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Número de publicaciónUS3308067 A
Tipo de publicaciónConcesión
Fecha de publicación7 Mar 1967
Fecha de presentación1 Abr 1963
Fecha de prioridad1 Abr 1963
También publicado comoDE1467656A1, DE1467656B2
Número de publicaciónUS 3308067 A, US 3308067A, US-A-3308067, US3308067 A, US3308067A
InventoresFrancis Louvaine Diehl
Cesionario originalProcter & Gamble
Exportar citaBiBTeX, EndNote, RefMan
Enlaces externos: USPTO, Cesión de USPTO, Espacenet
Polyelectrolyte builders and detergent compositions
US 3308067 A
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Descripción  (El texto procesado por OCR puede contener errores)

F. L. DIEHL March 7, 1967 POLYELECTROLYTE BUILDERS AND DETERGENT COMPOSITIONS Filed April 1, 1963 BUILDER CONCENTRATION (grams/I00 ml. water) FIGURE I Francis L. Diehl INVENTOR.

W a. w m

A T TORNE' Y United States Patent senses! PGLYELECTROLYTE BUILDERS AND DETERGENT QOMPOSITIONS Francis L. Diehl, Cincinnati, Ohio, assirrnor to The Procter & Gamble Company, Cincinnati, Ohio, a corporation of Uhio Filed Apr. 1, 1963, Ser. No. 269,359

Claims. (Cl. 252-461) v This invention relates to cleansing and laundering compositions, and more particularly, cleansing and laundering compositions containing polyelectrolyte builder mate rials that serve to enhance the cleaning capacity of detergent compounds.

The property possessed by some materials of improving detergency levels of soaps and synthetic detergents and the use of such materials in detergent compositions is known. Such cleaning boosters are called builders. Builders permit the attainment of superior cleaning performance both as regards quality of finished work and lower cost, than is possible when so-called unbuilt compositions are used.

The behavior and mechanism by which builders perform their function is not fully understood although several explanations for their behavior are available. Nevertheless, an unequivocal criterion does not exist which would permit one to perdict accurately which class of compounds possess valuable builder properties and which compounds do not.

This may be explained in part by the complex nature of deterency and the countless factors which contribute to overall performance results. Builder compounds have been found to have some effect, for instance, in such areas as stabilization of solid soil suspension, emulsification of soil particles, the surface activity of aqueous detergent solutions, solubilization of water-insoluble materials, foaming or sud producing characteristics of the washing solution, peptization of soil agglomerates, neutralization of acid soil, and the inactivation of mineral constituents present in the washing solution. Thus, any theoretical discussion of the boosting capacity of a builder compound should give due consideration to all the significant individual actions involved in the detergent process and must apply equally to all usual conditions of soiling and washing.

Examples of known builder materials are water-soluble inorganic alkaline builder salts which can be used alone or in combination, including alkali metal carbonates, borates, phosphates, polyphosphates, bicarbonates and silicates.

Examples of known organic builder materials are alkali metal, ammonium or substituted ammonium aminopolycarboxylates, e.g., sodium and potassium ethylenediaminetetraacetate, sodium and potassium N(2-hydroxyethyl)- ethylenediaminetriacetate, sodium and potassium and triethanolammonium N (Z-hydroxyethyl)-nitrilodiacetate. Alkali metal salts of phytic acid, e.g., sodium phytate, are also suitable as organic builders.

The ever increasing interest in built detergent compositions has resulted in an expanding list of available builder compounds. Despite the expanding list, however, certain disadvantages and shortcomings are recognized in known builder compounds. Perhaps the most widely acknowledged limitation regards the series of condensed inorganic polyphosphate compounds such as alkali metal tripolyphosphates, and higher condensed phosphates. These compounds, which constitute the most widely commercially used builders when used in detergent compositions have a strong tendency to hydrolyze into less condensed phosphorus compounds which are relatively inferior builders and, which may, in fact, form undesirable 3,398,967 Patented Mar. 7, 1967 precipitates in aqueous washing solutions. Such lower forms include orthophosphate.

It is a primary object of this invention to provide anew and improved class of polyelectrolyte builder compounds; A further object is to provide a new class of highly effective polyelectrolyte'builder compounds comprising Watersoluble salts of polymeric aliphatic polycarboxylic acids, as described hereinafter. Another object is to provide built detergent compositions containing members of the newly discovered class of polyelectrolyte builder materials. These and other objects will become apparent from the following detailed description of the invention.

The attached drawing, FIGURE'I, is a graph showing cleaning grades obtained as a function of builder con centration of several representative polyelectrolyte builder compounds, as hereinafter more fully described.

It has now been discovered that water-soluble salts of polymeric aliphatic polycarboxylic acids having certain specific structural relationships as to the position of thecarboxylate groups and meeting certain requirements as to molecular weight and equivalent weight possess ex- .traordinary builder properties capable of enhancing the deterency levels of a broad spectrum of detergent surfactants.

The water-soluble salt can be alkali metal or ammonium or substituted ammonium salt. The alkali metal can be sodium or potassium. The salt can be used in a partially or fully neutralized form.

According to this invention, the essential structural features which are necessary in order for the water-soluble salts of polymeric aliphatic polycarboxylic acids to have builder properties are the following:

(1) A minimum molecular weight of about 350 calcnlated as the acid form.

(2) An equivalent weight of about 50 to about calcuated as the acid form.

(3) At least 45 mole percent of the monomeric species comprising the polymer aliphatic polycarboxylic acid species having at least two carboxyl radicals separated from each other by not more than two carbon atoms.

(4) And, the site of attachment to the polymer chain of any carboxyl-containing radical being separated by not more than three carbon atoms along the polymer chain from the site of attachment of thenext carboxyl-containing radical.

Specific groups of compounds satisfying the requirements set forth above and illustrating the novel builder compounds of this invention are listed below:

(a) Water-soluble salts of a homopolyrner of an aliphatic p'olycarboxylic acid having the following empirical formula: Y

I l Y 00011 n wherein X, Y, and Z are each selected from the group consisting of hydrogen, methyl, carboxyl and canboxymethyl; at least one of X, Y, and Z being selected from the group consisting of carboxyl and carboxymethyl, provided that X and Y can be carboxymethyl only when Z is selected from carboxyl and carboxymethyl; wherein only one of X, Y and Z can he methyl, and wherein n is a whole integer having a value within a range, the lower limit of which is three and the upper limit of which is determined primarily by the solubility characteristics of the salts in an aqueous system.

Examples of these compounds are water-soluble salts of the following aliphatic polycarboxylic acids: Poly (maleic acid), poly (itaconic acid), poly(m-esaconic acid), poly(fumaric acid), poly(aconitic acid), poly(methylenemalonic acid), poly(citraconic acid), etc.

(b) Water-soluble salts of a copolymer of at least two of the monomeric species having the empirical formula described above in (a). Examples include (itaconic/ aconitic acid) copolymer, (itaconic/maleic acid) copolymer, (mesaconic/fumaric acid) copolymer, (methylenemalonic/citraconic acid) copolymer, etc.

(c) Water-soluble salts of a copolymer of a member from a group of alkylenes and monocarboxylic acids with the aliphatic polycarboxylic compounds described in (a), said copolymers having the general formula:

wherein each R is selected from the group consisting of hydrogen, methyl, carboxyl, carboxymethyl and carboxyethyl; wherein only one R can be methyl; where m is at least 45 mole percent of the copolymer, wherein X, Y, Z are each selected from the group consisting of hydrogen, methyl, carboxyl and carboxymethyl, at least one of X, Y, and Z being selected from the group consisting of carboxyl and carboxymethyl, provided that X and Y can be carboxymethyl only when Z is selected from carboxyl and carboxymethyl; wherein only one of X, Y, and Z can be methyl; and wherein n is a whole integer within a range, the lower limit of Which is three and the upper limit of which is determined primarily by the solubility characteristics of the salts in an aqueous system.

In writing the formula above in subparagraph (c) there is no implication as to the order in which the components appear; such components may be regularly or randomly placed along the polymer chain. Moreover, the polymers described herein can be linear polymers or they may even be of a branched or cross-linked variety, provided that they are soluble to the extent described hereinafter as being necessary.

Examples of compounds which suitably can be copolymerized with the polycarboxylic acids mentioned in subparagraph (a) and which do not interfere with desirable solubility characteristics in aqueous systems are ethylene, propylene, acrylic acid, methacrylic acid, crotonic acid, 3-butenoic acid, 3-methyl-3-buytenoic acid. Specific examples of copolymeric compounds, wherein the ratios are mole ratios, are 1:1 copolymer of ethylene and itaconic acid with an equivalent weight of 79; a 1:1 copolymer of propylene and maleic acid with an equivalent weight of 79; a 1:3 copolymer of acrylic acid and itaconic acid with an equivalent Weight of 66; a 1:4 copolymer of 3-buten0ic acid and maleicacid with an equivalent weight of 61.1; a 1:9 copolymer of isocrotonic acid and citraconic acid with an equivalent weight of 66.2; a 1:1.9 copolymer of methacrylic acid and aconitic acid with an equivalent weight of 62.2; a 1.211 copolymer of a 4- pentenoic acid and itaconic acid, with an equivalent weight of 78.3. The equivalent weights, as mentioned previously, are calculated as the acid form. The term equivalent weight as used herein has the usual meaning ascribed to that term. It implies the equivalent of a substance in grams, which is calculated by dividing its formula weight by its valency. In the present case of the acids, the valency is the number of replaceable hydrogen atoms.

