US3850832A - Washing, rinsing and cleansing agent compositions containing furan-maleic anhydride copolymer sequestering agents - Google Patents

Washing, rinsing and cleansing agent compositions containing furan-maleic anhydride copolymer sequestering agents Download PDF

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US3850832A
US3850832A US00314337A US31433772A US3850832A US 3850832 A US3850832 A US 3850832A US 00314337 A US00314337 A US 00314337A US 31433772 A US31433772 A US 31433772A US 3850832 A US3850832 A US 3850832A
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percent
weight
sequestering
copolymer
washing
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B Wegemund
H Lehmann
E Schmadel
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Henkel AG and Co KGaA
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Henkel AG and Co KGaA
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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
    • C11D3/16—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

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  • ABSTRACT Washing, rinsing and cleansing agent compositions containing from S to 95 percent by weight of the usual ingredients and from 95 to 5 percent by weight of copolymer-carboxylate sequestering agents capable of sequestering alkaline earth metal ions prepared from approximately equal molar amounts of maleic acid and furan, and having a molecular weight of from about 300 to 20,000, said copolymer-carboxylate sequestering agents being present as water-soluble salts capable of complex formation with alkaline earth metal ions.
  • the invention also resides in the process of sequestering alkaline earth metal ions using aqueous solutions of the washing, rinsing and cleansing agent compositions.
  • An object of the invention is to replace the known inorganic or organic sequestering agents, containing phosphorus and/or nitrogen, wholly or partly, by sequestering agents that do not contain such chemical elements and possess beyond that a good washing and cleansing power.
  • a further object of the present invention is the development of washing, rinsing and cleansing compositions consisting essentially of (a) from to 95 percent by weight of at least one compound having a cleaning action selected from the group consisting of l) anionic surface-active compounds, non-ionic surface-active compounds, amphoteric surface active compounds, and mixtures thereof, (2) organic builder salts and inorganic builder salts, and (3) mixtures of l) and (2), and (b) from 95 to 5 percent by weight of at least one copolymer-carboxylate sequestering agent capable of sequestering alkaline earth metal ions prepared from approximately equal molar amounts of maleic acid and furan, and having a molecular weight of from about 300 to 20,000, said copolymer-carboxylate sequestering agents being present as water-soluble salts capable of complex formation with alkaline earth metal ions.
  • a yet further object of the present invention is the development in the process of washing, rinsing and cleansing solid materials which comprises contacting solid materials having soil thereon with an aqueous solution containing from 0.5 to 80 gms/liter of a cleansing agent consisting of from 5 to 95 percent of at least one compound having a cleaning action and from 95 to 5 percent of a sequestering agent capable of sequestering alkaline earth metal ions, for a time sufiicient to disperse and dissolve said soil in said aqueous solution and removing said cleansed solid materials, the improvement consisting of utilizing, as said sequestering agent, at least one copolymer-carboxylate sequestering agent capable of sequestering alkaline earth metal ions prepared from approximately equal molar amounts of maleic acid and furan, and having a molecular weight of from about 300 to 20,000, said copolymer-carboxylate sequestering agents being present as water soluble salt capable of complex formation with alkaline earth metal ions.
  • This invention relates to washing. rinsing or cleansing agents, containing sequestering agents for alkaline earth metal ions, being present as solids, pastes, dispersions or solutions, of the following composition, based on the products free of water and/or solvents:
  • polymers prepared from approximately equal molar amounts of maleic acid and furan having a molecular weight of about 300 to 20,000, preferably 500 to 5,000, said polymers being present preferably in the form of their watersoluble salts capable of sequestering or of complex formation with alkaline earth metal ions.
  • compositions of the invention are washing, rinsing and cleansing compositions consisting essentially of (a) from 5 to 95 percent by weight of at least one compound having a cleaning action selected from the group consisting of l) anionic surface-active compounds, non-ionic surface-active compounds, amphoteric surface-active compounds, and mixtures thereof, (2) organic builder salts and inorganic builder salts, and (3) mixtures of l) and (2), and (b) from 95 to 5 percent by weight of at least one copolymercarboxylate sequestering agent capable of sequestering alkaline earth metal ions prepared from approximately equal molar amounts of maleic acid and furan, and having a molecular weight of from about 300 to 20,000, said copolymercarboxylate sequestering agents being present as water-soluble salts capable of complex formation with alkaline earth metal ions.
  • copolymercarboxylate may also be employed in their free acid form; however, since the copolymer as polymerized contains acid anhydride groups, it is preferable to convert the same to the water-soluble salts capable of sequestering alkaline earth metal ions.
  • the washing, rinsing and cleansing compositions of the invention contain at least one substance with a cleaning action.
  • This consists of an inorganic or organic builder salt or a surface-active basic detergent substance or a combination of these.
  • the agents usually contain several such substances having a cleaning action, the types of which depend on the ultimate use of the agents.
  • agents When the agents, according to the invention, are solids, they are mostly present as fine to grainy powders, as agglomerates or granulates. Such agents can be practically anhydrous; but they can also contain water of crystallization or water of hydration.
  • the agents of the invention may. however, also be utilized in the form of pastes, dispersions or solutions. In these forms. they contain smaller or larger amounts of liquid solvents.
  • solutions can be used that contain up to 1 percent by weight, preferably up to 4 percent by weight, of the solid agent.
  • the solutions, dispersions or pastes may also be substantially more concentrated, so that the amounts of the solvent constitutes up to 30 percent by weight, preferably up to 50 percent by weight.
  • dispersions or pastes also hydrotropic substances may be incorporated.
  • the present invention also includes in the process of washing, rinsing and cleansing solid materials which comprises contacting solid materials having soil thereon with an aqueous solution containing from 0.5 to 80 gms/liter of a cleansing agent consisting of from 5 to 95 percent of at least one compound having a cleaning action and from 95 to 5 percent of a sequestering agent capable of sequestering alkaline earth metal ions, for a time sufficient to disperse and dissolve said soil in said aqueous solution and removing said cleansed solid materials, the improvement consisting of utilizing, as said sequestering agent, at least one copolymer-carboxylate sequestering agent capable of sequestering alkaline earth metal ions prepared from approximately equal molar amounts of maleic acid and furan, and having a molecular weight of from about 300 to 20,000, said copolymer-carboxylate sequestering agents being present as water-soluble salts capable of complex formation with alkaline earth metal ions.
  • copolymers The polymers of the above definition that can be used according to the invention, particularly their salts, hereafter called copolymers, are described in the .loumal of Macromolecular Science-Chemistry, Vol. A 4(1), pages 52 to 54.
  • the products can be obtained by copolymerization of about equimolar amounts of furan and maleic acid anhydride or by polymerization of the Diels'Alder adduct of furan and maleic acid anhydride, for example, by reaction in a benzene solution with azobisisobutyronitrile as a catalyst.
