EP0063017B1 - Reinigungsmittelzusammensetzungen - Google Patents

Reinigungsmittelzusammensetzungen Download PDF

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EP0063017B1
EP0063017B1 EP82301776A EP82301776A EP0063017B1 EP 0063017 B1 EP0063017 B1 EP 0063017B1 EP 82301776 A EP82301776 A EP 82301776A EP 82301776 A EP82301776 A EP 82301776A EP 0063017 B1 EP0063017 B1 EP 0063017B1
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acid
weight
composition according
methyl
salts
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EP0063017A1 (de
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John Hampton
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Procter and Gamble Ltd
Procter and Gamble Co
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Procter and Gamble Ltd
Procter and Gamble Co
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    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/39—Organic or inorganic per-compounds
    • C11D3/3902—Organic or inorganic per-compounds combined with specific additives
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/02—Inorganic compounds ; Elemental compounds
    • C11D3/04—Water-soluble compounds
    • C11D3/06—Phosphates, including polyphosphates
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/37—Polymers
    • C11D3/3746—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • C11D3/3757—(Co)polymerised carboxylic acids, -anhydrides, -esters in solid and liquid compositions
    • C11D3/3761—(Co)polymerised carboxylic acids, -anhydrides, -esters in solid and liquid compositions in solid compositions

Definitions

  • This invention relates to built detergent compositions containing activators for oxygen releasing bleaching compounds, especially activators in the form of organic peroxy acid bleach precursors.
  • peroxygen bleaching agents e.g., perborates, percarbonates, perphosphates, persilicates etc.
  • bleaching agents are highly useful for chemical bleaching of stains found both coloured and white fabrics.
  • Such bleaching agents are most effective at high wash solution temperatures, i.e., above about 70°C.
  • attempts have been made to provide bleaching compositions that are effective at lower wash solution temperatures, i.e., between room temperature and 70°C.
  • bleaching agents have been investigated which exhibit their optimum bleach activity in this temperature range.
  • These low temperature bleaches are useful in a variety of products intended for use under machine or hand-wash conditions, e.g., additive, pre-additive or soak-type laundry compositions as well as all-purpose detergent compositions.
  • a very effective class of low temperature bleach system comprises a peroxy bleach compound and an organic peracid precursor which react together to form the organic peracid in the wash solution.
  • Examples of detergent compositions incorporating bleaching agents of this type are disclosed in US-A-2,362,401, US ⁇ A ⁇ 3,639,248, GB-A-836,988 and GB-A-855,735.
  • compositions containing a significant amount of water-soluble orthophosphate and/or water-soluble pyrophosphate salts as builder can experience problems of soil deposition onto fabrics with resulting loss in fabric whiteness.
  • Orthophosphates and pyrophosphates can occur as degradation products of sodium tripolyphosphate when the latter is incorporated in a detergent composition prepared by spray-drying.
  • the extent of degradation during spray-drying, and therefore the level of orthophosphates and pyrophosphates can vary widely from as little as 3% up to about 40% or more by weight of tripolyphosphate, the actual degree of degradation being determined by the particular process conditions applied, notably crutcher mix moisture, temperature and residence time, the inlet temperature of the drying tower and the moisture of the blown powder.
  • Ortho and pyrophosphates are, of course, useful builders in their own right, and have come into more prominence in recent years as the use of high levels of sodium tripolyphosphate has come under scrutiny because of the suspicion that soluble phosphate species accelerate the eutrophication or aging process of water bodies. This eutrophication is ordinarily evidenced by the rapid growth of algae in the water body.
  • ortho- and pyrophosphates specially orthophosphate, can remove more hardness ions (Ca H , Mg++) per unit of P 2 0 5 in their constitution than can tripolyphosphate.
  • Orthophosphates, and to greater or less extent, pyrophosphates act as detergency builders, however, by precipitating these hardness ions as insoluble phosphates whereas sodium tripolyphosphate retains them in solution as complex ions. Building detergency by means of this precipitating mechanism tends, therefore, to cause undesirable effects, in particular, deposition of insoluble phosphate onto fabrics.
  • a granular detergent composition comprising:
  • the phosphate builder comprises from 50% to 90%, preferably to 88% by weight thereof of water-soluble tripolyphosphate salt and from 10% to 50%, preferably from 12% to 40% by weight thereof of the mixture of water-soluble orthophosphate and pyrophosphate salts in a weight ratio of from 3:7 to 1:20. While the builder is present in the range from 5% to 90%, preferably 10% to 50% by weight, highly preferred compositions are low in phosphate, containing phosphorus in an amount not exceeding that contained in 28% by weight of anhydrous sodium tripolyphosphate. The benefits of the invention are readily apparent, however, even at builder:hardness ratios in excess of 1:1.
  • Preferred polymeric polycarboxylic acids for use herein have an average molecular weight in the range from 500 to 2,000,000, more preferably from 12,000 to 1,500,000, and are copolymers comprising:
  • Highly preferred polymeric polycarboxylic acids are copolymers of maleic acid or maleic anhydride with methyl vinyl ether, ethyl vinyl ether, or acrylic acid having an average molecular weight in the range from 12,000 to 1,500,000. Moreover, the weight ratio of organic peroxy acid bleach precursor to polymeric carboxylic acid lies in the range from 10:1 to 1:3, preferably from 5:1 to 1:2.
  • compositions of the invention can take the form of an additive product for addition at the point of consumption either to a wash liquor or to an auxiliary composition containing a peroxy salt bleaching agent. More usually, however, the compositions of the invention will themselves contain peroxy salt bleaching agent in a level of from 5% to 35% by weight.