There are, other monomeric species which can be copolymerized in minor amounts with the aliphatic polycarboxylic compounds described in (a) above and result in a copolymer having an equivalent weight within the range specified as being required in order to be a suitable builder. However, certain organic substituents when they appear in such additional monomeric species substantially and materially interfere with the builder properties of the salts of the copolymer especially when they are interposed between carboxyl groups on a methylene carbon along the polymer chain. These interfering substituents are essentially non-carboxyl containing organic radicals which have a molecular weight in excess of about 16. Examples of such interfering radical substituents include methoxy, acetoxy, dimethyl, and phenyl as illustrated by the following monomers; vinyl methyl ether, vinyl acetate, isobutylene, acrylamide and styrene.

Within the scope of this invention, it is possible to em ploy monomer units containing such exemplified interfering groups only if they are present in the copolymer in an amount limited to a maximum of about 27.5 moie percent of the total monomer units. Thus, the following copolymers are outside the limits of suitable compositions according to this invention: 1:1 copolymer of vinyl methyl ether and maleic acid, 1:1 copolymer of vinyl acetate and itaconic acid, 1:1 copolymer of isobutylenc and maleic acid, 1:1 copolymer of acrylamide and aconitic acid, and 1:1 copolymer of styrene and maleic acid.

The structural features of the operable and preferred polymers and copolymers have, as a matter of convenience, been defined herein in terms of the carboxylic-acid containing monomers from which such polymers and co polymers theoretically can be derived. It is recognized, however, that in many cases it is desirable or even preferable to form such polymers and copolymers in practice by employing derivatives or precursors of such carboxylicacid-containing monomers in the polymerizations leading to the desired polymers and copolymers. Thus, the monomeric species employed, can in many cases, be such derivatives or precursors of the designated acids as the anhydrides, the full or partial esters of such acids, amides, nitriles, etc., or mixtures of same, which after polymerization can be converted to the carboxylate salts by appropriate chemical reactions. For example, when maleic anhydride was polymerized using 5% benzoyl peroxide as initiator following the procedure described by Lang, Paveli-ch and Clarey in I. Polymer Sci., issue 162, p. S32 (1961) and subsequently converted to sodium polymaleate by treatment with aqueous sodium hydroxide, a highly preferred builder polymer was obtained. Use of potassium hydroxide in place of sodium hydroxide also yields a highly preferred builder which is particularly desirable for use in liquid formulations because of its excellent solubility.

Likewise, copolymers of ethylene and maleic anhydride, methyl acrylate and ethyl fumarate, ethyl aconitate and ethyl itaconate, acrylonitrile and butyl maleate, etc., and homopolymers of ethyl fumarate, itaconic anhydride, etc., will upon conversion to the carboxylate salts yield suitable builder materials provided that such materials are also within the limits defined hereinbefore and hereinafter.

Excellent cleaning results are obtained with salts of the homopolymers of the aliphatic polycarboxylic acids described in subparagraph (a) above. Specific examples of monomeric aliphatic polycarboxylic acids in this group include maleic acid, fumaric acid, itaconic acid and aconitic acid, and these constitute the preferred type builder compounds of this invention.

On inspection, it will be noted that the preferred builder compounds of this invention either have carboxyl groups attached to vicinal carbon atoms along the polymer chain such as in fumaric and maleic acids, or they have a carboxyl group and a carboxyl containing group attached geminally to a carbon atom of the polymer chain. An example of this latter configuration is itaconic acid. Aconitic acid, as illustrated hereinafter, has a carboxymethyl radical and a carboxyl radical attached to the same carbon atom as well as vicinally located carboxyl groups.

Also, according to this invention, two carboxyl groups can be geminally attached to a carbon along the polymer chain, for example, polytmethylenemalonic) acid. Such polymeric compounds may tend to decarboxylate under certain conditions of use. For this reason, the fact that such compounds may, on occasion, involve special processing and formulating considerations, this type of geminally carboxylated builder is less preferred. Maleic acid is a stereoisomer of fumaric acid having the formula CH(COOH)=CH(COOH). The relationship of these two acids is best shown by the following formulas:

H-C-COOI-I H%COOH HOOC -H HOCOOH Fumaria Acid Maleic Acid Aconitic acid, C H O also called 1,2,3-propenetricarboxylic acid is a tribasic acid obtained from Aconitum equisetum, Adones and Achellea species, or can be made from citric acid. It also occurs in beets and sugar cane and has the following structural formula:

( JOOH K JOOH Polymerized form of aconitic acid is: 1?; (g 0 OH I I C 0 o H H-CH O OH n The degree of polymerization, n, of the novel polyelectrolyte builder compounds of this invention has a significant and practical bearing on the builder effectiveness of these compounds. The lower limit for n has been established as three resulting in compounds having a molecular weight on the order of not less than about 350. Builder properties of the compounds of this invention drop off substantially as the molecular weight goes below 350.

It is somewhat more difficult to establish an absolute value for an upper limit of the degree of polymerization above which the polyelectrolyte builder compounds no longer function as efficient builders. The fact is that practical considerations appear to be the primary determining factor as the degree of polymerization increases. For instance, as the molecular weight of a polymeric material increases, it is generally acknowledged that the water solubility thereof decreases. It is essential to the present invention that the polyelectrolyte builder compounds must be adequately soluble in water under regular usage conditions. Recommended builder concentrations generally range from about .01% to about .50% by weight of the washing solution. The upper operable limit, therefore, so far as the scope of this invention is concerned, is reached when it is no longer possible to get enough of the builder compound into solution to act as a builder.

The higher builder concentrations on the order of 50% by weight may be found necessary under certain washing conditions such as a water hardness of 21 grains equivalent CaCO per gallon or higher. In such situations, any of the polyelectrolyte builder compounds of this invention could be selected whose solubility characteristics would allow a builder concentration in an aqueous solution to the necessary amount. In more general household situations builder concentrations of 03% to about .06% are found to be adequate.

It can be appreciated according to the preceding discussion that the degree of polymerization of these compounds can vary within a very wide range. Generally, however, the degree of polymerization, n, can be within the range of 3 to about 5,000. This corresponds to a molecular weight range for the compounds of this invention from 350 to about 1,500,000. A preferred range for the degree of polymerization, n, is from about 4 to about 500. This represents a preferred molecular weight range for the polyelectrolyte builder compounds of this invention of about 500 to about 175,000.

It is extremely difiicult to accurately determine molecular weights of polymeric compounds. Such figures will generally vary depending upon the method used to determine them. It is widely recognized, for instance, that any molecular weights of polymeric materials which are given by manufacturers constitute an average of the molecular weights of the molecules present. Moreover, molecular weight ranges are usually given which vary widely depending again upon the method used to measure the molecular weights. Among the several methods fre quently used to measure molecular weights of polymeric compounds are osmometric, end-group, cryoscopic, ebullioscopic, light-scattering and ultracentrifuge. Each of these methods are presently in varying degrees of development and each one has special types of polymeric compounds to which it is best adapted.

The minimum molecular weight of 350 mentioned above was arrived at empirically and, to a great extent, is based on the knowledge and experience acquired from working with these polyelectrolytic polycarboxylic polymers.

Viscosity is a property more frequently used by polymer chemists as characterizing polymeric compounds than are molecular weights. This is no doubt due to the comparatively easier and less complicated methods for obtaining viscosity data. To make such data meaningful, it is necessary to also give the test conditions under which the measurements were run. Since there is a recognized correlation between the viscosity of polymeric compounds and their relative molecular weights and since such figures can be more meaningful and can frequently be more available than molecular weights, the polymeric builder compounds used in the examples of this invention are characterized in terms of specific viscosity. In all cases the viscosity characterization corresponds to a molecular weight substantially above 350.

According to this invention extraordinary cleaning results can be obtained by using the above po-lyelectrolyte builder compounds with a wide range of active detergent surface active materials and mixtures thereof. The builder compounds are effective when used singly or mixtures thereof can be used.

In general, in the detergent compositions of this invention, the essential ingredients are (a) an organic water soluble detergent surface active material as defined and illustrated below and (b) a novel polyelectrolyte builder compound meeting the structural requirements specified and exemplified above. The detergent'compositions of this invention, therefore, contain the essential ingredients in a ratio of polyelectrolyte builder to detergent surfactant in the range of about 1:3 to about 10:1 by weight, with such compositions providing in aqueous solution a pH of about 9 to about 12. The preferred ratio of polyelectrolyte builder to detergent surfactant is about 1:2 to about 5:1 and the optimum pH range is 9.5 to about 11.5.

The detergent surface active compounds which can be used within the compositions of this invention include anionic, nonionic, zwitterionic, ampholytic detergent compounds and mixtures thereof. These suitable substances are outlined at length below.