  • the polymers thus obtained are converted into their salts by saponification with inorganic or organic bases.
  • copolymer compounds are preferably utilized as the sodium salts. They can also be present as other alkali metal salts such as potassium salts or as ammonium salts, as well as water-soluble salts of organic bases, particularly of the alkyl amines or alkylolamines with at most 6 carbon atoms in the molecule, for instance, as salts of dior trimethylamine, mono-, dior triethylamine, mono-, dior triethanolamine, monoor dihydroxypropylamine, etc.
  • alkali metal salts such as potassium salts or as ammonium salts
  • organic bases particularly of the alkyl amines or alkylolamines with at most 6 carbon atoms in the molecule, for instance, as salts of dior trimethylamine, mono-, dior triethylamine, mono-, dior triethanolamine, monoor dihydroxypropylamine, etc.
  • Copolymer-Sodium Salt 230 gm of a polymer produced by polymerization of l,2,3,6-tetrahydro-3,6-epoxy-phthalic acid anhydride with an average molecular weight of about 4000, were suspended in an eight-fold amount of water and stirred at 70C for a length of time (about 1 hour) until a clear solution was obtained. Then the solution was adjusted to a pH of 8 to 9 with a percent aqueous solution of sodium hydroxide, filtered, and the filtrate was evaporated to dryness. The preparation obtained after drying had a Hampshire Test Value of 610.
  • Copolymer-Ammonium Salt A suspension of 200 gm of a product obtained by copolymerization of equimolar amounts of maleic acid anhydride and furan, with an average molecular weight of 2500 was stirred in 1.8 liters of water at 70C until a clear solution was obtained. The solution was adjusted to a pH of 8 to 9 with concentrated aqueous ammoniz, and ammonia, ammonium salt was precipitated by the addition of ethanol. The ammonium salt thus obtained had a Hampshire Test Value of 500.
  • the Hampshire Test Value is a measure for the cal cium carbonate-binding power. An exact description of the method of determination is found in the Hampshire NTA Technical Bulletin," appendix p.A2 (June 1960) by Hampshire Chemical Corp.
  • the washing, rinsing or cleansing agent compositions of the invention may be applied in numerous fields of technical nature as well as of the home for the most varied cleaning problems.
  • fields of application are the cleaning of instruments, apparatus pipe lines and vessels of wood, plastics, metal, ceramics, glass, etc. in the industry or in commerical plants, the cleaning of furniture, walls, floors, of objects of ceramics, glass, metal, wood, plastics, the cleaning of polished or lacquered surfaces in the home, etc.
  • a particularly important application field is the washing and bleaching of textiles of any kind, as well as the automatic cleaning of dishes in industry, in commercial plants and in the home.
  • the above-defined copolymer-carboxylates are distinguished by a good sequestering power for alkaline earth metal ions and by a good cleansing and washing power.
  • composition of the products of the invention can be very different, according to their application field.
  • the products of the following composition are suitable:
  • agents may besides contain alkalineor neutral-reacting salts, corrosion inhibitors, disinfectants, other sequestering agents, particularly for heavy metals, and other customary ingredients of such agents.
  • cleaning agents for the production sector of the metal industry for instance, products of the following composition are suitable:
  • the soaking, prewashing, fine-washing, washing and bleaching agent compositions, according to the invention, containing copolymercarboxylates can be used with textiles derived from the most varied fibers of natural or synthetic origin. To them belong, for instance, cotton, viscose or linen as well as textiles, that contain highly processed cotton or synthetic fibers, such as polyamide, polyester, polyacrylonitrile, polyurethane, polyvinyl chloride or polyvinylidene chloride fibers.
  • the washing agent compositions of the invention can also be used for laundering of textiles, designated as easy care, occasionally also as no-iron, of synthetic flber-cotton-mixed fabrics.
  • composition of these agents possessing in a 1 percent aqueous solution a pl-l-value of at most H5, is within the range of the following recipe:
  • a tenside component consisting of anionic and- /or amphoteric and/0r nonionic tensides 5 to 95 percent, preferably to 80 percent by weight, of the copolymer-carboxylates, serving as builders 95 percent to 0, preferably 90 to percent by weight, of other inorganic and/or organic builders as well as optionally of a bleaching agent 0 to percent, preferably 1 to 25 percent by weight,
  • the bleaching component consists of bleaching-active, active chlorine or active oxygen compounds and optionally of activators and/or stabilizers for them.
  • condensed phosphates such as sodium tripolyphosphate as well as organic sequestering agents, containing phosphorus and/or nitrogen
  • these condensed phosphates are replaced in the present commercial agents, for instance, one-half by the copolymer-carboxylates and optionally by other conventional builders, free of P and/or N, this leads in the application in the conventional washing and cleansing liquors, already to a considerable reduction of the P and/or N concentration in the waste waters.
  • the sequestering power of the copolymercarboxylates is particularly pronounced with respect to the alkaline earth metals, so that they can support and enhance the washing and cleansing processes.
  • their sequestering power for heavy metals is, likewise as in other known sequestering builders,
  • sequestering agents for heavy metals in slight amounts of, for instance, from 0.1 to 5 percent, preferably 0.1 to 2 percent by weight.
  • sequestering agents for heavy metals particularly for copper. for instance. ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid or aminotriethylidene-diphosphonic acid or their salts are suitable.
  • the tenside component contains preferably at least 50 percent by weight of anionic tensides.
  • anionic tensides substantially surface-active sulfates and/or sulfonates and/or soaps are to be understood.
  • the amount of builders, including the copolymer-carboxylates constitutes preferably from 0.5- to 7-fold, and particularly from lto 5-fold of the total tenside component. If the invention preparations contain more than percent by weight of the tenside component, they are mostly used for commercial purposes, for instance in laundries and in the textile industry, where they are rarely applied alone, more frequently in combination with other conventional additives. r
  • composition of powdery preparations, according to the invention, used particularly as washing or cleansing agents is generally in the range of the following rec- 0 lpe:
  • a tenside component consisting substantially of anionic and/or amphoteric and/or nonionic tensides as well as, optionally, of one or more of the following substances:
  • foam stabilizers 0 to 10 percent, preferably 0.5 to 8 percent by weight of the tenside component.
  • washing agent ingredients such as soilsuspending agents, textile softeners, anti-microbial agents, enzymes, optical brighteners, dyes and perfumes, water.
  • the tenside component consists preferably at least to 50 percent by weight of anionic tensides from the group of the alkylbenzenesulfonates, alkanesulfonates, fatty-acid ester sulfonates, olefinsulfonates, fatty alcohol or fatty alcoholglycolether sulfates and of the soaps.
  • Foam-suppressing washing agents according to the preceding formula, suitable for use in drumwashing machines, contain either a combination of tensides of the sulfonate and/or sulfate type and soap in the quantitative ratio of from 30:l to 1:5, preferably from 20:1 to 1:2 and/or a non-tenside foam inhibitor.
