agents can be represented by all the oxygen activators known as being suitable for use in detergent technology. Specific examples of the preferred activators include acylated glycoluriles, tetra-acetyl methylene diamine, tetra-acetyl ethylene diamine, triacetyl isocyanurate and benzoylimidazole. Acid anhydride activators which bear at least one double bond between carbon atoms in 01,01 to the carbonyl group of the anhydride radical can be used as well. Examples thereof are phthalic and maleic anhydrides. Especially preferred bleach activators are based on aldehydes, ketones, and bisulfite adducts of aldehydes and ketones. Examples of these esp; cially preferred activators include: 1,4-cyclohexanedione; cyclohexanone; 3-oxo-cyclohexylacetic acid; 4-tertbutylcyclohexaneone; 5-diethylmethylammonio-Z-pentanone nitrate; N- methyLmorpholinioacetophenone nitrate; acetone, methyl ethyl ketone; 3-pentanone; methyl-pyruvate; N-methyl-4-oxo-piperidine oxide; l,4-bis(N-methyl-4- oxopiperidiniomethyl) benzene chloride; N-methyltropinonium nitrate; thiapyranonium nitrate; N-benzyl; N-methyl-4-oxopiperidinium nitrate; N ,N-dimethyl-4-oxo-piperidinium nitrate; di-Z-pyridyl ketone; and chloral hydrate.

In the event the peracid is prepared in situ, then the molar ratio of peroxygen bleach agent to bleach activator shall preferably be in the range from about 5:1 to 1:2, especially from 2:1 to 1:12.

Other detergent composition ingredients used herein include suds regulating agents such as suds boosters and suds suppressing agents, tarnish inhibitors, soil suspending agents, buffering agents, enzymes, brighteners, flurorescers, perfumes, dyes and mixture. The suds boosters can, e.g., be represented by diethanolamides. Silicones, hydrogenated fatty acid, and hydrophobic alkylene oxide condensates can be used in the like compositions for suds suppressing purposes or, more generally, for suds regulating purposes. Benzotn'azole and ethylenethiourea can be used as tarnish inhibitors. Carboxymethyl cellulose is a well-known soil suspensing agent. The above additional ingredients, when used in the instant compositions, shall be employed in the usual ranges. Enzymes are frequently added because of their contribution to degrade soil thereby rendering said soil more soluble and more easily removable which, in turn, amounts to a cleaning perfonnance improvement. Because of their specific soil degrading action, mixtures of different enzyme species are frequently preferred. Especially preferred for use in the instant compositions is an enzyme selected from the group consisting of proteases, amylases, lipases and peroxidases mixtures thereof. Said enzymes are used in an amount from 0.001% to 3.00% of the detergent composition.

The detergent compositions of the instant invention can be of any physical state, i.e., liquid, pasty, powdered and granular. Highly preferred are solid, including powdered and granular, detergent compositions.

The following examples are illustrative but do not limit the novel compositions of the present invention.

l-methyl-4-oxo-tetrahydro- EXAMPLE I Detergent compositions having the following formula provided comparable cleaning performance when used in comparative cleaning tests.

Composition A Example I Sodium dextrin succinate (average degree of polyl merization (n) about 50) OS 2.2 6 parts Sodium tripolyphosphate 6 pans Sodium B-acetoxyhexadecyl sulfonate 4 parts Sodium linear C alkyl benzene sulfonate 4 parts DS degree of substitution Substantially identical results are obtained in the event the sodium dextrin succinate is replaced with an equivalent amount of the water-soluble salts of any of the dextrin polycarboxylates listed in Table II hereinbefore.

The detergent compositions of Example I, especially the polycarboxylated dextrin builders, are substantially biodegradable. In contrast thereto, detergent compositions containing polycarboxylated corn starch builders are substantially non-biodegradable upon testing under identical conditions.

EXAMPLE II An effective and readily biodegradable detergent composition has the following formula:

Sodium tallow alkyl trioxyethylene sulfate 35 parts Sodium dextrin (n averages 60) oxydisuccinate (DS L8) parts Sodium sulfate 28 parts Minor ingredients including moisture, brightener, dyes, 40

perfumes Balance to 100 parts LII EXAMPLE "I The following composition provides excellent cleaning and is biodegradable.