(a) Anionic detergent compositions which can be used in the compositions of this invention include both soap and non-soap detergent compounds. Examples of suitable soaps are the sodium, potassium, ammonium and alkylolammonium salts of higher fatty acids (C -C Particularly useful are the sodium or potassium salts of the mixtures of fatty acids derived from coconut oil and tal low, i.e., sodium or potassium tallow and coconut soap. Examples anionic organic non-soap detergent compounds are the water soluble salts, alkali metal salts, of organic sulfuric reaction products having in their molecular structure an alkyl radical containing from about 8 to about 22 carbon atoms and a radical selected from the group consisting of sulfonic acid and sulfuric acid ester radicals. (Included in the term alkyl is the alkyl portion of higher acyl radicals.) Important examples of the synthetic detergents which form a part of the 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 coco-nut oil; sodium or potassium alkyl benzenesulfonates, such as are described in United States Letters Patents No. 2,220,009 and No. 2,477} 83 in which the alkyl group contains from about 9 to about carbon atoms; other examples of alkali metal alkylbenzene sulfonates are those in which the alkyl radical is a straight chain aliphatic radical containing from about 10 to about carbon atoms for instance, Z-phenyl-dodecanesulfcnate and 3-phenyl-dodcanesulfonate; sodium alkyl glyceryl ether sulfonates, especially those ethers of the higher alcohols derived from tallo-w 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 1 to 6 moles of ethylene oxide; sodium or potassium salts of alkylphenol ethylene oxide ether sulfate with about 1 to about 10 units of ethylene oxide per molecule end in which the alkyl radicals contain about 9 to about 12 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 tauride 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 Patents Nos. 2,486,921, 2,486,922 and 2,396,278.

(b) Nonionic synthetic detergents may be broadly defined as compounds alphatic or aikylaromatic in nature which do not ionize in water solution. 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 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 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 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 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, 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 ethylenediamine. For example, compounds containing from about 40% to about 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 hydrophobic base having a molecular weight of the order of 2,500 to 3,000, are satisfactory.

(3) 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 alsohol, the coconut alcohol fraction having from 10 to 14 carbon atoms.

(4) Long chain tertiary amine oxides corresponding to the following general formula, R R R N+O, wherein R is an alkyl radical of from about 8 to 18 carbon atoms, and R and R are each methyl or ethyl radicals. The arrow in the formula is a conventional representation of a semipolar bond. Examples of amine oxides suitable for use in this invention include dimethyldo-decylamine oxide, dimethyloctylamine oxide, dimethyldecylamine oxide, dimethyltetradecylamine oxide, dimethylhexadecylamine oxide.

(5) Long chain tertiary phosphine oxides corresponding to the following formula RRR"P O, wherein R is an alkyl, alkenyl or monohydroxyalkyl radical ranging from 10 to 18 carbon atoms in chain length and R and R" are each alkyl or monohydroxyalkyl groups containing from 1 to 3 carbon atoms. The arrow in the formula is a conventional representation of a semi-polar bond. Examples of suitable phosphine oxides are:

dimethyldodecylphosphine oxide, dimethyltetradecylphosphine oxide, ethylmethyltetradecylphosphine oxide, cetyldimethylphosphine oxide, dimethylstearylphosphine oxide, cetylethylpropylphosphine oxide, diethyldodecylphosphine oxide, diethyltetradecylphosphine oxide,

bis hydroxymethyl) dodecylphosphine oxide, bis(2-hydroxyethyl) dodecylphosphine oxide, 2-hydroxy propylmethyltetradecylphosphine oxide, dimethyloleylphosphine oxide, and dimethyl-Z-hydroxydodecylphosphine oxide.

(6) Dialkyl sulfoxides corresponding to the following formula, RRS O, wherein R is an alkyl, alkenyl, betaor gamma-monohydroxyalkyl radical or an alkyl or betaor gamma-monohydroxyalkyl radical containing one or two other oxygen atoms in the chain, the R groups ranging from 10 to 18 carbon atoms in chain length, and wherein R is methyl or ethyl. Examples of suitable sulfoxide compounds are:

dodecyl methyl sulfoxide tetradecyl methyl sulfoxide 3-hydroxytridecyl methyl sulfoxide 2-hydroxydodecyl methyl sulfoxide 3-hydroxy-4-decoxybutyl methyl sulfoxide 3-hydroxy-4-dodecoxybutyl methyl sulfoxidev 2-hydroxy-3-decoxypropyl methyl sulfoxide 2-hydroxy-3-dodecoxypropyl methyl sulfoxide dodecyl ethyl sulfoxide 2-hydroxydodecyl' ethyl sulfoxide The 3-hydroxy-4-decoxybutyl methyl sulfoxide has been found to be an especially effective detergent surfactant. An outstanding detergent composition contains this sulfoxide compound in combination with the polymaleate builder compound of this invention.

Ampholytic synthetic detergents can be broadly described as derivatives of aliphatic 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 one contains an anionic water solubilizing group. Examples of compounds falling within this definition are sodium-3-dodecylaminopropionate and sodium-3dodecylaminopropanesulfonate.

(d) Zwitterionic synthetic detergents can be broadly described as derivatives of aliphatic quarternary ammonium compounds 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 one contains an anionic water solubilizing group. Examples of compounds falling Within this definition are 3-(N,N-dimethyl-Nhexadecylammonio)propane-l-sulfonate and 3-(N,N-dimethyl-N-hexadecylammouio)-2-hydroxypropane-l-sulfonate which are especially preferred for their excellent cool water detergency characteristics.

The anionic, nonionic, ampholytic and zwitterionic detergent surfactants mentioned above can be used singly or in combination in the practice of the present invention. The above examples are merely specific illustrations of the numerous detergents which can find application within the scope of this invention.

The foregoing organic detergent surfactant compounds can be formulated into any of the several commercially desirable composition forms for example, granular, flake, liquid and tablet forms.

A granular detergent composition can contain a polyelectrolyte builder of this invention and a detergent surfactant in the weight ratio of about 1:3 to about 10:1. The preferred ratio of builder to surfactant is about 1:2 to about :1. Another embodiment of this invention is a built liquid detergent composition containing a polyelectrolyte builder described above and a detergent surfactant in a weight ratio of builder to detergent of about 1:3 to about :1. The prefer-red ratio for built liquid compositions of polyelectrolyte builder to detergent is about 1:2 to about 3: 1.

The detergent compositions described by this invention employing a polyelectrolyte builder compound as defined above can have special applicability in the area of built liquid detergents. This area presents special problems to the formulator in view of the peculiarities inherent in aqueous systems and the special requirements of solubility of the ingredients and, more especially their stability in such mediums. It is well known, for instance, that sodium tripolyphosphate, while outstanding in its behavior in granular compositions, is generally regarded as being unsuited for built liquid detergents. It has a strong propensity to hydrolyze into lower forms of phosphates. Thus, as a practical consideration there has been a necessity of resorting to alkali metal pyrophosphates, such as K P O in order to prepare a built liquid detergent. This has been true notwithstanding the known inferiority of pyrophosphates to sodium tripolyphosphate in some compositions, for example, as a builder for heavy duty detergency.

In view of the increasing acceptance by the general public of built liquid detergents for virtually all Washing and cleaning situations including laundering and dishwashing, it is a very significant contribution of this inventlon that an improved liquid detergent product is made possible that will provide detergent levels comparable to and in some aspects superior to a sodium tripolyphosphate built liquid product without the troublesome stability problem presented by sodium tripolyphosphate.

Most of the built liquid detergents commercially avail able at the present time are either water based or have a mixture of water and alcohol as the liquid vehicle. Such vehicles can be employed in formulating built liquid detergent compositions according to this invention without fear of encountering stability problems. Accordingly, a sample built detergent composition of this invention can consist essentially of a polyelectrolyte builder as defined herein and an organic detergent surfactant in the ratios described above and the balance being a vehicle medium, for example, water, a water-alcohol mixture, liquid nonionic surfactant compounds, etc.

In a finished detergent formulation of this invention there will often be added in minor amounts materials which make the product more effective or more attractive. The following are mentioned by way of example. Soluble sodium carboxymethylcellulose can be added in minor amounts to inhibit soil redeposition. A tarnish inhibitor such as benzotriazole or ethylenethiourea can also be added in amounts up to about 2%. Fluorescers, perfume and color, while not essential in the compositions of the invention, can be added in amounts up to about 1%. An alkaline material or alkali such as sodium hydroxide or potassium hydroxide can be added in minor amounts as supplementary pH adjusters. There might also be mentioned as suitable additives, water, brightening agents, bleaching agents, sodium sulfate, and sodium carbonate.

Corrosion inhibitors generally are also added. Soluble silicates are highly effective inhibitors and can be added to certain formulas of this invention at levels of from about 3% to about 8%. Alkali metal, preferably potassium or sodium, silicates having a weight ratio of SiO :M O of from 1:1 to 28:1 can be used. M in this ratio refers to sodium or potassium. A sodium silicate having a ratio of SiO :Na O of about 1.6:1 to 2.45:1 is especially preferred for economy and effectiveness.