  • ingredients of the present compositions include from 0.015% to 0.2% by weight of a water-soluble magnesium salt additive (percentages expressed in terms of magnesium content), and from 0.05% to 0.4% by weight (acid basis) of an aminopolyphosphonic acid, especially ethylenediamine- tetra(methylenephosphonic acid), diethylenetriaminepenta(methylenephosphonic acid) or salts thereof.
  • a water-soluble magnesium salt additive percentages expressed in terms of magnesium content
  • an aminopolyphosphonic acid especially ethylenediamine- tetra(methylenephosphonic acid), diethylenetriaminepenta(methylenephosphonic acid) or salts thereof.
  • An essential component of the present invention is an organic peroxy acid bleach precursor.
  • organic peroxy acid bleach precursors examples of the various classes are given below. Of these, highly preferred are bleach precursors providing peracetic acid bleach.
  • Esters suitable as peroxy compound precursors in the present invention include esters of monohydric substituted and unsubstituted phenols, substituted aliphatic alcohols in which the substituent group is electron withdrawing in character, mono- and disaccharides, N-substituted derivatives of hydroxylamine and esters of imidic acids.
  • the phenol esters of both aromatic and aliphatic mono- and dicarboxylic acids can be employed.
  • the aliphatic esters can have 1 to 20 carbon atoms in the acyl group, examples being phenyl laurate, phenyl myristate, phenyl palmitate and phenyl stearate.
  • 1-acetoxy benzoic acid and methyl o-acetoxy benzoate are especially preferred.
  • Diphenyl succinate, diphenyl azeleate and diphenyl adipate are examples of phenyl aliphatic dicarboxylic acid esters.
  • Aromatic esters include phenyl benzoate, diphenyl phthalate and diphenyl isophthalate.
  • ester of a substituted aliphatic alcohol is trichloroethyl acetate.
  • saccharide esters include glucose penta-acetate and sucrose octa-acetate.
  • An exemplary ester of hydroxylamine is acetyl aceto hydroxamic acid.
  • esters suitable for use as peroxy compound precursors in the present invention are fully described in GB-A-836988 and GB-A-1147871.
  • esters are the acyl phenol sulphonates and acyl alkyl phenol sulphonates.
  • An example of the former is sodium acetyl phenol sulphonate (alternatively described as sodium p-acetoxy benzene sulphonate).
  • Examples of acyl alkyl phenol sulphonates include sodium 2-acetoxy 5-dodecyl benzene sulphonate, sodium 2-acetoxy 5-hexyl benzene sulphonate and sodium 2-acetoxy capryl benzene sulphonate. The preparation and use of these and analogous compounds is given in GB-A-963135 and GB-A-1147871.
  • Esters of imidic acids have the general formula:- wherein X is substituted or unsubstituted C 1 ⁇ C 20 alkyl or aryl and Y can be the same as X and can also be -NH 2 .
  • An example of this class of compounds is ethyl benzimidate wherein Y is C 6 H S and X is ethyl.
  • esters include p-acetoxy acetophenone and 2,2-di-(4-hydroxyphenyl) propane diacetate. This last material is the diacetate derivative of 2,2-di(4-hydroxyphenyl) propane more commonly known as Bisphenol A which is an intermediate in the manufacture of polycarbonate resins. Bisphenol A diacetate and methods for its manufacture are disclosed in DE-A-1260479.
  • Imides suitable as organic peroxy compound precursors in the present invention are compounds of formula:- in which R, and R 2 , which can be the same or different are independently chosen from a C l -C 4 alkyl group or an aryl group and X is an alkyl, aryl or acyl radical (either carboxylic or sulphonic).
  • Typical compounds are those in which R, is a methyl, ethyl, propyl or phenyl group but the preferred compounds are those in which R 2 is also methyl, examples of such compounds being N,N-diacetylaniline, N,N - diacetyl - p - chloroaniline and N,N - diacetyl - p - toluidine.
  • Either one of R, and R 2 together with X may form a heterocyclic ring containing the nitrogen atom.
  • N-acyl lactams in which the nitrogen atom is attached to two acyl groups, one of which is also attached to the nitrogen in a second position through a hydrocarbyl linkage.
  • a particularly preferred example of this class is N-acetyl caprolactam.
  • the linkage of the acyl group to form a heterocyclic ring may itself include a heteroatom, for example oxygen, and N-acyl saccharides are a class of precursors of this type.
  • cyclic imides in which the reactive centre is a sulphonic radical are N-benzene sulphonyl phthalimide, N-methanesulphonyl succinimide and N-benzene sulphonyl succinimide. These and other N-sulphonyl imides useful herein are described in GB-A-1242287.
  • N-acylated dicarboxylic acid imides such as the N-acyl phthalimides, N-acyl succinimides, N-acyl adipimides and N-acyl glutarimides. Imides of the above-mentioned types are described in GB-A-855735.
  • Two further preferred groups of materials in this class are those in which X in the above formula is either a second diacylated nitrogen atom, i.e. substituted hydrazines, or a difunctional hydrocarbyl groups such as a C,-C 6 alkylene group further substituted with a diacylated nitrogen atom i.e. tetra acylated alkylene diamines.
  • TAMD tetra acetyl methylene diamine
  • TAED tetra acetyl ethylene diamine
  • TAHD tetra acetyl hexamethylene diamine
  • TH tetra acetyl hydrazine
  • Acylated glycolurils form a further group of compounds falling within the general class of imide peroxy compound precursors. These materials have the general formula:- in which at least two of the R groups represent acyl radicals having 2 to 8 carbon atoms in their structure. The preferred compound is tetra acetyl glycoluril in which the R groups are all CH 3 CO- radicals.