Sodium salt of sulfonated l-hexadecene 25 parts Sodium dextrin (n averages 40) succinate (DS 1.3) 20 parts Sodium sulfate 20 parts Sodium perborate 30 parts Substantially similar results are obtained in the event the sodium salt of sulfonated l-hexadecene is substituted by an equivalent amount of a surface-active mixture, said mixture consisting essentially of about 50% of a Component A, about 40% of a Component B, and about 10% of a Component C, wherein a. said Component A is a mixture of double-bond positional isomers of water-soluble salts of alkene-1- sulfonic acids containing from about 20 to about 24 carbon atoms, said mixture of positional isomers 5 including about 20% of an alpha-beta unsaturated f isomer, about 50% of a beta-gamma unsaturated j isomer, about 20% of gamma-delta unsaturated isomer, and about 10% of a delta-epsilon unsatu rated isomer; b. said Component B is a mixture of water-soluble positions; and

said Component C is a mixture comprising from about water-soluble salts of alkene disulfonates containing from about 20 to about 24 carbon atoms, and from about 30% water-soluble salts of hydroxy disulfonates containing from about 20 to j about 24 carbon atoms, said alkene disulfonates containing a sulfonic 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 5 the seventh carbon atoms, 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.

Substantially similar results are also obtained when the sodium salt of sulfonated l-hexadecene is replaced with an equivalent amount of a mixture of the sodium salts of 3-, 4-, and S-hydroxy alkyl sulfonates, whereby in a binary system of these, the 4-hydroxy is present in excess of 50% by reference to the sum of the 3-, or 5- hydroxy with the 4-hydroxy alkyl sulfonates.

EXAMPLE lV Another detergent composition of this invention which is readily biodegradable and provides excellent cleansing has the following formula:

Sodium salt of sulfonated 40 parts Substantially similar results are also obtained in the event the sodium perborate tetrahydrate is substituted 19 by an equivalent amount of perazelaic acid, monoperoxy-phthalic acid, diperoxy-terephthalic acid, 4 chlorodiperoxy-phthalic acid.

What is claimed is: l. A detergent composition, consisting essentially of a. from about to about 95% by weight of a watersoluble organic surface-active agent selected from the group consisting of anionic, nonionic, ampholytic and zwitterionic detergents and mixtures thereof; and b. from about 95% to about 5% by weight of a watersoluble builder consisting of dextrin esterified with a polycarboxylic acid selected from mellitic acid, benzene pentacarboxylic acid, benzene tetracarboxylic acid, benzene tn'carboxylic acid, oxydisuccinic acid, carboxymethyloxysuccinic acid, furan tetracarboxylic acid, and tetrahydrofuran tetracarboxylic acid, said builder being characterized by a degree of substitution from about 0.2 to 3 and a degree of esterification of l; the weight ratio of the surface-active agent to the builder being in the range from about :1 to about 1:15.

2. A detergent composition in accordance with claim 1 wherein the component (a) organic surface-active agent is used in an amount from about 20% to about 5 70% by weight.

; 3. A detergent composition in accordance with claim 2 wherein the component (b) builder salt is used in an amount from about 20% to about 70% by weight.

4. A detergent composition in accordance with claim 3 wherein the builder salt has a degree of substitution from about 0.8 to about 2.2.

S. A detergent composition in accordance with claim 1 4 which, in addition, contains from about 5% to about 40% by weight of a peroxy bleach compound.

6. A detergent composition in accordance with claim 5 wherein the peroxy bleach compound is a water-soluble salt selected from the group consisting of perazelaic acid, monoperoxy-phthalic acid, diperoxy-terephthalic acid, 4-chlorodiperoxyphthalic acid, diperisophthalic acid, m-chloroperbenzoic acid, p-nitroperbenzoic acid,

. and mixtures thereof.