In the embodiment of this invention which provides a built liquid detergent a hydrotropic agent may at times be found desirable. Suitable hydrotropes are water soluble alkali metal salts of toluenesulfonate, benzenesulfonate, and xylenesulfonate. The preferred hydrotropes are the potassium or sodium toluenesulfonates. The hydrotrope salt may be added if so desired, at levels of 0% to about 12%. While a hydrotrope will not ordinarily be found necessary, it can be added if so desired.

The specific action of the builders of this invention will vary to some extent, of course, depending upon the ratio of active detergent to builder mixture in any given detergent composition. There will be considerable variation in the strengths of the washing solutions employed by different users, i.e., some users may tend to use less or more of the detergent compositions than will others. Moreover, there will be variations in temperature and in soil loads as between different washing operations. Further the degree of hardness of the water used to make up the washing solutions will also bring about apparent differences in the cleaning power and whiteness maintenance results. Finally, different fabrics will respond in somewhat dilferen-t ways to different detergent compositions. The best type of detergent composition is one which accomplishes an excellent cleaning and whiteness maintenance effect under the most diverse cleaning conditions. The built detergent compositions of this invention are valuable in this respect.

The following examples serve to illustrate, but not limit, the novel compositions of the present invention. Each example provides in solution a pH within the range specified above as being necessary for builder action, that is, about 9 to about 12. All percentages in the examples are by weight.

EXAMPLE I An excellent granular detergent composition giving outstanding cleaning results in washing situations has the following composition in the percentages indicated.

Percent Sodium dodecylbenzenesulfonate (dodecyl) group derived from tetrapropylene) 17.5 Potassium toluene sulfonate 2.0

Sodium poly(itaconate-acrylate) (4:1 on a molar basis) (specific viscosity of 1% by weight, in dimethyl formamide at room temperature .40;

equivalent weight 65.8) s 47.0 Sodium silicate (ratio of SiO INa O of 2: 1) 6.0 Sodium sulfate s 13.8 Coconut fatty acid ethanolamide 2.7 Water Balanc The sodium poly(i-taconate-acrylate) builder in Example I can be replaced at an equal percentage basis by sodium salts of: a 1:1 copolymer of ethylene and itaiconic acid with an equivalent weight of 79; a 1:1 copolymer of propylene and maleic acid with an equivalent weight of 79; a 1:4 copolymer of 3-butenoic acid and maleic acid with an equivalent weight of 61.1; a 1:9 copolymer of isocrotonic acid and citraconic acid with an equivalent weight of 66.2; a 121.9 copolymer of methacrylic acid and aconitic acid with an equivalent weight of 62.2; a 1.211 copolymer of 4-pentenoio acid and itaconic acid, with an equivalent weight of 78.3, said equivalent weights calculated as the acid form, said salts having comparable viscosities to the builder of Example I.

EXAMPLE II Another excellent granular detergent composition has the following ingredients.

Percent Sodium dodecyl benzenesulfonate (dodecyl group being a straight chain aliphatic radical) 9.5 Hydrogenated marine oil fatty acid 2.2

Sodium polyitaconate (specific viscosity of 1% byv weight in dimethylforrnamide at room temperature .13; equivalent weight 65) 59.6 Sodium silicate (ratio of SiO :Na O of 2:1) 9.7 Sodium sulfate 13.5 Water Balance EXAMPLE 111 Excellent cleaning results are obtained using a granular detergent composition prepared according to this invention and having the following ingredients.

Percent Sodium dodecylbenzenesulfonate (dodecyl group derived from tetrapropylene) 20.0 Potassium toluene sulfonate 2.0

Trichlorocarbanilide .7 Sodium poly(itaconate-aconitate) (1:1 on molar basis) (specific viscosity of 1% by weight in dimethylformamide at room temperature .12;

equivalent weight 60.8) 33.0 Sodium silicate (ratio of SiO :Na O of 2: 1) 6.0 Sodium sulfate 32.3

Water 6.0

Sodium poly(it-aconate-rn'aleate), sodium poly(mesaconate-fumerate) and sodium poly(methylenemalonatecitraconate) copolymers can each be used as a builder in the above formula in place of the sodium poly(itaconateaconitate) copolymer of Example 111. These sodium salts have equivalent weights and viscosities comparable to the copolymer of Example 111.

EXAMPLE IV An especially effective and eificient granular detergent composition according to this invention has the following composition.

Percent 3 (N,N dimethyl N dodecylammonio) 2 hydroxyprop-ane-l-sulfonate 25.0

Sodium poly (ethylene-maleate) (1 :1 on molar basis) (specific viscosity of 1% by weight in dimethyl formamide at room temperature 1:58; equivalent weight 72) 25.0 Sodium sulfate 30.0 Sodium silicate (ratio of SiO :Na O of 1.5:1) 20.0

EXAMPLE V An excellent built liquid detergent composition according to this invention has the following composition.

Percent Sodium dodecylbenzenesulfonate (the dodecyl radical being a polypropylene, predominantly tetrapropylene averaging 12 carbon atoms) 6.0 Dimethyldodecylamine oxide 6.0 Monoethanolammonium polymaleate (specific viscosity of 1% by weight in dimethylformamide at room temperature .21; equivalent weight 58) 20.0 Potassium toluenesulfonate 8.0 Sodium silicate (SiO :Na O of 2.45: 1) 3.8 Carboxymethyl hydroxyethyl cellulose 0.3 Water Balance This composition performs equally well in laundry usage as well as dishwashing usage. The 'builders resistance to hydrolysis allows longer shelf life, a feature not found with sodium tripolyphosphate built liquid compositions.

EXAMPLE VI Superior cleaning and whiteness maintenance results are obtainable with a built liquid heavy duty granular detergent composition having the following ingredients.

Percent 3(N,N dimethyl N coconutammonio) 2 hy- This composition is effective at cool water temperatures on the order of about 40 F. to about F.

EXAMPLE VII Another effective cool water heavy duty built granular composition consists of the following ingredients.

Percent 3 (N,N dimethyl N hex'adecylammonio) propane-l-sulfonate 17.0 Sodium polyitaconate (specific viscosity of 1% by weight in dimethylformamide at room temperature .29; equivalent weight 65) 45.0 Sodium silicate (SiO :Na O=2.5:1) 6.0 Sodium carboxymethylcellulose .5 Sodium sulfate 28.0 Water 3.5

The sodium polyitaconate builder of Example VII can be replaced by water-soluble salts of: poly(maleic acid), poly(mesaconic acid), poly(furnaric acid), poly(methylenemalonic acid) or poly(citraconic acid) with equally good results, said salts having equivalent weights and viscosities comparable to the builder of Example VII.

.'..white dress shirts in the following manner. ing detachable collars and cuffs were worn by male sub- 13 EXAMPLE VIII An excellent built liquid composition of this invention has the following ingredients.

Percent Condensation product of dodecylphenol and ethyleneoxide, 11 moles of ethylene oxide per mole of dodecyl phenol Potassium poly(itaconate-acrylamide) :1) (specific viscosity of 1% by weight in dimethylformamide at room temperature .92; equivalent weight 72.1) 30.0

Sodium silicate (SiO :Na O=2.5:1) 8.0 Potassium toluene sulfo-nate 9.0 Sodium sulfate 5.0 Water 36.0

EXAMPLE IX tive, the dodecyl group being derived from tetrapropylene. This active will be referred to as ABS which is widely used in commercially available detergent compositions. The results of these tests, presented in FIGURE 1, conclusively show the outstanding performance advantages of the detergency compositions prepared according I to this invention.

The wash-wear tests involved washing naturally soiled Shirts carryjects under ordinary conditions for two normal working days. Following wearing, the collars and cuffs were washed for minutes in a small agitator-type machine using solutions of the detergent compositions to be evaluated. The washing conditions were as hereinafter specified. After a washing and drying cycle the collars and cuffs washed by a composition being evaluated were visu- 14 terminations and this type of grading scheme was to establish the relative builder performance of several compounds of this invention as compared to a known accepted standard in the detergent industry, i.e., sodium tripolyphosphate.

The washing solutions used in these white shirt detergency tests contained .03% by weight active detergent compound, in each instance ABS, and a representative polyelectrolyte builder at concentration levels ranging fro-m .03% to .06% by weight. No fluorescers, bleaches or anti-redeposition agents were used so as not to mask the builder properties. The washing solution was standardized to a pH of 10 and the water used contained 7 grams per gallon hardness. Temperature of washing solution was 140 F.

The respective grades obtained in the manner described above were charted on a graph and are presented in FIG- URE 1. It is readily apparent by observing the figure that the cleaning results produced by the polyelectrolyte built ABS-compositions of this invention are surprisingly and markedly superior to sodium tripolyphosphate (STP) built ABS-compositions at equal builder concentrations. Thus, in tests run at .03% builder concentration, only one builder compound of this invention performed relatively on a par with STP at 03%; all other builder samples tested at that concentration showed up very substantially better. The same relative superior results were obtained with tests run a .045 and .06% builder concentration. The cleaning grades obtained with such polyelectrolyte builder compounds as sodium polymaleate, sodium polyitaconate, sodium (itaconate-acrylate) copolymer, and sodium (itaconate-aconitate) copolymer were substantially better relatively, than the cleaning grades of sodium tripolyphosphate.