  • the acylated glycolurils are described in GB-A-1246338, GB-A-1246339, and GB-A-1247429.
  • imide-type compounds suitable for use as peroxy compound precursors in the present invention are the N-(halobenzoyl) imides disclosed in GB-A-1247857, of which N-m-chloro benzoyl succinimide is a preferred example, and poly imides containing an N-bonded-COOR group, e.g. N-methoxy carbonyl phthalimide, disclosed in GB-A-1244200.
  • N-acyl and N,N'-diacyl derivatives of urea are also useful peroxy compound precursors for the purposes of the present invention, in particular N-acetyl dimethyl urea, N,N'-diacetyl ethylene urea and N,N'-diacetyl. dimethyl urea.
  • Compounds of this type are disclosed in NL-A-6504416.
  • Other urea derivatives having inorganic persalt activating properties are the mono- or di-N-acylated azolinones disclosed in GB-A-1379530.
  • Acylated hydantoin derivatives also fall within this general class of organic peroxy compound precursors.
  • the hydantoins may be substituted e.g. with lower alkyl groups and one or both nitrogen atoms may be acylated.
  • Examples of compounds of this type are N-acetyl hydantoin, N,N-diacetyl, 5,5-dimethyl hydantoin, 1-phenyl, 3-acetyl hydantoin and 1-cyclohexyl, 3-acetyl hydantoin. These and similar compounds are described in GB ⁇ A ⁇ 965672 and GB ⁇ A ⁇ 1112191.
  • N,N-diacyl methylene diformamides of which N,N-diacetyl methylamine diformamide is the preferred member.
  • This material and analogous compounds are disclosed in GB-A-1106666.
  • N-acyl imidazoles and similar five-membered ring systems form a further series of compounds useful as inorganic peroxy compound precursors.
  • Specific examples are N-acetyl benzimidazole, N-benzoyl imidazole and its chloro- and methyl-analogues.
  • Compounds of this type are disclosed in GB-A-1234762, GB-A-1311765 and GB-A-1395760.
  • Oximes and particularly acylated oximes are also a useful class of organic peroxy compound precursors for the purpose of this invention.
  • Oximes are derivatives of hydroxylamine from which they can be prepared by reaction with aldehydes and ketones to give aldoximes and ketoximes respectively.
  • the acyl groups may be C l -C 12 aliphatic or aromatic in character, preferred acyl groups being acetyl, propionyl, lauroyl, myristyl and benzoyl.
  • Compounds containing more than one carbonyl group can react with more than one equivalent of hydroxylamine and the commonest class of dioximes are those derived from 1,2-diketones and ketonic aldehydes, such as dimethyl glyoxime.
  • the acylated derivatives of this compound are of particular value as organic peroxy compound precursors, examples being diacetyl dimethyl glyoxime, dibenzoyl dimethyl glyoxime and phthaloy
  • esters of carbonic and pyrocarbonic acid have also been proposed as organic peroxy compound precursors.
  • Typical examples of such esters are p-carboxy phenyl ethyl carbonate, sodium-p-sulphophenyl ethyl carbonate, sodium-p-sulphophenyl n-propyl carbonate and diethyl pyrocarbonate.
  • the use of such esters as inorganic persalt activators in detergent compositions is set forth in GB-A-970950.
  • organic peroxy compound precursors including triacyl guanidines of formula:- wherein R is alkyl, preferably acetyl or phenyl, prepared by the acylation of guanidine salt.
  • R is alkyl, preferably acetyl or phenyl
  • Other classes of compounds include acyl sulphonamides, e.g. N-phenyl N-acetyl benzene sulphonamide as disclosed in GB-A-1003310 and triazine derivatives such as those disclosed in GB-A-1104891 and GB-A-1410555.
  • triazine derivatives are the di- and triacetyl derivatives of 2,4,6 - trihydroxy - 1,3,5 - triazine, 2 - chloro - 4,6 - dimethoxy - S - triazine and 2,4 - dichloro - 6 - methoxy - S - triazine.
  • Piperazine derivatives such as 1,4 - diacylated - 2,5 - diketo piperazine as described in GB-A-1339256 and GB-A-1339257 are also useful as are water-soluble alkyl and aryl chloroformates such as methyl, ethyl and phenyl chloroformate disclosed in GB-A-1242106.
  • the preferred classes are those that produce a peroxycarboxylic acid on reaction with an inorganic persalt.
  • the preferred classes are the imides, oximes and esters especially the phenol esters and imides.
  • Specific preferred materials are solid and are incorporated in the instant compositions in finely divided form, i.e., with an average particle size of less than 500 11m, more preferably less than 250 ⁇ m, especially less than about 150 ⁇ m.
  • Highly preferred materials include methyl o-acetoxy benzoate, sodium-p-acetoxy benzene sulphonate, Bisphenol A diacetate, tetra acetyl ethylene diamine, tetra acetyl hexamethylene diamine and tetra acetyl methylene diamine.
  • the essential phosphate builder component preferably comprises at least 8% by weight thereof of orthophosphate, and/or pyrophosphate salts, the remainder preferably consisting mainly of tripolyphosphate salts, in particular, the alkali metal, ammonium and substituted ammonium salts.
  • the phosphate builder is present in the finished product at a level of from 5% to 90% by weight of the composition, preferably from 8% to 50%.
  • the low phosphate compositions of the invention preferably contain phosphorus in an amount less than that contained in 28% by weight of anhydrous sodium tripolyphosphate.