  • the foam suppression is particularly pronounced, if the soap portion contains at least 5 percent and preferably at least 10 percent by weight of soaps from saturated fatty acids with 20 to 24, preferably 20 to 22 carbon atoms.
  • the bleaching component amounts mostly to to 40 percent, preferably 7 to 35 percent by weight of the total washing agent.
  • the powdery washing, rinsing and cleansing agent compositions can be produced by various known methods.
  • the single ingredients present as more or less fine powders or as granulates, can be mixed with each other.
  • an aqueous mixture of those ingredients which are insensitive to water and heat is dried in a known manner, for instance, on hot surfaces or in a hot airstream.
  • further ingredients which by such a processing could lose their effect completely or partly, are admixed, To them belong, for example, foam inhibitors, bleaching agents, enzymes, anti-microbial agents, dyes and perfumes, etc.
  • the tensides contain in the molecular at least one hydrophobic residue of mostly eight to 26, preferably 10 to 22 and especially 12 to 18 carbon atoms, and least one anionic, nonionic or amphoteric water-solubilizing group.
  • the preferably saturated hydrophobic residue is mostly aliphatic, but possibly also alicyclic in nature. It may be combined directly with the water-solubilizing groups or through intermediate members, such as through benzene rings, carboxylic-acid ester links, carbonamide links or sulfonic-acid amide links as well as through etheror ester-like residues of polyhydric alcohols.
  • Soaps which are derived from natural or syntheic fatty acids, possibly also from resin acids or napthenic acids. are utilizable as anionic detergent substances, especially if these acids have iodine values of not more than 30 and preferably less than 10.
  • the synethetic anionic tensides the sulfonates and sulfates possess particularly practical importance.
  • the sulfonates include, for example, alkylbenzenesulfonates with preferably straight-chain C especially C alkyl residues, alkanesulfonates, obtainable from preferably saturated aliphatic C especially C hydrocarbons by sulfochlorination or sulfoxidation, mixtures of alkenesulfonates, hydroxyalkanesulfonates and alkanedisulfonates, known under the name ofolefinsulfonates," which are formed by acidic or alkaline hydrolysis of the sulfonation products which first result from terminal or non-terminal C and preferably C olefins by sulfonation with sulfur trioxide.
  • the sulfonates include also salts, preferably alkali metal salts of a-sulfo fatty acids and salts of esters of these acids with mono or-polyhydric alcohols with one to four, and preferably one to two carbon atoms.
  • sulfonates are salts of fatty acid esters of hydroxyethanesulfonic acid or of dihydroxypropanesulfonic acid, the salts of the fatty alcohol esters of acids, containing one to eight carbon atoms, the alkylglycerylether sulfonates and the salts of the amide-like condensation products of fatty acids or sulfonic acids with aminoethanesulfonic acid.
  • Tensides of the sulfate type include fatty alcohol sulfates, especially those derived from coconut fatty alcohols, tallow fatty alcohols or from oleyl alcohol, also sulfatized fatty acid alkylolamides or fatty acid monoglycerides and sulfated alkoxylation products of alkylphenols (C alkyl), fatty alcohols, fatty acid amides, or fatty acid alkylolamides with 0.5 to 20, preferably one to eight, and particularly two to four ethylene and- /or propyleneglycol residues in the molecule.
  • fatty alcohol sulfates especially those derived from coconut fatty alcohols, tallow fatty alcohols or from oleyl alcohol, also sulfatized fatty acid alkylolamides or fatty acid monoglycerides and sulfated alkoxylation products of alkylphenols (C alkyl), fatty alcohols, fatty acid amides, or fatty acid
  • anionic tensides of the carboxylate type for example, the fatty acid esters or fatty alcohol ethers of hydroxycarboxylic acids, are suitable as well as the amide-like condensation products of fatty acids or sulfonic acids with aminocarboxylic acids, such as glycocoll, sarcosine or with protein hydrolysates.
  • the anionic tensides are mostly present as salts of the alkali metals, particularly of sodium, as well as the ammonium salts and salts of lower alkylamines or lower alkylolamines.
  • Nonionics include the polycthyleneglycol ethers, obtained by addition of from four to 100, preferably six to 40 and especially eight to 20 mols of ethylene oxide to fatty alcohols, alkylphenols, fatty acids, fatty amines, fatty acid amides or sulfonic acid amides, as well as the still water-soluble adducts of propylene oxide or butylene oxide to the above.
  • Pluronics or Tetronics belong to the Nonionics.
  • Nonionics are fatty acid alkylolamides of sulfonic acid alkylolamides, derived, for example, from monoor diethanolamine, from dihydroxypropyl amine or other polyhydroxyalkyl amines, such as the glycamines. Also the oxides of higher tertiary amines with a hydrophobic alkyl residue and two shorter alkyl and/or alkylol residues, with up to four carbon atoms each, can be considered as Nonionics.
  • Amphoteric tensides contain in the molecule both acidic groups, such as carboxy], sulfonic acid, sulfuric acid half esters, phosphonic acid and phosphoric acid partial ester groups, and also basic groups, such as primary, secondary, tertiary and quaternary ammonium groups.
  • Amphoteric compounds with quaternary ammonium groups belong to the type of the betaines.
  • Carboxy, sulfate and sulfonate betaines have a particularly practical interest because of their good compatibility with other tensides.
  • the foaming powder of the tenside can be increased or reduced by combination of suitable tenside types, as well as changed by additions of non-tenside organic substances.
  • Suitable foam stabilizers particularly in tensides of the sulfonate or sulfate type, are surface-active carboxy or sulfobetaines, as well as the above-named non-ionics of the alkylolamide type. Moreover, fatty alcohols or higher terminal diols have been suggested for this purpose.
  • a reduced foaming power that is desirable for the use in washing machines, is often attained by combination of different tenside types, such as of sulfates and/or sulfonates and/or of nonionics, on the one hand, with soaps, on the other hand.
  • soaps the foam inhibition increases with the degree of saturation and the number of carbons in the fatty acid residue. Soaps derived from saturated C fatty acids have been proven good as foam inhibitors.
  • the non-tenside foam inhibitors included N- alkylated aminotriazines, optionally containing chlorine, which are obtained by the reaction of 1 mol of cyanuric acid chloride with 2 to 3 mols of a monoand/or dialkylamine with six to 20, preferably eight to 18 carbon atoms in the alkyl radicals.
  • N- alkylated aminotriazines optionally containing chlorine
  • propoxylated and/or butoxylated aminotriazines such as, products that are obtained by the addition of from 5 to mols of propylene oxide to 1 mol of melamine and further addition of from 10 to 50 mols of butylene oxide to this propylene-oxide derivative.