The polyelectrolyte polymeric builder compounds of this invention which were tested in the manner described above and for which performance data is presented in FIGURE 1 had the following properties and characteristics. The specific viscosity figures given below were obtained by using a conventional Cannon-Fenske flow-type viscometer under the specific conditions mentioned in the footnotes of Table I.

TABLE I Specific Viscosity Refer- Equivalent ences to Mole Weight Fig. 1 Ratio (as acid) 1% in 06% in dimethyl water formamide Sodium polymaleate. 58 13 05 Sodium polyitaconate 29 07 Do- 65 32 .08 Do. 65 16 Do V 65 1.01 .40 Sod um (itaconate-aconitate) copolymer VI 1:1 60.8 12 04 Sodium (itaconate-aci-ylate) copolymer VII 1. 6:1 66.6 .37 .13 Sodium (ethylene-maleate) copolymer VIII 1:1 72 1. 58 .81 Sodium (ethylene-maleate) copolymer (crossn ed) IX 1:1 72 1. 6-7.6 .48. 69

Sodium (vinylmethylethe maleate) copolymer. X 1:1 87 .88 .35 Sodium (isobutylene-maleate) copolymer XI 1:1 86 .72 .30

1 1% by weight as acid in dimethylforrnamide at room temperature. 2 .06% by weight as sodium salt in water at room temperature.

ally compared with similarly soiled collars and cuffs which were washed in a standard detergent composition under the same conditions. The visual comparison was made by a group of five people who were unfamiliar with the procedure and purpose of the test and who formed their judgment independently.

The combined data from the visual judgments were converted and were expressed on a scale such that a value of zero represents the cleaning ability of wateralone and a value of 10 represents the cleaning ability of a very excellent detergent composition used under optimum laboratory conditions. The primary purpose of these deassociated with the compositions of this invention.

Excellent builder performances were scored by sodium (ethylene-maleate) (1:1 cross-linked copolymer on a molar basis) as well as the sodium (itaconate-acrylate) (1.6:1 copolymer on a molar basis) and the sodium (itaconate-aconitate) (1:1 copolymer on a molar basis). These latter examples of polyelectrolyte builders also afford relatively higher cleaning levels than STP at each builder concentration tested.

The two graph lines at the lower right hand quadrant of the figure are samples of polyelectrolyte aliphatic polycarboxyli-c compounds which do not meet the specific essential structural requirements set forth previously for desirable builder characteristics. From the formulas below, it will be seen that they contain interfering branch groups which boost their equivalent weights outside of the required range.

Sodium poly(vinylmethylether/maleate) has the following structure:

whereas sodium (isobutylene-maleate) copolyrner has l l H 431 13 OOOH COOH 11 Both of these compositions have been used in detergency compositions for various purposes. FIGURE 1 clearly shows their inferior performance as detergency builders and such compounds are clearly excluded from this invention.

The points identified as A, B, C, and D represent cleaning grades scored by additional built compositions using different samples of builder compounds at builder concentrations of .O3% and .06%. Points A, B and D, for instance, represent cleaning levels accomplished by sodium polyitaconate-built ABS detergent compositions wherein the sodium polyitaconate builder compounds had specific viscosities different from the previous sample as seen from Table 1. Point C on the other hand represents a cleaning grade achieved by an additional evaluation of a different sample of sodium (ethylene-maleate) linear copolymer, also at a .03% builder concentration with ABS. It is significant to note that the cleaning levels reflected by these four additional examples, A, B, C and D are all markedly better than the STP cleaning results at the same concentration, and further, that the cleaning grades obtained by a polyitaconate builder and represented by points A and B are, respectivley, comparable to and superior to the cleaning grade obtained with sodium tripolyphosphate used at a builder concentration of .045%. All of these results attest to the improved efliciency of the polyelectrolyte builder compounds of this invention. Moreover, equally good results are obtained with other detergent compounds such .as any of those listed earlier.

While sodium tripolyphosphate was the builder used for comparison in these tests, similar comparative results are obtained if, in the testing procedure, an excellent organic alkaline builder salt such as sodium ethylenediaminetetraacetate or potassium nitrilotriacetate is used in place of STP, especially at lower concentrations.

Another of the many advantages offered by the polyelectrolyte builder compounds of this invention is the surprising discovery that they are less corrosive to aluminum and other metals than known builder compounds.

The foregoing description and examples describe and illustrate certain operable and 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 16 art, all of which are within the spirit and scope of this invention.

What is claimed is: 1. A cleansing and laundering composition comprising (1) an organic water-soluble detergent surfactant selected from the group consisting of anionic, nonionic, zwitterionic, and ampholytic deterent surfactants, and mixtures thereof, and (2) a polyelectrolyte builder material consisting of water-soluble salts of a polymeric aliphatic polycarboxylic acid selected from the group consisting of (a) water-soluble salt of the homopolymer of an aliphatic polycarboxylic acid having thefollowing empirical formula:

X Z [an it (JOOH :1

wherein X, Y, and Z are each selected from the group consisting of hydrogen, methyl, carboxyl, and car'boxymethyl, at least one of X, Y, and Z being selected from the group consisting of carboXyl and carboxymethyl, provided that X and Y can 'be carboxy methyl only when Z is selected from carboxyl and carboxymethyl, wherein only one of X, Y, and Z can be methyl, and wherein n is a whole integer having a value within a range, the lower limit of which is three and the upper limit of which is determined by the solubility characteristics in an aqueous system;

(b) a water-soluble salt of a coplymer of at least two of the monomeric species having the empirical formula described in (a); and,

(c) a water-soluble salt of a copolymer of a member selected from the group of alkylenes and monocarboxylic acids with the aliphatic polycarboxylic compounds described in (a), said copolymers having the general formula:

wherein R is selected from the group consisting of hydrogen, methyl, carboxyl, carboxy- 'rneth'yl, and carboxyethyl; wherein only one R can be methyl; wherein m is at least 45 mole percent of the copolymer; wherein X, Y, and Z are each selected from the group consisting of hydrogen, methyl, carboxyl, and carboxymethyl, at least one of X, Y, and Z being selected from the group of carboxyl and carboxy-methyl provided that X and Y can be carboxymethyl only when Z is selected from carboxyl and carboxymethyl, wherein only one of X, Y and Z can be methyl; and wherein n is a whole integer within a range, the lower limit of which is three and the upper limit of which is determined primarily by the solubility characteristics in an aqueous system; said polyelectrolyte builder material having a minimum molecular weight of 350 calculated as the acid form and an equivalent weight of about 50 to about 80, calculated as the acid form, the ratio of said polyelectrolyte builder to said detergent surfactant being in the range of from about 1:3 to about 10:1, by weight. 2. A cleansing and laundering composition compris- (I) an organic water-soluble detergent surfactant selected from the group consisting of anionic, nonionic,

17 zwitterionic, and ampholytic detergent surfactants and the mixtures thereof, and (2) as a polyelectrolyte builder material, a Watersolu ble salt of a homopolymer of an aliphatic polycarboxylic acid having the folowing empirical formula:

Y CODE 11 wherein X, Y and Z are each selected from the group consisting of hydrogen, methyl, carboxyl and carboxymethyl, at least one of X, Y and Z being selected from the group consisting of carboxyl and carboxymethyl, provided that X and Y can be carboxymethyl only when Z is selected from carboxyl and carboxymet-hyl, wherein only one of X, Y and Z can be methyl, and wherein n is a whole integer having a value within the range the lower limit of which is three and the upper limit of which is determined primarily by the solubility characteristics in an aqueous system, said polyelectrolyte builder material having a minimum molecular weight of 350 calculated as the acid form and an equivalent weight of about 50 to about 80 calculated as the acid form, the ratio of said polyelectrolyte builder to said detergent surfactant being in the range of from about 1:3 to about :1, by weight. 3. A cleansing and laundering composition comprising (1) an organic water soluble detergent surfactant selected from the group consisting of anionic, nonionic, zwitterionic, and ampholytic detergent surfactants, and mixtures thereof, and (2) as a polyelectrolyte builder material, a water-soluble salt of a coplymer of at least two of the monomeric species having the empirical formula described in claim 2, said polyelectrolyte builder material having a minimum molecular weight of 350, calculated as the acid form, and an equivalent weight of about 50 to about 80, calculated as the acid form, the ratio of said polyelectrolyte builder to said detergent surfactant being in the range of from about 1:3 to about 10 :1, by weight. 4. A cleansing and laundering composition comprising (1) an organic water soluble detergent surfactant selected from the group consisting of anionic, nonionic, zwitterionic, and ampholytic detergent surfactants and mixtures thereof, and (2) as a polyelectrolyte builder material, a water-soluble salt of a copolymer of a member selected from the group of alkylenes and monocarboxylic acids with the aliphatic polycarboxylic compounds described in claim 2, said copolymers having the general formula:

R R r l I R (l-m) Y COOH m :1

wherein R is selected from the group consisting of hydrogen, methyl, carboxyl, carboxyrnethyl, and carboxyethyl, wherein only one R can be methyl;

wherein m is at least 45 mole percent of the copolymer, wherein X, Y and Z are each selected from the group consisting of hydrogen, methyl, carboxyl and carboxymethyl, at least one of X, Y and Z being selected from the group consisting of carboxyl and carboxymethyl provided that X and Y can be carboxymethyl only when Z is selected from carboxyl and carboxymethyl, wherein only one of X, Y and Z can be methyl; wherein n is a whole integer Within a range, the lower limit of which is three and the upper limit of which is determined primarily by the solubility characteristics in an aqueous system, said polyelectrolyte builder material having a minimum molecular weight of 350, calculated as the acid form, and an equivalent weight of about 50 to about 80, calculated as the acid form, the ratio of said polyelectrolyte builder to said detergent surfactant being in the range of from about 1:3 to about 10:1, by weight.