  • the compositions of the invention will in general contain at least 2%, especially at least 3% by weight of the builder of orthophosphate salts, and at least 6%, especially at least 9% of the builder of pyrophosphate salts.
  • Suitable orthophosphate salts can be represented by the general formula wherein M is an alkali metal, ammonium or substituted ammonium cation, and x is 1, 2 or 3.
  • M is sodium or potassium, especially sodium, although liquid detergent compositions of the invention can contain builder in the form of the ammonium or alkanolammonium salts, e.g., the salts formed from monoethanolamine, diethanolamine, triethanolamine and mixtures thereof.
  • alkali metal salts are present in granular detergents in the form of crystalline hydrates having up to 12 moles of water associated with each mole of alkali metal phosphate.
  • Ammonium and substituted ammonium salts can be obtained commercially or can be formed by neutralization of orthophosphoric acid or acid salt.
  • Pyrophosphate is an additional preferred component of the present invention.
  • Monosodium pyrophosphate and trisodium pyrophosphate also exist, the latter as the anhydrous form or the mono- or nona-hydrate.
  • the generic formula for the anhydrous forms of these compounds can be expressed as M x H y P 2 O 7' where M is alkali metal and x and y are integers having the sum of 4.
  • polymeric polycarboxylates these are suitably derived from polycarboxylates selected from maleic acid, citraconic acid, aconitic acid, fumaric acid, mesaconic acid, phenyl maleic acid, benzyl maleic acid, itaconic acid and methylene malonic acid monomers, or from the anhydrides of the above monomers where these exist.
  • the polycarboxyl monomer provides at least 15, more preferably at least 33, especially at least 45 moles percent of the monomeric species comprising the polymer species.
  • the polymer can be selected from homopolymers of the above polycarboxyl monomers; or copolymers of two or more of the above polycarboxyl monomers; or copolymers of one or more of the above polycarboxyl monomers with an unsaturated polymerisable monomer other than the specified polycarboxyl monomers.
  • suitable polymerizable unsaturated monomers include wherein R 1 is a C, to C, 2 alkyl group or a C, to C 12 acyl group, R 1 optionally being hydroxy substituted.
  • R 2 is H or CH 3 and R 3 is H, or a C, to C, o alkyl group, R 2 , R 3 optionally being hydroxy substituted, wherein each of R 4 to R 7 is H or an alkyl group such that R 4 to R 7 together have from 1 to 20 carbon atoms, R 4 -R 7 each optionally being hydroxy substituted.
  • Highly preferred polymeric polycarboxylates in the present invention are the copolymers of maleic acid with the above unsaturated monomers, optionally wholly or partly neutralised by sodium or potassium. All may be made by heating together maleic anhydride and the other monomer in an appropriate solvent, such as benzene, cyclohexene, or in some cases in excess of one of the monomers, in the presence of a catalyst such as an organic peroxide or azo-bisbutyronitrile.
  • an appropriate solvent such as benzene, cyclohexene, or in some cases in excess of one of the monomers, in the presence of a catalyst such as an organic peroxide or azo-bisbutyronitrile.
  • a catalyst such as an organic peroxide or azo-bisbutyronitrile
  • the molecular weight of the polymeric polycarboxylate is expressed as that of the unneutralised acid form thereof. Generally, the average molecular weight falls in the range from 500 to 2,000,000.
  • the alkyl vinyl ethers of class (a) above are preferably methyl vinyl ethers.
  • Preferred molecular weights for these copolymers are in the range from 12,000 to 1,500,000, more preferably 50,000 to 300,000.
  • Copolymers in anhydride form believed to be of this class are commercially available from GAF Corporation under the trade names Gantrez (RTM) AN119 (MWt. 200,000 in anhydride form), Gantrez (RTM) AN139 (MWt. 500,000 in anhydride form), AN149 (MWt. 750,000 in anhydride form) and AN169 (MWt. 1,125,000 in anhydride form).
  • Ethyl and methyl vinyl ether/maleic anhydride copolymers are also available from BASF under the trade name Sokalan (RTM) and having molecular weight about 30,000.
  • the molecular weight of these copolymers is the viscosity average molecular weight and is determined as follows:
  • the acrylic-maleic copolymer derived from monomers of class (b) above are preferably based upon acrylic acid or methyl methacrylate, although higher alkyl esters can be employed.
  • the manufacture of these polymers, and the control of the molar ratio of the monomers one to other is described by Seymour, Harris and Branum in Industrial and Engineering Chemistry, Volume 41, pages 1509 to 1513, 1949.
  • copolymers wherein the molar ratio of acrylate ester to maleic acid is from 4:1 to 1:1 are employed herein, their molecular weight is preferably in the range from 3,000 to 1,500,000, especially from 12,000 to 100,000.
  • the molecular weight of these copolymers is determined by the method described above.
  • the copolymers are preferably of high molecular weight and are preferably based on ethylene.
  • the preferred molecular weight range is from 275,000 to 1,500,000.
  • Another preferred group of materials within this class are copolymers of maleic anhydride or acid with propylene, isobutylene, alkyl substituted isobutylene and, especially, di-isobutylene, having molecular weight in the range from 500 to 50,000 and molar ratio of olefine to maleic acid in the range from 1:1 to 1:2.
  • Suitable materials of this type are availale under the trade names "Empicryl (RTM” of Albright and Wilson Limited, and "Orotan (RTM)” of Rohm and Haas.
  • the vinyl pyrrolidone maleic copolymers preferably have molecular weight in the range from 3,000 to 50,000, especially 20,000 to 30,000.
  • the molecular weight is determined by the method described above but employing 1 M NaOH as solvent and using the equation II above.
  • the styrene-maleic acid copolymers preferably have molecular weight about 300,000.
