US3673096A - Protein solubilizing washing rinsing and soaking compositions - Google Patents

Protein solubilizing washing rinsing and soaking compositions Download PDF

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US3673096A
US3673096A US853498A US3673096DA US3673096A US 3673096 A US3673096 A US 3673096A US 853498 A US853498 A US 853498A US 3673096D A US3673096D A US 3673096DA US 3673096 A US3673096 A US 3673096A
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percent
alkali metal
weight
salts
washing
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Dieter Walter
Walter Fries
Ernst Gotte
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Henkel AG and Co KGaA
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    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/002Surface-active compounds containing sulfur
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16Organic compounds
    • C11D3/38Products with no well-defined composition, e.g. natural products
    • C11D3/386Preparations containing enzymes, e.g. protease or amylase

Definitions

  • composition for washing, rinsing and soaking comprising (a) a content of at least one com ound selected from the 8s3498 group consisting of dialkyldisulfimit i es and their alkali metal salts, ammonium salts and organic amine salts, wherein the [30] Foreign Application Priority Data alkyl groups have from 6 to 10 carbon atoms and (b) a content Sept.
  • compositions are use- 260/556 SN ful in solubilizing proteinaceous soil when used alone or in combination with other washing agent additives.
  • An object of the present invention is the production of washing, rinsing and soaking agents with good protein-solubilizing properties, in which enzymes are wholly or partially replaced by readily available compounds not liable to be rendered inactive.
  • Another object of the invention is the production of a composition for washing, rinsing and soaking comprising (a) a content of at least one compound selected from the group consisting of dialkyldisulfimides and their alkali metal salts, ammonium salts and organic amine salts, wherein the alkyl groups have from 6 to 10 carbon atoms and (b) a content of at least one compound selected from the group consisting of alkali metal and ammonium polyphosphates, alkali metal silicates and alkali metal and ammonium salts of aminopolycarboxylic acids and polyphosphonic acids, wherein said components (a) and (b) are present in amounts offrom 05:99.5 to 1:3 by weight.
  • a further object of the invention is the production of washing, rinsing and soaking compositions containing from to 100 percent by weight on an anhydrous basis of the above composition.
  • the present invention is directed to a protein-solubilizing washing, rinsing and cleaning agent comprising a content of:
  • the dialkyldisulfimides have a strong acid reaction in the free state and may suitably be used in the form of their alkali metal salts such as the sodium or potassium salts, or ammonium salts or mixtures thereof, the ammonium salts also including the salts of organic bases, preferably organic amines such as mono-, di-, or tri-lower alkylamines or lower alkanolamines such as mono-, dior tri-ethanolamine.
  • the dialkyldisulfimides may also be utilized in their free state particularly where an inorganic builder is utilized as the component (b).
  • the alkyl residues contained in the dialkyldisulfimides may be the same or different or may be branched.
  • dialkyldisulfimides with straight-chain alkyl residues are preferably used, among which di-n-octyl-disulfimide has been found particularly active.
  • the dialkyldisulfimides are selected from the group consisting of l) dialkyldisulfimide having 6 to 10 carbon atoms in the preferably straight-chain alkyls and (2) their alkali metal salts, ammonium salts and salts with lower alkylamines and lower alkanolamines.
  • the washing, rinsing and soaking agents according to the invention contain at least one inorganic or organic builder salt from the class of polymeric alkali metal phosphates, alkali metal silicates and the alkali metal salts of aminopolycarboxylic acids and polyphosphonic acids.
  • Suitable polymeric phosphates are pyrophosphates, triphosphates, tetraphosphates, trimetaphosphates, tetrametaphosphates, and more highly condensed phosphates, in the form of the neutral or acid sodium, potassium or ammonium salts.
  • Alkali metal triphosphates and their mixtures with pyrophosphates are preferably used.
  • Alkali metal silicates, especially sodium silicate, are also suitable in which the ratio of Na o to SiO is from- 123.5 to M.