5. A cleansing and laundering composition as defined in claim 1, wherein the ratio of the polyelectrolyte builder to the detergent surfactant is from about 1:2 to about 5:1, 'by weight.

6. A cleansing and laundering composition as defined in claim 1, which provides in solution a pH of from about 9 to about 12.

7. A cleansing and laundering composition as defined in claim 6, which provides in solution a pH of from 9.5 to 11.5.

8. A built liquid composition of claim 1 wherein the ratio of the polyelectrolyte builder to the detergent surfactant is from about 1:2 to about 3:1, by weight.

9. A cleansing and laundering composition comprising as a detergent surfactant an anionic water-soluble alkali metal salt of an organic sulfuric reaction product having in its molecular structure an alkyl radical having from 8 to 22 carbon atoms and a radical selected from the group consisting of sulfonic acid and sulfuric acid ester radicals, and a builder compound as defined in claim 1, the ratio of said builder compound to said detergent surfactant being in the range of from about 1:3 to about 10:1, by weight, and said composition providing in aqueous solution a pH between about 9 and about 12.

10. A cleansing and laundering composition as defined in claim 9 wherein the anionic detergent surfactant is selected from the group consisting of alkali metal sulfates in which the alkyl substituent contains from about 8 to about 18 carbon atoms, alkali metal alkylbenzenesulfonates in which the alkyl group contains from about 9 to about 15 carbon atoms, and a builder compound as defined in claim 1, the ratio of said builder compound to said detergent surfactant being in the range of from about 1:3 to about 10:1, by weight, and said composition providing in aqueous solution a pH between about 9 and about 12.

11. A cleansing and laundering composition as defined in claim 2 wherein the polyelectrolyte builder compound is a water soluble salt of a homopolymer of an aliphatic polycarboxylic acid selected from the group consisting of poly(maleic acid), poly(itaconic acid), poly(measconic acid), poly(fumaric acid), poly(methylenemalonic acid), and poly(citraconic acid), wherein the ratio of said polyelectrolyte builder to said detergent surfactant is from about 1:3 to 10:1 by weight, and the composition provides in an aqueous solution a pH of from about 9 to about 12.

12. A cleansing and laundering composition as defined in claim 11 wherein the ratio by weight of builder to detergent is from 1:2 to about 5:1 and the pH in aqueous solution is between 9.5 and 11.5.

.13. A cleansing and laundering composition as defined in claim 3 wherein the polyelectrolyte builder compound is a water soluble salt of a copolymer selected from the group consisting of (itaconic acid and aconitic acid) copolymer (itaconic acid and maleic acid) copolymer, (mesaconic acid and fumaric acid) copolymer and (methylenemalonic acid and citronic acid) copolymer.

14. A cleansing and laundering composition as defined in claim 4 wherein the polyelectrolyte builder compound is selected from the group consisting of a 1:1 copolymer of ethylene and itaconic acid with an equivalent weight of 79; a 1:1 copolymer of propylene and maleic acid with an equivalent weight of 79; a 1:3 copolymer of acrylic acid and itaconic acid with an equivalent weight of 66; a 1:4 copolymer of 3-butenoic acid and maleic acid with an equivalent Weight of 61.1; a 1:9 copolymer of isocrotonic acid and citraconic acid with an equivalent weight of 66.2; a 1:1.9 copolymer of methacrylic acid and aconitic acid with an equivalent Weight of 62.2; a 1.221 copolyrner of 4-pentenoic acid and itaconic acid, with an equivalent weight of 78.2, said equivalent Weights calculated as the acid form, and said ratios being mole ratios.

15. A cleansing and laundering composition comprising 3-hydroxy-4-decoxybutyl methyl sulfoxide as a detergent surfactant and a sodium polymaleate builder compound, said polymaleate builder compound having a minimum molecular weight of 350, calculated as the acid form, and an equivalent Weight of about 50 to about 80, calculated as the acid form, the ratio of said builder to said detergent surfactant being from about 1:3 to about 10:1, by weight.

No references cited.

LEON D. ROSDOL, Primary Examiner.