  • the molecular weight is determined by the same method but employing acetone as solvent and using the equation I above.
  • copolymers are those of methyl and ethyl vinyl ether-maleic anhydride or acid described above.
  • a further essential ingredient of the detergent compositions of the invention is a surfactant selected from anionic, nonionic, zwitterionic or ampholytic surfactants.
  • the surfactant is present at a level of from 2% to 35%, more preferably from 3% to 20% of the composition.
  • a typical listing of the classes and species of these surfactants is given in US-A-3,663,961.
  • Suitable synthetic anionic surfactants are water-soluble salts of alkyl benzene sulfonates, alkyl sulfates, alkyl polyethoxy ether sulfates, paraffin sulfonates, alpha-olefin sulfonates, alpha-sulfo-carboxylates and their esters, sulfonates, alpha-sulfo-carboxylates and their esters, alkyl glyceryl ether sulfonates, fatty acid monoglyceride sulfates and sulfonates, alkyl phenol polyethoxy ether sulfates, 2 - acyloxy - alkane - 1 - sulfonate, and beta-alkyloxy alkane sulfonate.
  • a particularly suitable class of anionic surfactants includes water-soluble salts, particularly the alkali metal, ammonium and alkanolammonium salts or organic sulfuric reaction products having in their molecular structure an alkyl or alkaryl group containing from 8 to 22, especially from 10 to 20 carbon atoms and a sulfonic acid or sulfuric acid ester group. (Included in the term “alkyl” is the alkyl portion of acyl groups).
  • Examples of this group of synthetic detergents which form part of the detergent compositions of the present invention are the sodium and potassium alkyl sulfates, especially those obtained by sulfating the higher alcohols (C 8 - 18 ) carbon atoms produced by reducing the glycerides of tallow or coconut oil and sodium and potassium alkyl benzene sulfonates, in which the alkyl group contains from 9 to 15, especially 11 to 13, carbon atoms, in straight chain or branched chain configuration, e.g.
  • anionic detergent compounds herein include the sodium C 10 - 1S 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; and sodium or potassium salts of alkyl phenol ethylene oxide ether sulfate containing 1 to 10 units of ethylene oxide per molecule and wherein the alkyl groups contain 8 to 12 carbon atoms.
  • Other useful anionic detergent compounds herein include the water-soluble salts or esters of a-sulfonated fatty acids containing from 6 to 20 carbon atoms in the fatty acid group and from 1 to 10 carbon atoms in the ester group; water-soluble salts of 2 - acyloxy - alkane - 1 - sulfonic acids containing from 2 to 9 carbon atoms in the acyl group and from 9 to 23 carbon atoms in the alkane moiety; alkyl ether sulfates containing from 10 to 18, especially 12 to 16, carbon atoms in the alkyl group and from 1 to 12, especially 1 to 6, more especially 1 to 4 moles of ethylene oxide; water-soluble salts of olefin sulfonates containing from 12 to 24, preferably 14 to 16, carbon atoms, especially those made by reaction with sulfur trioxide followed by neutralization under conditions such that any sultones present are hydrolysed to the corresponding hydroxy alkane sulfonates; water-
  • alkane chains of the foregoing non-soap anionic surfactants can be derived from natural sources such as coconut oil or tallow, or can be made synthetically as for example using the Ziegler or Oxo processes. Water solubility can be achieved by using alkali metal, ammonium or alkanolammonium cations; sodium is preferred. Magnesium and calcium are preferred cations under circumstances described by BE-A-843,636.
  • a preferred mixture contains alkyl benzene sulfonate having 11 to 13 carbon atoms in the alkyl group or paraffin sulfonate having 14 to 18 carbon atoms and either an alkyl sulfate having 8 to 18, preferably 12 to 18, carbon atoms in the alkyl group, or an alkyl polyethoxy alcohol sulfate having 10 to 16 carbon atoms in the alkyl group and an average degree of ethoxylation of 1 to 6.
  • Nonionic surfactants suitable for use in the detergent component of the present composition include compounds produced by the condensation of ethylene oxide groups (hydrophilic in nature) with an organic hydrophobic compound, which may be aliphatic or alkyl aromatic in nature.
  • the length of the polyoxyethylene group 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.
  • Suitable nonionic surfactants include:
  • Suitable cationic surfactants are those having a critical micelle concentration for the pure material of at least 200 ppm and preferably at least 500 ppm specified at 30°C and in distilled water. Literature values are taken where possible, especially surfact tension or conductimetric values-see Critical Micelle Concentrations of Aqueous Surfactant System, P. Mukerjee and K. J. Mysels, NSRDS-NBS 37 (1971).
  • a highly preferred group of cationic surfactants of this type have the general formula:- wherein R' is selected from C 8-20 alkyl, alkenyl and alkaryl groups; R 2 is selected from C 1-4 alkyl and benzyl groups; Z is an anion in number to give electrical neutrality; and m is 1, or 3; provided that when m is 2 R 1 has less than 15 carbon atoms and when m is 3, R' has less than 9 carbon atoms.
  • compositions of this mono-long chain type include those in which R' is C 10 to C 16 alkyl group.
  • Particularly preferred compositions of this class include C 12 alkyl trimethylammonium halide and C 14 alkyl trimethylammonium halide.
  • the R' chains should have less than 14 carbon atoms.
  • Particularly preferred cationic materials of this class include di-C 8 alkyldimethylammonium halide and di-C 1O alkyldimethylammonium halide materials.
  • the R' chains should be less than 9 carbon atoms in length.
  • An example is trioctyl methyl ammonium chloride.