  • non'tenside foam inhibitors are waterinsoluble organic compounds, such as paraffins or halogenated paraffins with melting points below 100C, aliphatic C m to C ketones as well as aliphatic carboxylic acid esters which contain in the acid or alcohol residue, optionally also in both of these residues, at least 18 carbon atoms (such as triglyceride or fatty acid/fatty alcohol esters). These compounds can be used for the inhibition of foam, above all in combinations of tensides of the sulfate and/or sulfonate type with soaps.
  • addition products of propylene oxide to the above-described surface-active polyethyleneglycol ethers are suitable as well as the also above-described Pluronic, Tetronic" and Ucon-Fluid" types.
  • Weakly acidic, neutral or alkaline reacting salts usable according to the invention are, for example, the bicarbonates, carbonates, borates or silicates of the alkali metals, also mono-, dior trialkali metal orthophosphates, dior tetraalkali metal pyrophosphates, alkali metal metaphosphates known as sequestering agents, alkali metal sulfates as well as the alkali metal salts of organic non-surface-active sulfonic acids, carboxylic acids and sulfocarboxylic acids, containing from one to eight carbon atoms.
  • the bicarbonates, carbonates, borates or silicates of the alkali metals also mono-, dior trialkali metal orthophosphates, dior tetraalkali metal pyrophosphates, alkali metal metaphosphates known as sequestering agents, alkali metal sulfates as well as the alkali metal salts of organic non-surface
  • water-soluble salts of benzene-, tolueneor xylene-sulfonic acid water-soluble salts of sulfoacetic acid, sulfobenzoic acid or salts of sulfodicarboxylic acids as well as the salts of the acetic acid, lactic acid, citric acid and tartaric acid.
  • water-soluble salts such as the alkali metal salts, of higher-molecular weight polycarboxylic acids, particularly polymerizates of maleic acid, itaconic acid, mesaconic acid, fumaric acid, aconitic acid, methylenemalonic acid and citraconic acid, Also mixed polymerizates of these acids with each other, or with other polymerizable substances, such as, ethylene, propylene, acrylic acid, methyacrylic acid, crotonic acid, 3-butenecarboxylic acid,
  • 3-methyl-3-butenecarboxylic acid as well as with vinylmethyl ether, vinyl acetate, isobutylene, acrylamide and styrene, are usable.
  • alkaline reacting polyphosphates particularly tripolyphosphate.
  • the organic sequestering agents include, for example, nitrilotriacetic acid, ethylenediaminetetraacetic acid, N-hydroxyethyl-ethylenediaminetriacetic acid, polyalkylene-polyamine-N-polycarboxylic acids and other known organic sequestering agents. Also combinations of different sequestering agents may be used.
  • the other known sequestering agents include also diand polyphosphonic acids of the following constitutions:
  • R represents alkyl and R represents alkylenc residues with one to eight, preferably one to four carbon atoms
  • X and Y represent hydrogen atoms or alkyl radicals with one to four carbon atoms
  • Z represents the groups -OH, -NH or -NXR.
  • the following compounds are considered above all: methylenediphosphonic acid, l-hydroxyethancl l diphosphonic acid, l-aminoethane-amino-tri-(methylenephosphonic acid), -diphosphonic acid. aminotri-(methylelephosphonic methylaminoor ethylamino-di-(methylenephosphonic acid). and ethylenediaminetetra-(methylenephosphonic acid). All these sequestering agents may be present as free acids. or preferably as their alkali metal salts.
  • the higher molecular weight polycarboxylic acids that are suitable as sequestering builders also include the practically uncross-linked polyhydroxycarboxylic acids and polyaldehydecarboxylic acids containing primarily C--C bonds in the principal chain, which are composed substantially of ethylene units with one carboxyl-, formyl-, hydroxymethylor hydroxyl group each.
  • the polyhydroxycarboxylic acids have a ratio of carboxyl groups to hydroxyl groups of 1.1 to 15, preferably two to nine, and a degree of polymerization of preferably three to 600 units. They can be produced, for example, by copolymerization of acrolein and acrylic acid in the presence of hydrogen peroxide and subsequent Cannizzaro reaction.
  • the polyaldehydecarboxylic acids have a ratio of carboxyl to formyl groups of at least one, and a degree of polymerization of preferably three to units, optionally the polymers have terminal hydroxyl groups. They can be produced, for example, by oxidative-polymerization of acrolein with hydrogen peroxide.
  • Soil-suspending agents which keep the dirt, loosened from the fiber, suspended in the liquor, and thus preventing graying, can also be utilized in the washing agents and washing auxiliaries of the invention.
  • water-soluble colloids mostly organic in nature, are suitable, such as the water-soluble salts of polymeric carboxylic acids. glue, gelatins, salts of ethercarboxylic acids or ethersulfonic acids of starch or cellucw m-ms lose or salts of acidic sulfuric acid esters of cellulose or starch.
  • water-soluble polyamides, containing acidic groups are suitable for this purpose.
  • soluble starch preparations and starch products other than the above-named such as degraded starch, aldehyde starches, etc. may be used. Also polyvinylpyrrolidone is usable.
  • the ingredients of the washing agents and washing auxiliaries of the invention are mostly so selected, that the preparations react neutral to distinctly alkaline in aqueous solution.
  • the pH-valve of a 1 percent solution of the preparation mostly lies in the range from seven to a maximum of 11.5.
  • H O releasing borates are usable, such as perborax Na- ,B,O,-4H O.
  • These compounds may partly or completely be replaced by other carriers of active oxygen, particularly by peroxyhydrates, such as percarbonates, (Na CO -l .5H O perpyrophosphates, citrate perhydrate, percarbamide or melamine-H 0 compounds as well as by H O releasing peracidic salts, such as caroates (KHSO perbenzoates or perphthalates.
  • Water-insoluble and/or water-insoluble stabilizers for percompounds in amounts from 0.25 percent to percent by weight.
  • Water-insoluble percompound stabilizers which amount to, for example, from I to 8 percent, preferably 2 to 7 percent of the weight of the whole preparation, are, for example, the magnesium silicates,
  • MgO SiO 4:l to 1:4, preferably 2:1 to 1:2 and particularly H.
  • other alkaline earth metal, cadmium or tin silicates ofa corresponding composition are usable.
  • water containing oxides of tin are suitable as stabilizers.
  • Water-soluble stabilizers which may be present together with the water-insoluble ones, are the organic sequestering agents whose quantity may amount to 0.25 to 5 percent, preferably 0.5 to 2.5 percent of the weight of the whole preparation.
  • the active chlorine compounds serving as bleaching agents, may be inorganic or organic.
  • the inorganic active-chlorine compounds include alkali metal hypochlorites, which can be used particularly in the form of their mixed salts or addition compounds to orthophosphates or to condensed phosphates, such as to pyro and polyphosphates or to alkali metal silicates. If the washing and cleansing agents of the invention contain monopersulfates and chlorides, in aqueous solution active chlorine is formed.