J. T. FEDIGAN, Assistant Examiner.

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Patente citante Fecha de presentación Fecha de publicación Solicitante Título
US3454500 *8 Feb 19668 Jul 1969Procter & GambleSoap compositions having improved curd-dispersing properties
US3535258 *4 Dic 196720 Oct 1970Grace W R & CoMachine dishwashing composition and process
US3627686 *30 Sep 196814 Dic 1971Chemed CorpMachine dishwashing compositions containing sodium polyacrylate and nta
US3635830 *24 Nov 196918 Ene 1972Lever Brothers LtdDetergent compositions containing oxydisuccing acid salts as builders
US3671440 *16 Ene 197020 Jun 1972Chemed CorpProcess of cleaning
US3691106 *28 Ago 197012 Sep 1972Stauffer Chemical CoNovel detergent compositions
US3691107 *28 Ago 197012 Sep 1972Stauffer Chemical CoNovel detergent compositions
US3706672 *8 Dic 197019 Dic 1972Celanese CorpDetergent polyelectrolyte builders
US3844982 *11 May 197129 Oct 1974Procter & GambleBuilt detergent composition
US3853781 *17 Ene 197310 Dic 1974DegussaWashing and cleansing composition
US3870648 *14 Ene 197111 Mar 1975Gaf CorpPolyelectrolytes as detergent builders
US3883446 *9 Feb 197313 May 1975Continental Oil CoPhosphorus-free detergent formulation
US3896056 *2 Mar 197322 Jul 1975Procter & GambleBuilt detergent composition
US3933673 *22 Dic 197020 Ene 1976Lever Brothers CompanyDetergent compositions containing polymeric builders
US3950260 *10 Abr 197213 Abr 1976Ibrahim Andrew EldibPolyacrylates of selective viscosity as detergent builders
US3953382 *30 May 197327 Abr 1976Lever Brothers CompanyDetergent compositions
US3954643 *24 Ago 19734 May 1976Henkel & Cie GmbhFoam-regulated washing compositions, especially for drum washing machines
US3954662 *2 Ene 19744 May 1976Monsanto Research CorporationAqueous foam compositions to suppress coal dust
US3962100 *18 Ago 19758 Jun 1976The Procter & Gamble CompanyFabric softening agents
US4000080 *11 Oct 197428 Dic 1976The Procter & Gamble CompanyLow phosphate content detergent composition
US4025444 *7 Jun 197624 May 1977The Procter & Gamble CompanyFabric softening agents
US4072621 *11 Nov 19757 Feb 1978The Procter & Gamble CompanyDetergent composition
US4083794 *27 May 197611 Abr 1978Ciba-Geigy CorporationDetergent composition
US4299739 *22 Ago 197710 Nov 1981Lever Brothers CompanyUse of aluminum salts in laundry detergent formulations
US4303557 *23 Sep 19801 Dic 1981The Procter & Gamble CompanyAbrasion resistant spray dried aluminosilicate detergent composition
US4323465 *23 Abr 19816 Abr 1982Fmc CorporationStabilized sodium sulfate-hydrogen peroxide-sodium chloride adduct and alkaline bleach composition containing same
US4374572 *17 Feb 198122 Feb 1983The Procter & Gamble CompanyMethod and composition to inhibit staining of porcelain surfaces by manganese
US4388205 *6 Nov 198114 Jun 1983Sandoz Ltd.Phosphate-free cleaning compositions
US4485223 *22 Jul 198227 Nov 1984Pfizer Inc.(Meth)acrylic acid/itaconic acid copolymers, their preparation and use as antiscalants
US4501847 *9 Jul 198126 Feb 1985Monsanto CompanyPolymeric antitumor agent
US4559159 *16 Feb 198417 Dic 1985Basf AktiengesellschaftCopolymers, their preparation and their use as assistants in detergents and cleansing agents
US4595394 *2 Abr 198417 Jun 1986Kao CorporationAgent for improving processability of cellulose fibers: acid polymer salts for improved scouring
US4600524 *8 Dic 198315 Jul 1986W. R. Grace & Co.Composition and method for inhibiting scale
US4622370 *1 May 198411 Nov 1986Diamond Shamrock Chemicals CompanyAqueous drilling fluids containing fluid loss additives
US4627931 *29 Ene 19859 Dic 1986A. E. Staley Manufacturing CompanyMethod and compositions for hard surface cleaning
US4687592 *11 Jul 198518 Ago 1987The Procter & Gamble CompanyDetergency builder system
US4689167 *30 Ene 198625 Ago 1987The Procter & Gamble CompanyDetergency builder system
US4709091 *27 Mar 198524 Nov 1987Kao CorporationProduction of polymaleic acid
US4786433 *2 Jul 198622 Nov 1988Ecolab Inc.Method of preparing phosphorous-free stable detergent emulsion
US4797223 *11 Ene 198810 Ene 1989Rohm And Haas CompanyWater soluble polymers for detergent compositions
US4874540 *3 Sep 198717 Oct 1989Ecolab Inc.Graft copolymers of a polyether moiety on a polycarboxylate backbone
US4914167 *8 Jul 19853 Abr 1990Basf AktiengesellschaftPolymeric organic acids, their preparation and their use in detergents and cleansers
US4938888 *5 Ene 19893 Jul 1990Lever Brothers CompanyDetergent sheet with alkyl polyglycoside composition
US4980088 *7 Dic 198925 Dic 1990Basf AktiengesellschaftDetergent compositions with copolymers of 1,2-dialkoxyethylenes and monoethylenically unsaturated dicarboxylic anhydrides
US4983317 *8 Abr 19888 Ene 1991The Drackett CompanyAll purpose cleaner concentrate composition
US5032646 *28 Sep 198416 Jul 1991Pfizer Inc.(Meth)acrylic acid/itaconic acid copolymers, their preparation and use as antiscalants
US5062995 *6 Feb 19905 Nov 1991Lever Brothers Company, Division Of Conopco, Inc.Polymeric carbamate detergent builders
US5159041 *13 Dic 199027 Oct 1992Lever Brothers CompanyPolymers and detergent compositions containing them
US5174927 *6 Sep 199129 Dic 1992The Procter & Gamble CompanyProcess for preparing brightener-containing liquid detergent compositions with polyhydroxy fatty acid amines
US5202045 *5 Ene 198913 Abr 1993Lever Brothers Company, Division Of Conopco, Inc.S-shaped detergent laminate
US5254281 *8 Ene 199219 Oct 1993The Procter & Gamble CompanySoap bars with polyhydroxy fatty acid amides
US5298195 *9 Mar 199229 Mar 1994Amway CorporationLiquid dishwashing detergent
US5332528 *17 Jun 199326 Jul 1994The Procter & Gamble CompanyPolyhydroxy fatty acid amides in soil release agent-containing detergent compositions
US5443757 *12 Nov 199322 Ago 1995Amway CorporationLiquid dishwashing detergent
US5454982 *13 Dic 19943 Oct 1995The Procter & Gamble CompanyDetergent composition containing polyhydroxy fatty acid amide and alkyl ester sulfonate surfactants
US5494488 *4 Feb 199427 Feb 1996Degussa AktiengesellschaftDetergent composition and method of use with surfactant, silicate, and polycarboxylate
US5545348 *2 Nov 199413 Ago 1996Church & Dwight Co., Inc.Non-Phosphate high carbonate machine dishwashing detergents containing maleic acid homopolymer
US5552078 *21 Dic 19943 Sep 1996Church & Dwight Co., Inc.Carbonate built laundry detergent composition
US5698511 *23 Abr 199616 Dic 1997Colgate-Palmolive CompanyGranular detergent compositions containing deflocculating polymers and process for preparing such compositions
US5700771 *7 Mar 199523 Dic 1997The Procter & Gamble CompanyPolyhydroxy fatty acid amide surfactants in percarbonate bleach-containing compositions
US5723427 *18 Sep 19953 Mar 1998Colgate-Palmolive CompanyGranular detergent compositions containing deflocculating polymers and processes for their preparation
US5834414 *17 Oct 199610 Nov 1998Ecolab Inc.Detergent composition having improved chlorine stability characteristics, novel chlorine containing product format and method of making chlorine stable composition
US5858117 *31 Ago 199412 Ene 1999Ecolab Inc.Proteolytic enzyme cleaner
US5861366 *21 May 199619 Ene 1999Ecolab Inc.Proteolytic enzyme cleaner
US5905065 *27 Jun 199618 May 1999The Procter & Gamble CompanyCarpet cleaning compositions and method for cleaning carpets
US5928384 *31 Oct 199527 Jul 1999The Procter & Gamble CompanyMethod of cleaning carpets
US5932532 *16 Sep 19973 Ago 1999Procter & Gamble CompanyBleach compositions comprising protease enzyme
US6034045 *25 Feb 19977 Mar 2000Church & Dwight Co., Inc.Liquid laundry detergent composition containing a completely or partially neutralized carboxylic acid-containing polymer
US6040288 *20 Feb 199821 Mar 2000Rhodia Inc.Fabric color protection compositions and methods
US6051541 *16 Dic 199818 Abr 2000Unilever Home & Personal Care, Division Of Conopco, Inc.Process for preparing pourable, transparent/translucent liquid detergent with continuous suspending system
US6066612 *3 May 199623 May 2000The Procter & Gamble CompanyDetergent compositions comprising polyamine polymers with improved soil dispersancy
US6096704 *21 Mar 19971 Ago 2000Bryant, Jr.; Lonnie LiddellPro-fragrance compound
US6159918 *16 Dic 199812 Dic 2000Unilever Home & Personal Care U.S.A., Division Of Conopco, Inc.Transparent/translucent liquid enzyme compositions in clear bottles comprising UV absorber
US619773919 Ago 19976 Mar 2001Ecolab Inc.Proteolytic enzyme cleaner
US625877116 Dic 199810 Jul 2001Unilever Home & Personal Care, Usa Division Of ConopcoProcess for preparing pourable, transparent/translucent liquid detergent with non-continuous suspending system
US626201315 Oct 199917 Jul 2001Ecolab Inc.Sanitizing laundry sour
US62907329 Nov 199918 Sep 2001Ecolab Inc.Laundry process with enhanced ink soil removal
US636215616 Dic 199826 Mar 2002Unilever Home & Personal Care, Usa, Division Of Conopco, Inc.Pourable transparent/translucent liquid detergent composition with suspended particles
US636901827 Nov 20009 Abr 2002Unilever Home & Personal Care, Usa, Division Of Conopco, Inc.Process for preparing pourable, transparent/translucent liquid detergent with non-continuous suspending system
US64639394 Feb 200015 Oct 2002Unilever Home & Personal Care, Usa, Division Of Conopco, Inc.Dish washing process
US661730030 Ago 20019 Sep 2003Procter & Gamble CompanyGranular bleach activators having improved solubility profiles
US663043716 Dic 19987 Oct 2003Unilever Home & Personal Care Usa , Division Of Conopco, Inc.Transparent/translucent liquid compositions in clear bottles comprising colorant and fluorescent dye or UV absorber
US666071113 Jul 20009 Dic 2003The Procter & Gamble CompanyLaundry detergent compositions comprising zwitterionic polyamines and mid-chain branched surfactants
US668028614 Nov 200020 Ene 2004Sanyo Chemical Industries, Ltd.Detergent composition comprising a quaternary ammonium salt of a carboxyl containing polymer