  • R' represents a C 6-24 alkyl or alkenyl group or a C 6-12 alkaryl group
  • each R 2 independently represents a (C n H 2n O) x H group where n is 2, 3 or 4 and x is from 1 to 14, the sum total of C n H 2n O groups in R 2 m being from 1 to 14
  • each R 3 independently represents a C 1-12 alkyl or alkenyl group, an aryl group or a C 1-6 alkaryl group
  • m is 1, 2 or 3
  • A is an anion.
  • R' is selected from C 6-24 alkyl or alkenyl groups and C 6-12 alkaryl groups
  • R 3 is selected from C 1-12 alkyl or alkenyl groups and C 1-6 alkaryl groups.
  • m is 2, however, it is preferred that the sum total of carbon atoms in R' and R 3 3 - m is no more than about 20 with R' representing a C 8-18 alkyl or alkenyl group. More preferably the sum total of carbon atoms in R' and R1 3-m is no more than about 17 with R' representing a C 10-16 alkyl or alkenyl group.
  • m 1, it is again preferred that the sum total of carbon atoms in R' and R 3 3 - m is no more than about 17 with R' representing a C 10-16 alkyl or alkaryl group.
  • the total number of alkoxy radicals in polyalkoxy groups (R 2 m ) directly attached to the cationic charge centre should be no more than 14.
  • the total number of such alkoxy groups is from 1 to 7 with each polyalkoxy group (R 2 ) independently containing from 1 to 7 alkoxy groups; more preferably, the total number of such alkoxy groups is from 1 to 5 with each polyalkoxy group (R 2 ) independently containing from 1 to 3 alkoxy groups.
  • cationic surfactants having the formula: wherein R' is as defined immediately above, n is 2 or 3 and m is 1, 2 or 3.
  • Particularly preferred cationic surfactants of the class having m equal to 1 are dodecyl dimethyl hydroxyethyl ammonium salts, doecyl dimethyl hydroxypropyl ammonium salts, myristyl dimethyl hydroxyethyl ammonium salts and dodecyl dimethyl dioxyethylenyl ammonium salts.
  • particularly preferred cationic surfactants are dodecyl dihydroxyethyl methyl ammonium salts, dodecyl dihydroxypropyl methyl ammonium salts, dodecyl dihydroxyethyl ethyl ammonium salts, myristyl dihydroxyethyl methyl ammonium salts, cetyl dihydroxyethyl methyl ammonium salts, stearyl dihydroxyethyl methyl ammonium salts, oleyldihydroxyethyl methyl ammonium salts, and dodecyl hydroxyethyl hydroxypropyl methyl ammonium salts.
  • particularly preferred cationic surfactants are dodecyl trihydroxyethyl ammonium salts, myristyl trihydroxyethyl ammonium salts, cetyl trihydroxyethyl ammonium salts, stearyl trihydroxyethyl ammonium salts, oleyl trihydroxyethyl ammonium salts, dodecyl dihydroxyethyl hydroxypropyl ammonium salts and dodecyl trihydroxypropyl ammonium salts.
  • salt counterions can be employed, for example, chlorides, bromides and borates.
  • Salt counterions can also be selected from organic acid anions, however, such as the anions derived from organic sulphonic acids and from sulphuric acid esters.
  • organic acid anion is a C 6-12 alkaryl sulphonate.
  • cationic surfactants especially preferred are dodecyl dimethyl hydroxyethyl ammonium salts and dodecyl dihydroxyethyl methyl ammonium salts.
  • the above water-soluble cationic surfactants can be employed in nonionic/cationic surfactant mixtures in a weight ratio of from 10:6 to 20:1, more preferably from 10:2 to 10:6, and particularly from 10:3 to 10:5.
  • ingredients which can be added to the present composition include suds modifiers, chelating agents, anti-redeposition and soil suspending agents, optical brighteners, bactericides, anti-tarnish agents, enzymatic materials, fabric softeners, antistatic agents, perfumes, antioxidants and bleach catalysts.
  • US-A-3,933,672 discloses a silicone suds controlling agent.
  • the silicone material can be represented by alkylated polysiloxane materials such as silica aerogels and xerogels and hydrophobic silicas of various types.
  • the silicone material can be described as siloxane having the formula: wherein x is from 20 to 2,000 and R and R' are each alkyl or aryl groups, especially methyl, ethyl, propyl, butyl and phenyl.
  • the polydimethylsiloxanes (R and R' are methyl) having a molecular weight within the range of from 200 to 2,000,000, and higher, are all useful as suds controlling agents.
  • Additional suitable silicone materials wherein the side chain groups R and R' are alkyl, aryl, or mixed alkyl or aryl hydrocarbyl groups exhibit useful suds controlling properties.
  • the like ingredients include diethyl-, dipropyl-, dibutyl-, methyl-, ethyl-, phenylmethylpolysiloxanes and the like.
  • Additional useful silicone suds controlling agents can be represented by a mixture of an alkylated siloxane, as referred to hereinbefore, and solid silica. Such mixtures are prepared by affixing the silicone to the surface of the solid silica.
  • a preferred silicone suds controlling agent is represented by a hydrophobic silanated (most preferably trimethylsilanated) silica having a particle size in the range from 10 nm to 20 nm and a specific surface area above 50 M 2 /g intimately admixed with dimethyl silicone fluid having a molecular weight in the range from 500 to 200,000 at a weight ratio of silicone to silanated silica of from 1:1 to 1:2.
  • the silicone suds suppressing agent is advantageously releasably incorporated in a water-soluble or water-dispersible, substantially non-surface-active detergent-impermeable carrier.