  • organic active-chlorine compounds particularly the N-chlorinated compounds are of interest, in which one or two chlorine atoms are bound to one nitrogen atom, while the third valence of the nitrogen atoms is bonded to an electrophilic, particularly to a CO- or $0 group.
  • These compounds include dichloroand trichlorocyanuric acid or their salts, chlorinated alkylguanides or alkylbiguanides, chlorinated hydantoins and chlorinated melamines.
  • N-acyl-O-acyl compounds forming with the H 0 organic peracids, as well as carbonic acid or pyrocarbonic acid esters, whose activation value for the percompounds titer) is at least three. preferably at least 4.5, serve as activators for the percompounds. releasing H O in water. This activation value is determined in the following manner.
  • Solutions that contain 0.615 gm/liter of NaBO H O '3H O 4 m mol/liter) and 2.5 gm/liter of Na,,P- 0 -10 H O are treated, after heating to C, with 4 m mol/liter of activator and kept for 5 minutes at this temperature with stirring. Then 100 ml of this liquid is added to a mixture of 250 gm ofice and 15 ml of glacial acetic acid and titrated, immediately after the addition of 0.35 gm of potassium iodide. with 0.1N sodium thiosulfate solution with starch as indicator. The amount of thiosulfate solution used in ml is the activation value titer). At a 100 percent activation of the peroxide used, it would amount to 8.0 ml.
  • the equivalent weight of these compounds should be at most 170. preferably at most and especially at most 1 l0.
  • the activators usable according to the invention, include:
  • N-diacylated and N,N-tetraacylated amines such as N,N,N,N -tetraacetyl-methylenediamine, N,N,N', N'-tetraacetyl-ethylenediamine, N,N- diacetylaniline and N,N-diacetyl-p-toluidine or 1,3diacylated hydantoins, such as the compounds 1,3-diacctyl-5,S-dimethylhydantoin and l,3-dipropionyl-hydantoin;
  • N-alkyl-N-sulfonyl-carbonamides for example, the compounds N-methyl-N-mesyl-acetamide, N-methyl-N-mesyl-benzamide, N-methyl-N-mesylp-nitrobenzamide and N-methyl-N-mesyl-pmethoxybenzamide;
  • N-acylated cylic hydrazides such as the monoacetylmaleic acid hydrazide;
  • hydroxyl amines such as O-benzoyl-N,N-succinylhydroxylamine, O- acetyl-N,N- succinylhydroxylamine, O-pmethoxybenzoyl-N,N-succinyl-hydroxylamine, O- p-nitrobenzyol-N,N-succinylhydroxylamine and O,N,N-triacetylhydroxylamine;
  • N,N-diacyl-sulfurylamides such as N,N'-
  • triacylcyanurates such as triacetylcyanurate anurate and tribenzoylcyanurate
  • the earboxylic acid anhydrides such as benzoic acid anhydride, m-chlorobenzoic acid anhydride, phthalic acid anhydrie, 4-chlorophthalic acid anhydride;
  • sugar esters such as glucosepentaacetate
  • l,3-diacyl-4,5-diacyloxy-imidazolidincs such as the compounds l,3-diformyl-4,5- diacetoxyimidazolidine, l,3-diacetyl-4,5- diacetoxy-imidazolidine, l ,3-diacetyl-4,5- dipropionyloxy imidazolidine;
  • acylated glycoluril compounds such as tetraacetylglycoluril and tetrapropionylglycoluril
  • diacylated 2,5-diketopiperazines such as 1,4- diacetyl-Z,S-diketo-piperazine, 1,4-dipropionyl- 2,5-diketo-piperazine, l,4-dipropionyl-3,6- dimethyl-Z,S-diketo-piperazine;
  • acylation products of propylenediurea or 2,2- dimethylpropylenediurea (2,4,6,8-tetraaza-bicyclo-(3,3,l l-nonane- 3,7-dione or its 9,9-dimethyl derivative), particularly tetraacetylpropylenediurea, tetrapropionyl-propylenediurea or their dimethyl derivatives;
  • the carbonic acid esters for example. the sodium salts of p-(ethoxycarbonyloxy)-benzoic acid and p-(propoxycarbonyloxy)-benzenesulfonic acid.
  • optical brighteners which can be utilized in the compositions are mostly, if not exclusively, derivatives of aminostilbenesulfonic acid, or of diaminostilbenedisulfonic acid, of diarylpyrozolines, of earbostyril, of l,- 2-di-( Z-benzoxazolyl )-ethylene or l,2-di-( 2- benzimidazolyl)-ethylene, of benzoxazolyl-thiophene and of the coumarins.
  • Examples of brighteners from the class of the diaminostilbenedisulfonic acid derivatives are compounds, according to formula I:
  • R and R represent alkoxy, amino, or residues of aliphatic, aromatic or heterocyclic, primary or secondary amines as well as residues of aminosulfonic acids, where the aliphatic residues present in the above groups, contain preferably one to four and particularly two to four carbon atoms, while the heterocyclic ring systems are mostly five to six membered rings.
  • aromatic amines the residues of the aniline, of the anthranilic acid or the anilinesulfonic acid are preferred.
  • Brighteners, derived from the diaminostilbenedisulfonic acid, are mostly used as cotton brighteners.
  • R represents the residue NHC l-l and R may represent the following residues: NH NHCH NHCH CH Ol-l, NHCH CH OCH -NHCH CH OCH )2, molpholino-, NHC H NHC H SO H, 'OCH
  • Some of these brighteners are, in regard to their fiber affinity, regarded as transitional types to the polyamide brighteners, such as the brightener with R -NHC H
  • the compound 4.4'-bis-(4-phenyl-l.2,3triazole-2-yl)-2,2' -stilbenedisulfonic acid belongs also to the cotton brighteners of the diaminostilbenedisulfonic acid type.
  • Diarypyrazolines of the formulae ll and Ill belong to the polyamide brighteners.
  • R; and R represent hydrogen, alkyl and aryl, optionally substituted by carboxyl. carbonamide or carboxylic acid ester groups, R and R, represent hydrogen or lower alkyl, Ar l and Ar 2 represent aryl radicals, such as phenyl, diphenyl or naphthyl, which may carry further substituents, such as hydroxy, alkoxy, hydroxyalkyl, amino. alkylamino, acylamino, carboxyl, carboxylic acid esters, sulfonic acid, sulfonamide and sulfone groups or halogen atoms.
  • the polyamide brighteners further include aliphatically or aromatically substituted aminocoumarins, such as 4-methyl-7-dimethylamino-coumarin or 4 methyl-7- diethylaminocoumarin.
  • aliphatically or aromatically substituted aminocoumarins such as 4-methyl-7-dimethylamino-coumarin or 4 methyl-7- diethylaminocoumarin.
  • polyamide brighteners are the compounds l(2-benzimidazolyl)-2- l-hydroxyethyl-2-benzimidazolyl )-ethylene and lethyl-3-phenyl-7-diethyl-amino-carbostyril.