  • Suitable organic builder salts are the complexforming alkali metal or ammonium salts of aminopolycarboxylic acids and/or aminopolyphosphonic acids, especially the sodium or potassium salts of aminotriacetic acid, ethylene diamine tetraacetic acid, diethylenetriaminepentaacetic acid, triethylenetetraminehexaacetic acid and their higher homologues, ethylenediaminehydroxyethanetriacetic acid, aminotri-(methylenephosphonic acid), ethylenediaminetetra- (methylenephosphonic acid), l-hydroxyalkane-1,ldiphosphonic acids such as l-hydroxyethanel l diphosphonic acid, methylenediphosphonic acid,
  • the protein-solubilizing compositions of the invention may be used as such for the washing, rinsing and soaking of textiles and dishes. They may also contain up to percent on the dry basis of other suitable components of washing, rinsing and soaking agents such as neutral salts, pH regulators, enzymes, detergents, bleaching agents and other usual additives.
  • Suitable components of the mixtures are neutral salts such as sodium sulfate and sodium chloride, and also substances for regulating the pH value such as bicarbonates, carbonates, borates and hydroxides of sodium or potassium, and acids such as lactic acid and citric acid.
  • the quantity of alkalinereacting substances including the alkali metal silicates and phosphates should be such that a liquor utilizable for mechanical dishwashing devices has a pH of from 10 to 14; for coarse washing the pH of the washing liquor should be from 9 to 12 and for fine washing, from 6 to 9.
  • these may also contain enzymes from the class of proteases, lipases and amylases.
  • the enzymes may be of animal or vegetable origin, for example, they may be obtained from digestive ferments or yeasts, such as pepsin, pancreatin, trypsin, papain, catalase and diastase.
  • enzymic substances obtained from strains of bacteria or fungi, such as Bacillus subtilis and Streptomyces griseus, are used which are relatively stable towards alkalis, percompounds and anionic detergent substances and even at temperatures between 45. and 70 C are not appreciably inactivated. Their relatively great stability towards oxidizing agents possibly is due to their low content of free sulfliydryl groups.
  • the enzymes represent a valuable addition to the agents of the invention, since they are already active at temperatures at which the dialkyldisulfimides have not yet developed their full activity.
  • the disulfimides are completely stable towards strongly alkaline or active chlorine-containing compounds even at temperatures above 70 C. while most of the known enzymes are already inactivated to a considerable extent under the said conditions. This is of special advantage in that the amount of enzymes required can be considerably reduced by the use of the cheaper dialkyldisulfimides.
  • the agents according to the invention may contain further detergent substances, oxygenor chlorine-containing bleaching agents and the usual additives, depending on the purpose for which they are to be used.
  • weakly foaming compounds are of primary importance for all fields of application in which the development of foam is to be completely or largely excluded.
  • these are especially the non-ionic polyglycol ether derivatives of alcohols, fatty acids and alllv kylphenols which contain 3 to 30 glycol ether groups and 8 to 20 carbon atoms in the hydrocarbon residue.
  • Polyglycol ether derivatives in which the number of ethylene glycol ether groups amounts to to and the hydrocarbon residues are derived from straight-chain primary alcohols with 12 to 18 carbon atoms or from alkylphenols with a straight chain alkyl chain containing 6 to 14 carbon atoms are specially suitable.
  • non-ionic basic detergent substances are the water-soluble adducts containing to 250 ethylene glycol ether groups and 10 to 100 propylene glycol ether groups of polyethylene oxide to polypropylene glycol, ethylenediamine-polypropylene glycol and alkylpolypropylene glycol with l to 10 carbon atoms in the alkyl chain.
  • the said compounds usually contain 1 to 5 ethylene glycol units per propylene glycol unit.
  • Washing and cleaning agents in which the development of foam is not harmful or is desirable may contain anionic basic detergent substances detergent the sulfonate or sulfate type.
  • basic detergent substances are olefinsulfonates such as are obtained, for example, by sulfonation of primary or secondary aliphatic monoolefins with gaseous sulfur trioxide and subsequent alkaline or acid hydrolysis, and also alkylsulfonates such as are obtainable from n-alkanes by sulfochlorination or sulfoxidation and subsequent hydrolysis or neutralization or by addition of a bisulfite to olefins.
  • alkylbenzenesulfonates, a-sulfo-fatty acid esters, primary and secondary alkyl sulfates and the sulfates of ethoxylated or propoxylated alcohols are suitable.