  • Particularly useful suds suppressors are the self-emulsifying silicone suds suppressors, described in DE-A-2,646,126.
  • An example of such a compound is DC-544, commercially available from Dow Corning, which is a siloxane/glycol copolymer.
  • Suds modifiers as described above are used at levels of up to 5%, preferably from 0.1 to 2% by weight of the nonionic surfactant. They can be incorporated into the particulates of the present invention or can be formed into separate particulates that can then be mixed with the particulates of the invention.
  • the incorporation of the suds modifiers as separate particulates also permits the inclusion therein of other suds controlling materials such as C 20 -C 24 fatty acids, microcrystalline waxes and high MWt copolymers of ethylene oxide and propylene oxide which would otherwise adversely affect the dispersibility of the matrix. Techniques for forming such suds modifying particulates are disclosed in the previously mentioned US ⁇ A ⁇ 3,933,672.
  • the detergent compositions of the invention can also contain supplemental detergency builders such as organic builders and aluminosilicates.
  • Suitable organic alkaline detergency builder salts are:
  • a further class of builder salts is the insoluble alumino silicate type which functions by cation exchange to remove polyvalent mineral hardness and heavy metal ions from solution.
  • a preferred builder of this type has the formulation Naz(AI02)z(Si02)y . xH 2 0 wherein z and y are integers of at least 6, the molar ratio of z to y is in the range from 1.0 to 0.5 and x is an integer from 15 to 264.
  • Compositions incorporating builder salts of this type form the subject of GB-A-1,429,143, DE-A-2,433,485 and DE-A-2,525,778.
  • the detergent compositions of the invention can also be supplemented by bleaches, especially sodium perborate tetrahydrate or sodium percarbonate at levels from 5% to 35% by weight.
  • the compositions also preferably include from 0.05% to 0.6% by weight (acid basis), preferably from 0.06% to 0.3% of aminopolyphosphonic acid, or salt thereof, having the general formula: wherein n is an integral number from 0 to 3, and each R is individually hydrogen or CH 2 PO 3 H 2 provided that at least half of the radicals represented by R are CH 2 PO 3 H 2 .
  • Preferred aminopolyphosphonic acids are selected from nitrilotri(methylenephosphonic acid), ethylene - diaminetetra(methylenephosphonic acid), diethylenetriamine(pentamethylenephosphonic acid), and mixtures thereof.
  • alkali metal, or alkaline earth metal, silicate can also be present.
  • the alkali metal silicate is preferably from 3% to 8% by weight.
  • Suitable silicate solids have a molar ratio of Si0 2 /alkali metal 2 0 in the range from 1.0 to 3.3, more preferably from 1.5 to 2.0.
  • Other suitable ingredients include soil-suspending agents such as the water-soluble salts of carboxymethyl cellulose and of methyl vinylether/maleic anhydride copolymer, nonionic cellulose materials such as hydroxyethyl cellulose, and polyethylene glycols.
  • the above products provide good cleaning and whiteness maintenance performance at both low and high wash temperatures on both synthetic and natural fabrics.
  • the copolymer is replaced by an equal weight of a copolymer of acrylic acid and maleic acid having a molecular weight of about 70,000 and an acrylic/maleic mole ratio of about 3:1 (Examples VII to XII).
  • the products again provide good cleaning and whiteness maintenance performance at both low and high wash temperatures on both synthetic and natural fabrics.

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Claims (10)

1. Eine körnige Reinigungsmittelzusammensetzung, enthaltend
(a) 2 Gew.-% bis 35 Gew.-% organisches oberflächenaktives Mittel, ausgewählt aus anionischen, nichtionischen, amphoteren und zwitterionischen oberflächenaktiven Mitteln und Mischungen davon,
(b) 5 Gew.-% bis 90 Gew.-% Phosphatdetergensgerüststoff, enthaltend wenigstens 6 Gew.-% davon eines Gemisches von wasserlöslichen Orthophosphat- und Pyrophosphatsalzen in einem Gewichtsverhältnis von 3:7 bis 1:20, und
(c) 0,1 Gew.-% bis 2 Gew.-% einer homo- oder copolymeren Polycarbonsäure, oder eines Salzes oder eines Anhydrides davon, wobei die Polycarbonsäure wenigstens 2 Carboxylreste voneinander durch nicht mehr als zwei Kohlenstoffatome getrennt aufweist,

dadurch gekennzeichnet, daß die Zusammensetzung zusätzlich 0,5 Gew.-% bis 20 Gew.-% an organischem Peroxysäurebleichmittelprecursor enthält, wobei das Gewichtsverhältnis von organischem Peroxysäurebleichmittelprecursor zu polymer Polycarbonsäure 10:1 bis 1:3 beträgt.
2. Eine Zusammensetzung nach Anspruch 1, dadurch gekennzeichnet, daß der Phosphatdetergensgerüststoff 50 Gew.-% bis 90 Gew.-% davon an wasserlöslichen Tripolyphosphatsalzen und 10 Gew.-% bis 50 Gew.-% davon des Gemisches von wasserlöslichen Orthophosphat- und Pyrophosphatsalzen enthält.
3. Eine Zusammensetzung nach Anspruch 1 oder 2, enthaltend Phosphor in einer Menge, die jene nicht überschreitet, welche in 28 Gew.-% wasserfreiem Natriumtripolyphosphat enthalten ist.