US679081427 Nov 200014 Sep 2004Procter & Gamble CompanyDelivery system having encapsulated porous carrier loaded with additives, particularly detergent additives such as perfumes
US695358729 May 200311 Oct 2005Proacter & Gamble CompanyProcess for making a water-soluble foam component
US752480012 Jun 200828 Abr 2009Rhodia Inc.Mono-, di- and polyol phosphate esters in personal care formulations
US752480812 Jun 200828 Abr 2009Rhodia Inc.Hard surface cleaning composition with hydrophilizing agent and method for cleaning hard surfaces
US755041912 Jun 200823 Jun 2009Rhodia Inc.Mono-, di- and polyol alkoxylate phosphate esters in oral care formulations and methods for using same
US755707212 Jun 20087 Jul 2009Rhodia Inc.Detergent composition with hydrophilizing soil-release agent and methods for using same
US760857112 Jun 200827 Oct 2009Rhodia Inc.Method for recovering crude oil from a subterranean formation utilizing a polyphosphate ester
US763847521 Mar 200729 Dic 2009Georgia-Pacific Consumer Products LpSpace saving toilet cleaning system
US76824039 Ene 200423 Mar 2010Ecolab Inc.Method for treating laundry
US779066427 Oct 20087 Sep 2010The Procter & Gamble CompanyMethods for making a nil-phosphate liquid automatic dishwashing composition
US78679636 Ene 200911 Ene 2011Rhodia Inc.Mono-, di- and polyol phosphate esters in personal care formulations
US791907325 May 20095 Abr 2011Rhodia OperationsMono-, di- and polyol alkoxylate phosphate esters in oral care formulations and methods for using same
US791944925 May 20095 Abr 2011Rhodia OperationsDetergent composition with hydrophilizing soil-release agent and methods for using same
US805837424 Nov 200915 Nov 2011Akzo Nobel N.V.Hybrid copolymers
US819255220 Feb 20095 Jun 2012Rhodia ChimieDetergent composition comprising a block copolymer
US822738123 Sep 201024 Jul 2012Akzo Nobel N.V.Low molecular weight graft copolymers for scale control
US826876530 Nov 201018 Sep 2012Rhodia OperationsMono-, di- and polyol phosphate esters in personal care formulations
US82936996 Ene 200923 Oct 2012Rhodia OperationsHard surface cleaning composition with hydrophilizing agent and method for cleaning hard surfaces
US829901010 Sep 201030 Oct 2012The Procter & Gamble CompanyLaundry care compositions with thiazolium dye
US83619467 Abr 200529 Ene 2013Akzo Nobel N.V.Detergent composition
US83947529 Dic 200912 Mar 2013The Procter & Gamble CompanyPearlescent agent slurry for liquid treatment composition
US863314620 Sep 201121 Ene 2014The Procter & Gamble CompanyNon-fluoropolymer surface protection composition comprising a polyorganosiloxane-silicone resin mixture
US863691830 Jul 201228 Ene 2014Ecolab Usa Inc.Cleaning composition containing a polysaccharide hybrid polymer composition and methods of controlling hard water scale
US863744220 Sep 201128 Ene 2014The Procter & Gamble CompanyNon-fluoropolymer surface protection composition comprising a polyorganosiloxane-silicone resin mixture
USH1514 *1 Jun 19942 Ene 1996The Procter & Gamble CompanyDetergent compositions with oleoyl sarcosinate and polymeric dispersing agent
DE2110665A1 *5 Mar 197123 Sep 1971Pennwalt CorpWasserloesliches Aerylsaeure-Copolymeres
DE2159172A1 *29 Nov 19718 Jun 1972Ciba Geigy AgTítulo no disponible
EP0009171A2 *5 Sep 19792 Abr 1980BASF AktiengesellschaftProcess for the preparation of polymaleic acid from maleic anhydride in the presence of acetic anhydride and hydrogen peroxyde, and the use of the polymaleic acid thus prepared as builder and as incrustation inhibitor in detergent compositions
EP0150532A112 Dic 19847 Ago 1985THE PROCTER & GAMBLE COMPANYPeroxygen bleach activators and bleaching compositions
EP0679714A225 Abr 19952 Nov 1995THE PROCTER & GAMBLE COMPANYDetergent compositions containing cellulase enzyme and selected perfumes for improved odor and stability
EP0693549A119 Jul 199424 Ene 1996THE PROCTER & GAMBLE COMPANYSolid bleach activator compositions
EP0699472A115 Jun 19956 Mar 1996Agro Industrie Recherches Et Developpements (A.R.D.)Process for the production of surfactants from wheat by-products and their uses
EP0748864A118 Dic 199518 Dic 1996THE PROCTER & GAMBLE COMPANYCleaning composition and method for the cleaning of delicate surfaces
EP0752466A15 Jul 19958 Ene 1997THE PROCTER & GAMBLE COMPANYNonaqueous detergent compositions comprising effervescent systems
EP0753571A110 Jul 199515 Ene 1997THE PROCTER & GAMBLE COMPANYProcess for making granular detergent composition
EP0763594A118 Sep 199519 Mar 1997THE PROCTER & GAMBLE COMPANYProcess for making granular detergents
EP0771785A12 Nov 19957 May 1997THE PROCTER & GAMBLE COMPANYBeta-amino ester compounds of perfume alcohols and their use in cleaning or laundry compositions
EP0778342A16 Dic 199511 Jun 1997THE PROCTER & GAMBLE COMPANYDetergent compositions
EP0786515A219 Dic 199630 Jul 1997Unilever N.V.Prewash stain remover composition with siloxane based surfactant
EP0786516A216 Ene 199730 Jul 1997Unilever N.V.Liquid detergent
EP1702975A123 Feb 200620 Sep 2006Unilever N.V.Laundry detergent with polyamine mono-anionic surfactant
EP1854869A19 May 200614 Nov 2007The Procter and Gamble CompanyWater-soluble, liquid-containing pouch
EP1975225A125 Feb 20081 Oct 2008The Procter and Gamble CompanyDetergent composition
EP2106704A123 Mar 20097 Oct 2009Symrise GmbH & Co. KGParticles having a high load of fragrance or flavor oil
EP2135934A117 Dic 200823 Dic 2009Unilever PLCUse of a laundry detergent composition
EP2169042A130 Sep 200831 Mar 2010The Procter and Gamble CompanyComposition comprising microcapsules
EP2426192A120 Mar 20077 Mar 2012The Procter and Gamble CompanyLiquid treatment composition
EP2495300A14 Mar 20115 Sep 2012Unilever Plc, A Company Registered In England And Wales under company no. 41424 of Unilever HouseStructuring detergent liquids with hydrogenated castor oil
WO1996015308A1 *31 Oct 199523 May 1996Procter & GambleMethod of cleaning carpets
WO1996017919A1 *30 Nov 199513 Jun 1996Colgate Palmolive CoGranular detergent compositions containing deflocculating polymers
WO1996025478A16 Feb 199622 Ago 1996Gerard Marcel BaillelyDetergent composition comprising an amylase enzyme and a nonionic polysaccharide ether
WO1997011785A1 *12 Sep 19963 Abr 1997Procter & GambleMethod of treating household surfaces using high volume sprayer
WO1997042282A13 May 199613 Nov 1997Ayako MuramatsuDetergent compositions comprising polyamine polymers with improved soil dispersancy
WO2001021499A122 Sep 199929 Mar 2001Citra Wijaya NgA hand-held liquid container
WO2001049575A120 Dic 200012 Jul 2001Lever Hindustan LtdTransparent/translucent bottles containing fluorescent dye in sidewall
WO2007111892A220 Mar 20074 Oct 2007Procter & GambleLiquid treatment composition
WO2008109384A229 Feb 200812 Sep 2008Celanese Acetate LlcMethod of making a bale of cellulose acetate tow
WO2010080326A110 Dic 200915 Jul 2010The Procter & Gamble CompanyPearlescent agent slurry for liquid treatment composition
WO2011072968A116 Nov 201023 Jun 2011Unilever PlcMeasured dosing cap assembly
WO2011100405A110 Feb 201118 Ago 2011The Procter & Gamble CompanyBenefit compositions comprising crosslinked polyglycerol esters
WO2011100411A110 Feb 201118 Ago 2011The Procter & Gamble CompanyBenefit compositions comprising polyglycerol esters
WO2011100420A110 Feb 201118 Ago 2011The Procter & Gamble CompanyBenefit compositions comprising crosslinked polyglycerol esters
WO2011100500A111 Feb 201118 Ago 2011The Procter & Gamble CompanyBenefit compositions comprising polyglycerol esters
WO2011100667A114 Feb 201118 Ago 2011Ls9, Inc.Surfactant and cleaning compositions comprising microbially produced branched fatty alcohols
WO2011120799A116 Mar 20116 Oct 2011Unilever PlcStructuring detergent liquids with hydrogenated castor oil
WO2011144921A212 May 201124 Nov 2011Reckitt & Colman (Overseas) LimitedComposition and method
WO2012009525A214 Jul 201119 Ene 2012The Procter & Gamble CompanyCompositions comprising a near terminal-branched compound and methods of making the same
WO2012040130A120 Sep 201129 Mar 2012The Procter & Gamble CompanyNon-fluoropolymer surface protection composition
WO2012040131A220 Sep 201129 Mar 2012The Procter & Gamble CompanyFabric care formulations and methods
WO2012040171A120 Sep 201129 Mar 2012The Procter & Gamble CompanyNon-fluoropolymer surface protection composition
WO2013043803A220 Sep 201228 Mar 2013The Procter & Gamble CompanyDetergent compositions comprising specific blend ratios of isoprenoid-based surfactants
WO2013043805A120 Sep 201228 Mar 2013The Procter & Gamble CompanyDetergent compositions comprising primary surfactant systems comprising highly branched surfactants especially isoprenoid - based surfactants
WO2013043852A220 Sep 201228 Mar 2013The Procter & Gamble CompanyEasy-rinse detergent compositions comprising isoprenoid-based surfactants
WO2013043855A220 Sep 201228 Mar 2013The Procter & Gamble CompanyHigh suds detergent compositions comprising isoprenoid-based surfactants
WO2013043857A120 Sep 201228 Mar 2013The Procter & Gamble CompanyDetergent compositions comprising sustainable surfactant systems comprising isoprenoid-derived surfactants
WO2013070559A16 Nov 201216 May 2013The Procter & Gamble CompanySurface treatment compositions including shielding salts
WO2013070560A16 Nov 201216 May 2013The Procter & Gamble CompanySurface treatment compositions including shielding salts
WO2014018309A116 Jul 201330 Ene 2014The Procter & Gamble CompanyLow ph liquid cleaning compositions with enzymes
WO2014039302A126 Ago 201313 Mar 2014Lubrizol Advanced Materials, Inc.Polyurethane/polyacrylic hybrid dispersions for shine applications in home care
Clasificaciones
Clasificación de EE.UU.510/346, 510/339, 510/355, 510/361, 510/337, 510/356, 510/237, 510/476, 510/350, 510/341, 510/325
Clasificación internacionalC08F22/00, C07C59/305, C11D3/37, C11D3/00, C07C55/24
Clasificación cooperativaC07C59/305, C07C55/24, C11D3/3757, C08F22/00
Clasificación europeaC08F22/00, C07C59/305, C07C55/24, C11D3/37C6