7. A detergent composition in accordance with claim 6 wherein the peroxy bleach compound is prepared in i situ and whereby the precursors for said peroxy bleach compounds consist of an inorganic compound selected 1 from the alkaline metal salts of perborates, percarbonj ates, persilicates, persulfates, perphosphates, and mixtures thereof; and a peroxygen bleach activator selected from the group consisting of acylated glycoluriles, tetra-acetyl methylene diamine, tetra-acetyl ethylene diamine, triacetyl isocyanurate, benzoylimidazole, maleic anhydride, phthalic anhydride,

" 1,4-cyclohexanedione; cyclohexanone; 3-oxo cyclohexylacetic acid; 4-tertbutylcyclohexanone; 5-

; diethylmethylammonio-Z-pentanone nitrate; 4-methylmorpholinioacetophenone nitrate; acetone; methyl ethyl ketone; 3-pentanone; methyl pyruvate; N-methyl- 4-oxo-piperidone oxide; l,4-bis( N-methyl-4- f oxopiperidiniomethyl) benzene chloride; N-methyl- 20 tropinonium nitrate; l-methyl-4-oxotetrahydrothiapyranonium nitrate; N-benzyl; N-methyl-4- oxopiperidinium nitrate; N,N-dimethyl-4-oxopiperidinium nitate; di-2-pyridyl ketone; chloral hydrate and mixtures thereof; the molar ratio of peroxygen bleach agent to bleach activator being in the range of from about 5:1 to about 1:2.

8. A detergent composition in accordance with claim 3 wherein the weight ratio of the component (a) organic surfaceactive agent to component (b) detergent builder is in the range from 12:1 to 1:8.

9. A detergent composition in accordance with claim 8 wherein the organic surface-active agent is selected from the group consisting of i. olefin sulfonates having from about 12 to about 24 carbon atoms; and ii. alkylethersulfates having the general formula wherein R is alkyl or alkenyl of about 10 to about 20 carbon atoms, x is 1 to 30 and M is a salt-fonning cat- I011.

10. A detergent composition in accordance with claim 9 wherein the alkyl ether sulfate organic surfaceactive agent is selected from the group consisting of sodium coconut alkyl ethylene glycol ether sulfate; lithium tallow alkyl glycol ether sulfate; sodium tallow alkyl pentaoxyethylene sulfate; ammonium tetradecylpentaoxy ethylene sulfate; ammonium lauryl hexaoxyethylene sulfate; sodium tallow alkyl trioxyethylene sulfate; and alkyl ether sulfate mixture having an average carbon chain length of from about 14 to 15 carbon atoms and an average degree of ethoxylation between about 2 and 3 moles of ethylene oxide, said alkyl ether sulfate mixture comprising from about 0.05% to 5% by weight of said alkyl ether sulfate mixture of compounds containing 12 to 13 carbon atoms;

from about 55% to by weight of said alkyl ether sulfate mixture of compounds containing 14 to 15 carbon atoms;

from about 25% to 40% by weight of said alkyl ether sulfate mixture of compounds containing 16 or 17 carbon atoms;

from about 0.1% to 5% by weight of said alkyl ether sulfate mixture of compounds containing 18 or 19 carbon atoms;

from about 15% to 25% by weight of said alkyl ether sulfate mixture of compounds having a degree of ethoxylation of zero; from about 50% to 65% by weight of said alkyl ether sulfate mixture of compounds having a degree of ethoxylation of from 1 to 4;

from about 12% to 22% by weight of said alkyl ether sulfate mixture of compounds having a degree of ethoxylation of from 5 to 8; and

from about 0.5% to 10% by weight of said alkyl ether sulfate mixture of compounds having a degree of ethoxylation greater than 8; and mixtures thereof.

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Referenced by
Citing PatentFiling datePublication dateApplicantTitle
US4011392 *Sep 2, 1975Mar 8, 1977The Sherwin-Williams CompanyMixed starch esters and the use thereof
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Classifications
U.S. Classification510/375, 510/312, 510/533, 510/376, 536/103, 510/310, 510/357, 252/180, 510/471, 510/472, 510/313, 510/307
International ClassificationC11D3/00, C11D3/22
Cooperative ClassificationC11D3/226
European ClassificationC11D3/22E8