  • Suitable as brighteners for polyester and polyamide fibers are the compounds 2,5-di-( Z-benzoxazolyl )-thiophene, 2-( 2- benzoxazolyl)-naphtho[2,3-bl-lhiuphene, and l,2-di- (S-methyl-Z-benzoxazolyl )-ethy
  • the brighteners together with other ingredients of the invention products are present as aqueous solution or paste, and are to be transformed to solids by heat drying, it is recommended to incorporate organic sequestering agents in amounts of at least 0.l percent, preferably 0.2 percent to 1 percent by weight of the SOlld products in order to stabilize the brighteners.
  • the enzyme preparations to be used are mostly a mixture of enzymes with different effects, such as proteases, carbohydrases, esterases, lipases, oxidoreductases, catalases, peroxidases, ureases, isomerases, lyases, transferases, desmolases or nucleases.
  • enzymes obtained from bacteria strains or from fungi, such as Bacillus subtilis or Streptomyces griseus, particularly proteases and amylases, which are relatively stable towards alkalis, percompounds, and anionic tensides and are still effective at temperatures up to C.
  • Enzyme preparations are marketed by the manufacturers mostly as aqueous solutions of the active substances or as powders, granulates or as cold-sprayed products. They frequently contain sodium sulfate, sodium chloride, alkali metal ortho-, pyroand polyphosphates, particularly tripolyphosphate, as fillers. Dustfree preparations are particularly valued. These are obtained in a known manner by incorporating of oily or pasty Nonionics or by granulation with the aid of melts of water-of-crystallization-containing salts in their own water-of-crystallization.
  • Enzymes may be incorporated which are specific for certain types of soil, for example, proteases or amylases or lipases. Preferably, combinations of enzymes with different effects are used, particularly combinations of proteases and amylases.
  • compositions of some washing agents, washing auxiliaries, rinsing and cleaning agents according to the invention.
  • the percentage amounts of the ingredients were, unless stated otherwise, calculated on anhydrous agent compositions, with the exception of the ingredients borax'and perborate, wherein the content of water-of-crystallization is stated.
  • the agents, prepared by heatdrying of an aqueous mixture contain generally to 20 percent by weight of water in the form of water-of-crystallization or of hydration. If the agents contain borax or pcrborate, they are admixed to the heat-dried powder.
  • Synthetic tensides of the sulfate or sulfonate type contain generally as impurities slight amounts of sodium sulfate, insignificant for the formulation. The presence of this sodium sulfate is marked in the Na SO lines of the table of the examples with a x.
  • salt-like ingredients contained in the agents of the examples, such as salt-like tensides, other organic salts, as well as inorganic salts, are present as the sodium salts, unless expressively stated as otherwise.
  • the notations or abbreviations used have the following meanings:
  • ABS the salt of an alkylbenzenesulfonic acid with to 15, preferably l l to 13 carbon atoms, in the alkyl chain, obtained by condensation of straight-chain terminal olefins with benzene and sulfonation of the thus-formed alkylbenzene,
  • Alkanesulfonate a sulfonate obtained from paraffins with 12 to 16 carbon atoms by sulfoxidation
  • Fs-estersulfonate a sulfonate obtained from the methyl ester of a hardened tallow fatty acid, by sulfonation with S0
  • Olefinsulfonate a sulfonate obtained from olefin mixtures with 12 to l8 carbon atoms by sulfonation with S0 and hydrolysis of the sulfonation product with aqueous sodium hydroxides.
  • the olefmsulfonate consists substantially of alkenesulfonate and hydroxyalkanesulfonate, and contains, however, also a slight amount of disulfonates,
  • CA-sulfate or TA-sulfate the salts of sulfated, substantially saturated fatty alcohols, prepared by reduction of coconut fatty acid or tallow fatty acid respectively,
  • Soap the salts derived from fatty acid mixtures of an iodine number of at most seven, whose composition was within the following range: 0 to 20 percent by weight of C 0 to 15 percent by weight of C 5 percent to 40 percent by weight of C 5 percent to percent by weight of C,,,, 0 to 20 percent by weight of C 0 to percent by weight of C whereby the foam inhibiting effect of this soap increases with rising average carbon number,
  • CA +9 EO 12 PO" a Nonionic, obtained by reaction of 1 mol of CA 9 E0 with 12 mols of propylene oxide,
  • Copolymera polymer having a molecular weight of about 4,000 obtained by polymerization of 1,2,- 3,6-tetra-hydro-3,6-epoxy-phthalic acid anhydride, followed by hydrolysis and conversion to the disodium salt.
  • agents whose composition is described in the Examples 1 to 7, are preferably intended for the following application purposes:
  • Example 1 Cleaning agent for the metal industry
  • Example 2 Cleaning agent for the food industry (both prepared by mixing of the powdery ingredients)
  • Example 3 Foam-inhibited boiling washing agent
  • Example 4 Strongly foaming product, also usable as fine washing agent
  • Example 5 Soaking agent (all prepared by heatspraying)
  • Example 6 Soaking agent prepared by spraying of the Nonionic onto the mixture of the powdery ingredients)
  • Example 7 Cleaning agent, also usable in the home, for non-textile materials (heat-dried).
  • the quantitative data for the copolymercarboxylate refer to the technically pure product (Copolymer").
  • the quantitative data for the copolymer mixture refer both to the technically pure eopolymer" and also to the mixture of equal parts of weight of this copolymer with the following builders:
  • a salt obtainable in a known way from polymerized acrolein by treatment with alkali metal hydroxides, according to Cannizzaro, optionally in the presence of formaldehyde, of a polyhydroxypoly-carboxylic acid of the average degree of polymerization of 40 and a molar ratio COOH OH 7.3
  • Example 8 Soaking or pre-washing agent
  • Examples 9 to 11 and 13 to 17 All-purpose washing agents. particularly bleaching, boiling washing agents
  • Examples 12 and 18 Colored goods washing agent
  • Examples 19 and 20 Fine-washing agents
  • a di-(a1kylamino)-monochlorotriazine and about 55 percent of a N.N.N"-trialkylmelamine was used.
  • the alkyl residues were present as mixtures of homologs with eight to 18 carbon atoms.
  • the monochlorotriazine derivative or the trialkylmelamine can be used. If the described products contained synthetic sulfates or sulfonates together with soap, the other non-tenside foam inhibitors named in the specification. could be utilized, such as paraffin oil or paraffin.
  • the foam inhibitor used was dissolved in a suitable organic solvent or sprayed in the molten state, with the aid of a nozzle, onto the moving As foam inhibitor, a mixture of about 45 percent of 30 p y p p TABLE I1 by wt.