  • Further compounds of this class which if desired may be present in the washing agents are the higher molecular weight sulfated partial ethers and partial esters of polyhydric alcohols, such as the alkali metal salts of the monoalkyl ethers or the mono-fatty acid esters of glycerine monosulfuric acid ester or, 1,2- dihydroxypropanesulfonic acid.
  • Sulfates of ethoxylated or propoxylated fatty acid amides and alkylphenols as well as fatty acid taurides and fatty acid isothionates are also suitable.
  • the agents may also contain alkali metal soaps of higher fatty acids, ampholytes such as alkylbetaines and alkylsulfobetaines and nonionic surface-active compounds of the amine oxide and sulfoxide type.
  • the anionic basic detergent substances may be present in the form of the sodium, potassium and ammonium salts as well as salts of organic bases as, for example, mono-, dior triethanolamine.
  • the said vdetergent compounds have an aliphatic hydrocarbon residue, this should preferably have a straight-chain and contain 8 to 22 carbon atoms.
  • the preferably unbranched alkyl chains should contain an average of 6 to 16 carbon atoms.
  • Increases in activity for example, an improved washing power or a reduced foaming power
  • Such improvements are possible, for example, by combinations of anionic with nonionic and/or amphoteric compounds, by combinations of different anionic compounds with one another, by combinations of different nonionic compounds with one another and by mixing basic detergent substances of the same type which differ with respect to the number of carbon atoms or the number and position of double bonds or the branching of chains in the hydrocarbon residue.
  • Mixtures of inorganic and organic builder salt components with a synergistic action may also be used or combined with the above-mentioned mixtures.
  • the agents may also contain oxygen-yielding or active chlorine-containing bleaching agents, such as alkali metal perborates, alkali metal percarbonates, alkali metal perphosphates, urea perhydrate, alkali metal hypochlorites,
  • clflorinated trisodium phosphates and chlorinated cyanuric acid or its alkali metal salts and bleaching agent activators and stabilizers, such as magnesium silicate.
  • greying inhibitors such as sodium cellulose glycollate, disinfecting and freshening agents, fillers, e.g., urea, abrasives, dyestuffs and perfumes as well as optical brighteners, for example, of the diaminostilbenedisulfonic acid type according to the following formula 1 in which X and Y have the following meanings: NH Nil-CH NH--CH CH,OH,
  • Compounds in which X represents an anilino group and Y a diethanolamino or morpholino group are particularly suitable.
  • optical brighteners of the diarylpyrazo-line type according to the following formula may be present:
  • R represents a hydrogen atom or an alkyl or aryl residue which, if desired, may be substituted
  • Ar and Ar represent aryl residues such as phenyl, diphenyl or naphthyl, which may carry further substituents such as hydroxy, alkoxy, hydroxyalkyl, amino, alkylamino, acylamino, carboxyl, sulfonic acid and sulfonamide groups or halogen atoms.
  • Agents which are intended for use in drum washing machines or automatic dishwashing machines may contain in addition known anti-foaming agents, for example, saturated fatty acids or their alkali metal soaps with 20 to 24 carbon atoms or triazine derivatives, which are obtainable by reaction of 1 mol of cyanuric chloride with 2 to 3 mols of an aliphatic, straight-chain, branched or cyclic primary monoamine or by propoxylation or butoxylation of melamine.
  • anti-foaming agents for example, saturated fatty acids or their alkali metal soaps with 20 to 24 carbon atoms or triazine derivatives, which are obtainable by reaction of 1 mol of cyanuric chloride with 2 to 3 mols of an aliphatic, straight-chain, branched or cyclic primary monoamine or by propoxylation or butoxylation of melamine.
  • the washing and cleaning agents may be present in liquid, pasty or solid forms, for example, pulverulent, granulated or lump form.
  • Liquid preparations may contain solvents miscible with water, especially ethanol and isopropanol, and solution aids such as the alkali metal salts of benzene-, toluene-,
  • alkylolamides' such as fatty acid monoand di-ethanolamides, may be added.
  • the preparation of the agents according to the invention may be carried out in the usual way by mixing, granulating or spray drying.