4. Eine Zusammensetzung nach einem der Ansprüche 1 bis 3, dadurch gekennzeichnet, daß die polymeren Polycarbonsäure ein mittleres Molekulargewicht im Bereich von 500 bis 2,000.000 aufweist, und ein Copolymer ist, welches
(a) Polycarbonsäureeinheiten der allgemeinen Formel I
Figure imgb0030
worin X, Y und Z jeweils aus der Gruppe ausgewählt sind, die aus Wasserstoff, Methyl, Aryl, Alkaryl, Carboxyl, Hydroxy und Carboxymethyl besteht; wenigstens einer der Reste X, Y und Z aus der Gruppe ausgewählt ist, die aus Carboxyl und Carboxymethyl besteht, mit der Maßgabe, daß X und Y nur dann Carboxymethyl sein können, wenn Z aus Carboxyl und Carboxymethyl ausgewählt ist, und wobei nur einer der Reste X, Y und Z Methyl, Aryl, Hydroxyl oder Alkaryl sein kann, und
(b) Monomereinheiten, ausgewählt aus
Figure imgb0031
worin R, eine C1―C12-Alkylgruppe oder eine C1―C12-Acylgruppe, die gegebenenfalls Hydroxy-substituiert ist, bedeutet,
Figure imgb0032
worin R2 H oder CH3 ist, und R3 H oder eine C1―C10-Alkylgruppe ist, wobei R2 und/oder R3 gegebenenfalls Hydroxysubstituiert sein können,
Figure imgb0033
worin jeder der Reste R4 bis R7 H oder eine Alkylgruppe derart sind, daß R4 bis R7 gemeinsam 1 bis 20 Kohlenstoffatome aufweisen, wobei R4 bis R7 jeweils gegebenenfalls Hydroxysubstituiert sein können, und
Figure imgb0034
worin R8 Benzyl oder Pyrrolidon ist, enthält.
5. Eine Zusammensetzung nach Anspruch 4, dadurch gekennzeichnet, daß die polymere Polycarbonsäure ein Copolymer von Maleinsäure oder Maleinsäureanhydrid mit Methylvinylether oder Ethylvinylether oder Acrylsäure ist, das ein mittleres Molekulargewicht im Bereich von 12.000 bis 1,500.000 aufweist.
6. Eine Zusammensetzung nach einem der Ansprüche 1 bis 5, dadurch gekennzeichnet, daß das Gewichtsverhältnis von organischem Peroxysäureblechmittelprecursor zu polymerer Polycarbonsäure 5:1 bis 1:2 beträgt.
7. Eine Zusammensetzung nach einem der Ansprüche 1 bis 6, dadurch gekennzeichnet, daß der organische Peroxysäure bleichmittelprecursor ein Peressigsäurebleichmittelprecursor ist.
8. Eine Zusammensetzung nach einem der Ansprüche 1 bis 7, dadurch gekennzeichnet, daß sie weiterhin 5 Gew.-% bis 35 Gew.-% eines Peroxysalzbleichmittels enthält.
9. Eine Zusammensetzung nach einem der Ansprüche 1 bis 8, dadurch gekennzeichnet, dass sie weiterhin 0.05% bis 0.2%, bezogen auf das Magnesiumgewicht, eines wasserlöslichen Magnesiumsalzes enthält.
10. Eine Zusammensetzung nach einem der Ansprüche 1 bis 9, dadurch gekennzeichnet, dass sie weiterhin 0.05 Gew.-% bis 0.4 Gew.-% (bezogen auf die Säureform) Äthylendiamin - tetramethylenphosphonsäure, Diäthylentriamin - pentamethylenphosphonsäure, oder entsprechende Salze enthält.
EP82301776A 1981-04-08 1982-04-05 Reinigungsmittelzusammensetzungen Expired EP0063017B1 (de)

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ATE30738T1 (de) * 1981-05-30 1987-11-15 Procter & Gamble Reinigungsmittelzusammensetzung enthaltend einen wirkungsfoerdernden zusatz und ein kopolymer zum gewaehrleisten der vertraeglichkeit desselben.
ATE21930T1 (de) * 1982-06-01 1986-09-15 Procter & Gamble Detergens-fluessigkeiten und zusammensetzungen fuer ihre verwendung.
US4455249A (en) * 1982-10-21 1984-06-19 Colgate-Palmolive Company Stabilized bleach and laundering composition
EP0132792A1 (de) * 1983-07-20 1985-02-13 DISPO-Kommerz AG Wasserlösliche, pulverförmige Reinigungsmittel für harte Oberflächen
EP0373691A3 (de) * 1988-12-16 1991-05-15 Unilever N.V. Stabilisierte, granulare Bleichmittel
US6117357A (en) * 1996-07-29 2000-09-12 The Procter & Gamble Company Unsymmetrical acyclic imide bleach activators and compositions employing the same
BR9712318A (pt) * 1996-10-15 2002-01-15 Procter & Gamble Composto ativador de alvejante, composição de aditivo alvejante, composição de alvejamento e método para alvejar tecidos
DE69808966T2 (de) * 1997-11-10 2003-06-18 Procter & Gamble O-substitutierte n,n-diacylhydroxylamine als bleichaktivatoren und diese enthaltende zusammensetzungen
DE19935258A1 (de) * 1999-07-27 2001-02-01 Henkel Kgaa Bleichmittelzusammensetzungen

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GB1460893A (en) * 1973-01-31 1977-01-06 Unilever Ltd Fabric washing powder
BE848034R (fr) * 1976-09-21 1977-05-05 Composition detergente avec adjuvants a base d'ortho- et de pyrophosphates hydrosolubles
GB1596756A (en) * 1977-04-22 1981-08-26 Procter & Gamble Ltd Detergent compositions
DE2960405D1 (en) * 1978-10-03 1981-09-17 Unilever Plc Detergent compositions

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GR76045B (de) 1984-08-03

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