  • Example 23 Antimicrobial, bleaching after-rinsing agent for washed laundry, which simultaneously dissolves fiber incrustations, particularly lime-containing fiber incrustations 30.0 percent by weight of perborate 30.0 percent by weight of copolymer 15.0 percent by weight of Na CO 2.6 percent by weight of 2-hydroxy-2, 4,4"-trichlorodiphenylether 8.0 percent by weight of MgSiO 14.4 percent by weight of Na SO
  • Example 24 Dishwashing agent for industrial and household dishwashing machines:
  • Example 25 A disinfecting surface-cleaning agent:
  • the washing agents, rinsing agents and cleaning agents described in the examples have a good washing and cleaning power, which is equal or even superior to the corresponding preparations on the basis of tripolyphosphate. Because of the excellent sequestering power of the copolymer carboxylates for alkaline earth metal ions, the excellent properties of the preparations according to the invention appear primarily when washing and cleaning in hard water.
  • the copolymer carboxylates that can be used according to the invention are in addition practically non-hydroscopic. which is of great importance for the storability and pouring behavior of the powdery preparations.
  • perborate-containing agents particularly those to be utilized below C (after-rinsing agents) are compounded with activators for percompounds, for example, with tetraacetylglycoluril, tctraacetylmcthylene-diamine or tetraacetylethylenediamine, a good bleaching effect is obtained also at temperatures of from 20 to 70C.
  • Washing, rinsing and cleansing compositions consisting essentially of (a) from 5 percent to percent by weight of at least one compound having a cleaning action selected from the group consisting of l anionic surface-active compounds, non-ionic surface-active compounds, amphoteric surface-active compounds, and mixtures thereof, (2) organic builder salts and inorganic builder salts, and (3) mixtures of l) and (2), and (b) from 95 to 5 percent by weight of at least one copolymercarboxylate sequestering agent capable of sequestering alkaline earth metal ions prepared from approximately equal molar amounts of maleic acid and furan, and having a molecular weight of from about 300 to 20,000, said copolymer-carboxylate sequestering agents being present as water-soluble salts capable of complex formation with alkaline earth metal ions.
  • copolymer-carboxylate sequestering agent capable of sequestering alkaline earth metal ions is selected from the group consisting of a saponified polymer of l,2,3,6-tetrahydro-3,6-epoxyphthalic acid anhydride in the free acid form having a molecular weight of from 500 to 5000, a saponifled copolymer of substantially equal molar amounts of furan and maleic acid anhydride in the free acid form having a molecular weight of from 500 to 5000, their alkali metal salts, their ammonium salts, their lower alkylamine salts and their lower alkylolamine salts.
  • copolymer-carboxylate sequestering agent capable of sequestering alkaline earth metal ions is the sodium salt of a polymer of 1,23,6- tetrahydro-3,o-epoxy-phthalic acid having an average molecular weight of from 500 to 5,000.
  • copolymer-carboxylate sequestering agent capable of sequestering alkaline earth metal ions is the ammonium salt of a copolymer of equal molar amounts of furan and maleic acid anhydride saponifled with aqueous ammonia and having an average molecular weight of from 500 to 5,000.
  • the washing, rinsing and cleansing composition of claim 1 containing from 10 to 30 percent by-weight of alkali metal silicates, from 10 to 80 percent by weight of caustic alkalis, from to 10 percent by weight of nonionic tensides and from to 30 percent by weight of said copolymer-carboxylate sequestering agent capable of sequestering alkaline earth metal ions, for use in the industrial cleaning of solid material other than testiles.
  • the washing, rinsing and cleansing composition of claim 1 containing from 5 to 40 percent by weight of tensides selected from the group consisting of anionic surface-active compounds, nonionic surface-active compounds and amphoteric surface-active compounds, from 20 to 90 percent by weight of builders selected from the group consisting of organic builder salts and inorganic builder salts and from to 80 percent by weight of said copolymer-carboxylate sequestering agent capable of sequestering alkaline earth metal ions, said compositions having a pH in a 1 percent aqueous solution of from 7 to H5.
  • composition of claim 6 wherein said tenside component includes from 0.5 to 10 percent by weight of the tenside component of foam stabilizers and from 0.5 to 10 percent by weight of the tenside component, of non-tenside foam inhibitors.
  • composition of claim 6 wherein said builder component includes from 5 to 40 percent by weight of the composition of a bleaching component selected from the group consisting of percompounds, their mixtures with bleach activators and stabilizers, and activechlorine compounds 9.
  • the composition of claim 6 including a further content of from 0.1 to 5 percent of soil-suspending agents, from 0 to 5 percent by weight of enzymes selected from the group consisting of proteases, lipeases and amylases, and from 0 to 1 percent by weight of an optical brightener.
  • washing, rinsing and cleansing composition of claim I wherein said at least one compound having a cleaning action is selected from the group consisting of alkali metal silicates, and mixtures thereof with alkali metal hydroxides and alkali metal carbonates, wherein said composition in aqueous solution has a pH of between 8 to 12 for use in automatic dishwashing machines.
  • composition of claim 10 having a further content of from 0.5 to 10 percent by weight of nonionic surface-active compounds, from 0 to percent by weight of active-chlorine compounds, from 0 to 5 per- .sisting of from 5 to percent of at least one compound having a cleaning action and from 95 to 5 percent of a sequestering agent capable of sequestering alkaline earth metal ions, for a time sufficient to disperse and dissol e said soil in said aqueous solution and removing said cleansed solid materials, the improvement consisting of utilizing, as said sequestering agent.
  • copolymer-carboxylate sequestering agent capable of sequestering alkaline earth metal ions prepared from approximately equal molar amounts of maleic acid and furan, and having a molecular weight of from about 300 to 20,000, said copolymer-carboxylate sequestering agents being present as water-soluble salts capable of complex formation with alkaline earth metal ions.
  • said co-polymer-carboxylate sequestering agent capable of sequestering alkaline earth metal ions is selected from the group consisting of a saponified polymer of 1.2.3.6- tetrahydro-3,6-epoxy-phthalic acid anhydride in the free acid form having a molecular weight of from 500 to 5,000, a saponified copolymer of substantially equal molar amounts of furan and maleic acid anhydride in the free acid form having a molecular weight of from 500 to 5,000, their alkali metal salts, their ammonium salts, their lower alkylamine salts and their lower alkylolamine salts.
  • co-polymer-carboxylate sequestering agent capable of sequestering alkaline earth metal ions is the sodium salt of a polymer of l,2,3,6-tetrahydro-3,6-epoxy-phthalic acid :having an average molecular weight of from 500 to 16.
  • co-polymer-carboxylate sequestering agent capable of sequestering alkaline earth metal ions is the ammonium salt of a copolymer of equal molar amounts of furan and maleic acid anhydride saponified with aqueous ammonia and having an average molecular weight of from 500 to 5,000.