  • enzymes it is advisable to mix these with nonionic basic detergent substances and possibly perfumes or to disperse them in the melt of a salt containing water of crystallization, for example, Glaubers salt, and then to unite this mixture with the remaining power constituents.
  • the enzymes are thereby cemented with the usual powder particles, so that the mixtures do not tend to form dust or to ether g p 1 separate into their components, 50 I 95 percent of pentasodium triphosphate,
  • the mixtures of the invention may have the fol- 1 to 40 P' of Sodium Silicate -z 2 111 I0 lowing comptosition, and the figllowing compositions, in weight 5 5 p f -f i il g percent, are aged on a wateree recipe; 0 percent 0 potassium 1C oroisocyanurate.
  • alkylpolyglycol ether sulfate C -C 0 to 40 percent, preferably 1 to 20 percent, of at least one 10 y ethyleneglycol ether g p compound from the class of anionic, nonionic and 0 I0 30 percent of neutral or acid potassium amphoteric surface-active compounds.
  • a bleaching g l f Pg n f' lrli i-ifoamingigentl:l h l l l h agent especially per-compounds and their mixtures with 0 P 0 y 3C1 Y 61168 W 6! er bleaching agent activators or stabilizers, and active- Condensate l0 18 y acid, 1 to 10 eihyleneglycol chlorine-containing compounds, ether g p 0 to 5 percent, preferably 0. l to 2.5 percent of enzymes, 0 to 10 percent of solution aid from the class of alkali metal 0 to 20 percent, preferably 1 to 12 percent, of other washing Salts of benzene q or y lf acid,
  • agent components such as greying inhibitors, anti-foam- 20 0 to 10 F of orga-mc Solvent from the Class of za ing agents, skin-protecting agents, biocides, optical alcohols and ethei: alcohols, brighteners, solution aids, and dyestuffs and perfumes. 0 to 1 Percent of Optical bnghtenel'r
  • alkylpolyglycol ether C C alkyl
  • alkylphenolpolyglycol ether C C, alkyl
  • the sulfate and sulfonate basic detergent substances and soaps are generally used as the sodium salts.
  • the anionic detergent substances g 23 percent g gg h may advantageously be used in the form of the mono-, dior to percent 0 so um mp osphate and its mixtures with sodium pyrophosphate,
  • the proportion by weight of texto 50 Percent of a Condensed alkali metal Phosphate tiles to washing liquor was 1:10
  • the hardness of the tap water from the class of PY tri'phoiiphmesr was 16 German hardness
  • the concentration of the wash- 0 to 20 Percent ofmP1X'forming agents from the class of ing agent mixtures, utilized in the following table, was 5 gm alkali metal salts of aminopolycarboxylic acids, aminoalper liter
  • the percentage brightening was determined kylenepolyphosphonic acids and y y photometrically.
  • the brightening of the soiled fabrics was 14 kanephosphonic acids, percent.
  • Dishwashing agent for automatic machines 45 percent pentasodium triphosphate 0.5 to 3 percent of the sodium salt of di-n-octyl-disulfimide, 45 percent sodium sulfate 0 to 3 percent of alkylpolyglycol ether (C, C,,,alkyl) or
  • alkylpolyglycol ether C, C,,,alkyl
  • the structure of the dialkyldisulfimides utilized in the experialkylphenolpolyglycol ether (C,,C, alkyl) with 5 to ments and the percentage brightening of the rinsed fabrics are 30 ethylene glycol ether and 5 to 30 propylene glycol 7 shown in the table II.
  • a composition for washing, rinsing and soaking consisting essentially of (a) at least one compound selected from the group consisting of (l) dialkyldisulfimide having straightchain alkyls with 6 to 10 carbon atoms and (2) alkali metal salts, ammonium salts and lower alkylamine and lower alkanolamine salts of said dialkyldisulfimide and (b) at least one builder salt selected from the group consisting of alkali metal and ammonium polyphosphates, alkali metal silicates and alkali metal and ammonium salts of aminopolycarboxylic acids and polyphosphonic acids, wherein said components (a) and (b) are present in amounts offrom 05:99.5 to 1:3 by weight.
  • dialkyldisulfimide is a salt of di-n-octyldisulfimide selected from the group consisting of the alkali metal salt, ammonium salt and lower alkylamine and lower alkanolamine salts.
  • a protein-solubilizing composition for washing, rinsing and soaking consisting essentially of:
  • dialkyldisulfimide having straight-chain alkyls with 6 to l0 carbon atoms and 2) alkali metal salts, ammonium salts and lower alkylamine and lower alkanolamine salts of said dialkyldisulfimide,
  • At least one builder salt selected from the group consisting of alkali metal and ammonium polyphosphates, alkali metal silicates, and alkali metal and ammonium salts of aminopolycarboxylic acids and polyphosphonic acids,

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Abstract

A composition for washing, rinsing and soaking comprising (a) a content of at least one compound selected from the group consisting of dialkyldisulfimides and their alkali metal salts, ammonium salts and organic amine salts, wherein the alkyl groups have from 6 to 10 carbon atoms and (b) a content of at least one compound selected from the group consisting of alkali metal and ammonium polyphosphates, alkali metal silicates and alkali metal and ammonium salts of aminopolycarboxylic acids and polyphosphonic acids, wherein said components (a) and (b) are present in amounts of from 0.5:99.5 to 1:3 by weight. These compositions are useful in solubilizing proteinaceous soil when used alone or in combination with other washing agent additives.

Description

O United States Patent 1151 3,673,096 Walter et al. 1 June 27, 1972 [54] PROTEIN SOLUBILIZING WASHING 2,698,304 12 1954 Henkel eta] 252/312 x RINSING AND SOAKING 3,066,104 11 1962 Dasch etal. ..252 137 colt/[POSITIONS 3,321,497 5 1967 Matzner 252/137x 3,451,935 6/1969 Roald ..252/I35 [72] Inventors: Dieter Walter, H1lden; Walter Fries, Er-
krath-Unterbach; Ernst Gotte, Ratingen- Primary Examiner Mayer weinbkm Tlcfenbrolch' an of Germany Attorney-Hammond & Littell [73] Assignee: Henkel & Cie GmbI-l, Henkelstrasse, Dusseldorf, Germany [57] ABSTRACT [22] Filed: Aug. 27, 1969 A composition for washing, rinsing and soaking comprising (a) a content of at least one com ound selected from the 8s3498 group consisting of dialkyldisulfimit i es and their alkali metal salts, ammonium salts and organic amine salts, wherein the [30] Foreign Application Priority Data alkyl groups have from 6 to 10 carbon atoms and (b) a content Sept. 26 I968 Germany ..P 17 92 617.9 1635mm Selected fmm misting of alkali metal and ammonium polyphosphates, alkali metal 521 u.s.c1 ..252/89,252/526, 252/545, silicates and alkali metal and ammonium Salts of 260/556 SN aminopolycarboxylic acids and polyphosphonic acids, 51 1m. 01. ..Clld 3/34 whcrein Said components and are present in amounts. [58] Field of Search ..252/89, 137, I38, I61; OfffOm 199.5 to I23 by weight. These compositions are use- 260/556 SN ful in solubilizing proteinaceous soil when used alone or in combination with other washing agent additives. [56] References Cited 3 Claims, No Drawings PROTEIN SOLUBILIZING WASHING RINSING AND SOAKING COMPOSITIONS THE PRIOR ART Protein-containing soil is known to be relatively difficult to remove, and for this reason proteolytically active enzymes are OBJECTS OF THE INVENTION An object of the present invention is the production of washing, rinsing and soaking agents with good protein-solubilizing properties, in which enzymes are wholly or partially replaced by readily available compounds not liable to be rendered inactive.
Another object of the invention is the production of a composition for washing, rinsing and soaking comprising (a) a content of at least one compound selected from the group consisting of dialkyldisulfimides and their alkali metal salts, ammonium salts and organic amine salts, wherein the alkyl groups have from 6 to 10 carbon atoms and (b) a content of at least one compound selected from the group consisting of alkali metal and ammonium polyphosphates, alkali metal silicates and alkali metal and ammonium salts of aminopolycarboxylic acids and polyphosphonic acids, wherein said components (a) and (b) are present in amounts offrom 05:99.5 to 1:3 by weight.