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US3983078A (en) * 1973-10-15 1976-09-28 The Procter & Gamble Company Oil removal detergent compositions
US3990983A (en) * 1973-12-03 1976-11-09 Lever Brothers Company Builder compositions
US4079015A (en) * 1975-03-06 1978-03-14 Solvay & Cie. Liquid detergent compositions
US4083793A (en) * 1973-05-23 1978-04-11 Henkel Kommanditgesellschaft Auf Aktien Washing compositions containing aluminosilicates and nonionics and method of washing textiles
US4086146A (en) * 1975-11-12 1978-04-25 W. R. Grace & Co. Water treating process
US4797223A (en) * 1988-01-11 1989-01-10 Rohm And Haas Company Water soluble polymers for detergent compositions
DE3744592A1 (de) * 1987-12-31 1989-07-13 Basf Ag Wasserloesliche polymerisate enthaltende geschirrspuelmittel
US5290470A (en) * 1992-11-25 1994-03-01 Agri-Products Special Markets, Inc. Aqueous cleaning composition containing a chlorinated bleach, an alcohol and a surfactant
WO1995012652A1 (en) * 1993-11-03 1995-05-11 The Procter & Gamble Company Detergent compositions
EP0700265B1 (de) * 1993-05-25 1997-07-30 Henkel-Ecolab GmbH & Co. OHG Verfahren und vorrichtung zur maschinellen geschirreinigung
US5733857A (en) * 1993-07-20 1998-03-31 Nippon Shokubai Co., Ltd. Maleic acid based copolymer and its production process and use
US5846339A (en) * 1993-11-20 1998-12-08 Diversey Lever, Inc. Machine dishwashing process
US6472361B1 (en) * 2002-04-09 2002-10-29 Colgate-Palmolive Company Liquid cleaning composition comprising a salt of polycarboxylic acid

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GR62863B (en) * 1976-10-06 1979-07-09 Procter & Gamble Laundry additive product
GB8311002D0 (en) * 1983-04-22 1983-05-25 Unilever Plc Detergent compositions
DE3328882A1 (de) * 1983-08-10 1985-02-28 Vsesojuznyj naučno-issledovatel'skij biotechničeskij institut, Moskva Fermenthaltiges reinigungsmittel zur behandlung von medizinischen instrumenten und geraeten vor der sterilisation
DE3443963A1 (de) * 1983-12-10 1985-06-20 Sandoz-Patent-GmbH, 7850 Lörrach Phosphatfreie fluessige waschmittel
DE3832989A1 (de) * 1988-09-29 1990-04-05 Dispo Kommerz Ag Huenenberg Fluessiges phosphatfreies reinigungsmittel fuer geschirrspuelmaschinen (geschirrspuelmittel)
NL9000272A (nl) * 1990-02-05 1991-09-02 Sara Lee De Nv Hoofdwasmiddel.

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US3459670A (en) * 1966-07-01 1969-08-05 Monsanto Co Builders for synthetic detergents
US3557005A (en) * 1967-07-14 1971-01-19 Procter & Gamble Detergent compositions containing 3-substituted 2,5 diphenyl-heterocycle brighteners
US3635830A (en) * 1968-05-24 1972-01-18 Lever Brothers Ltd Detergent compositions containing oxydisuccing acid salts as builders
US3655569A (en) * 1968-08-08 1972-04-11 Mo Och Domsjoe Ab Detergent compositions containing a sequestrant and optionally a bleaching agent having a reduced tendency to attack copper, zinc and aluminum
US3663444A (en) * 1969-05-02 1972-05-16 Henkel & Cie Gmbh Washing and cleansing agents with polyamides having improved dirtcarrying capacity
US3700599A (en) * 1970-09-25 1972-10-24 Economics Lab Composition for mechanically cleaning hard surfaces
US3764559A (en) * 1968-12-10 1973-10-09 Economics Lab Detergent compositions

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US3557005A (en) * 1967-07-14 1971-01-19 Procter & Gamble Detergent compositions containing 3-substituted 2,5 diphenyl-heterocycle brighteners
US3635830A (en) * 1968-05-24 1972-01-18 Lever Brothers Ltd Detergent compositions containing oxydisuccing acid salts as builders
US3655569A (en) * 1968-08-08 1972-04-11 Mo Och Domsjoe Ab Detergent compositions containing a sequestrant and optionally a bleaching agent having a reduced tendency to attack copper, zinc and aluminum
US3764559A (en) * 1968-12-10 1973-10-09 Economics Lab Detergent compositions
US3663444A (en) * 1969-05-02 1972-05-16 Henkel & Cie Gmbh Washing and cleansing agents with polyamides having improved dirtcarrying capacity
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Cited By (16)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4083793A (en) * 1973-05-23 1978-04-11 Henkel Kommanditgesellschaft Auf Aktien Washing compositions containing aluminosilicates and nonionics and method of washing textiles
US3983078A (en) * 1973-10-15 1976-09-28 The Procter & Gamble Company Oil removal detergent compositions
US3990983A (en) * 1973-12-03 1976-11-09 Lever Brothers Company Builder compositions
US4079015A (en) * 1975-03-06 1978-03-14 Solvay & Cie. Liquid detergent compositions
US4086146A (en) * 1975-11-12 1978-04-25 W. R. Grace & Co. Water treating process
DE3744592A1 (de) * 1987-12-31 1989-07-13 Basf Ag Wasserloesliche polymerisate enthaltende geschirrspuelmittel
US4797223A (en) * 1988-01-11 1989-01-10 Rohm And Haas Company Water soluble polymers for detergent compositions
US5376296A (en) * 1992-11-25 1994-12-27 Armor All Products Corporation Aqueous cleaning composition containing chlorinated bleach, an alcohol and a surfactant
US5290470A (en) * 1992-11-25 1994-03-01 Agri-Products Special Markets, Inc. Aqueous cleaning composition containing a chlorinated bleach, an alcohol and a surfactant
EP0700265B1 (de) * 1993-05-25 1997-07-30 Henkel-Ecolab GmbH & Co. OHG Verfahren und vorrichtung zur maschinellen geschirreinigung
US5733857A (en) * 1993-07-20 1998-03-31 Nippon Shokubai Co., Ltd. Maleic acid based copolymer and its production process and use
US5993666A (en) * 1993-07-20 1999-11-30 Nippon Shokubai Co., Ltd. Maleic acid based copolymer, and its production process and use
WO1995012652A1 (en) * 1993-11-03 1995-05-11 The Procter & Gamble Company Detergent compositions
US5846339A (en) * 1993-11-20 1998-12-08 Diversey Lever, Inc. Machine dishwashing process
US6472361B1 (en) * 2002-04-09 2002-10-29 Colgate-Palmolive Company Liquid cleaning composition comprising a salt of polycarboxylic acid
US6551979B1 (en) * 2002-04-09 2003-04-22 Colgate-Palmolive Company Liquid cleaning composition

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DE2162673A1 (de) 1973-07-19
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