A further object of the invention is the production of washing, rinsing and soaking compositions containing from to 100 percent by weight on an anhydrous basis of the above composition.
These and other objects of the invention will become more apparent as the description thereof proceeds.
DESCRIPTION OF THE INVENTION The present invention is directed to a protein-solubilizing washing, rinsing and cleaning agent comprising a content of:
a. at least one compound from the class of dialkyl-disulfimides or their alkali metal salts, ammonium salts and organic amine salts, in which the preferably straight-chain alkyl groups have from 6 to 10 carbon atoms, and
b. at least one compound from the class of polymeric alkali metal phosphates, alkali metal silicates and alkali metal salts of aminopolycarboxylic acids and polyphosphonic acids, 7
wherein the components (a) and (b) are present in amounts from 05:99.5 to 1:3 by weight.
The dialkyldisulfimides have a strong acid reaction in the free state and may suitably be used in the form of their alkali metal salts such as the sodium or potassium salts, or ammonium salts or mixtures thereof, the ammonium salts also including the salts of organic bases, preferably organic amines such as mono-, di-, or tri-lower alkylamines or lower alkanolamines such as mono-, dior tri-ethanolamine. The dialkyldisulfimides may also be utilized in their free state particularly where an inorganic builder is utilized as the component (b). The alkyl residues contained in the dialkyldisulfimides may be the same or different or may be branched. However, dialkyldisulfimides with straight-chain alkyl residues are preferably used, among which di-n-octyl-disulfimide has been found particularly active. The dialkyldisulfimides are selected from the group consisting of l) dialkyldisulfimide having 6 to 10 carbon atoms in the preferably straight-chain alkyls and (2) their alkali metal salts, ammonium salts and salts with lower alkylamines and lower alkanolamines.
Besides the dialkyldisulfimides, the washing, rinsing and soaking agents according to the invention contain at least one inorganic or organic builder salt from the class of polymeric alkali metal phosphates, alkali metal silicates and the alkali metal salts of aminopolycarboxylic acids and polyphosphonic acids.
Suitable polymeric phosphates are pyrophosphates, triphosphates, tetraphosphates, trimetaphosphates, tetrametaphosphates, and more highly condensed phosphates, in the form of the neutral or acid sodium, potassium or ammonium salts. Alkali metal triphosphates and their mixtures with pyrophosphates are preferably used. Alkali metal silicates, especially sodium silicate, are also suitable in which the ratio of Na o to SiO is from- 123.5 to M. Suitable organic builder salts are the complexforming alkali metal or ammonium salts of aminopolycarboxylic acids and/or aminopolyphosphonic acids, especially the sodium or potassium salts of aminotriacetic acid, ethylene diamine tetraacetic acid, diethylenetriaminepentaacetic acid, triethylenetetraminehexaacetic acid and their higher homologues, ethylenediaminehydroxyethanetriacetic acid, aminotri-(methylenephosphonic acid), ethylenediaminetetra- (methylenephosphonic acid), l-hydroxyalkane-1,ldiphosphonic acids such as l-hydroxyethanel l diphosphonic acid, methylenediphosphonic acid,
ethylenediphosphonic acid and also the higher homologues of the above polyphosphonic acids.
The protein-solubilizing compositions of the invention may be used as such for the washing, rinsing and soaking of textiles and dishes. They may also contain up to percent on the dry basis of other suitable components of washing, rinsing and soaking agents such as neutral salts, pH regulators, enzymes, detergents, bleaching agents and other usual additives.
Suitable components of the mixtures are neutral salts such as sodium sulfate and sodium chloride, and also substances for regulating the pH value such as bicarbonates, carbonates, borates and hydroxides of sodium or potassium, and acids such as lactic acid and citric acid. The quantity of alkalinereacting substances including the alkali metal silicates and phosphates should be such that a liquor utilizable for mechanical dishwashing devices has a pH of from 10 to 14; for coarse washing the pH of the washing liquor should be from 9 to 12 and for fine washing, from 6 to 9.
For further improvement of the dirt-loosening properties of the agents according to the invention, these may also contain enzymes from the class of proteases, lipases and amylases. The enzymes may be of animal or vegetable origin, for example, they may be obtained from digestive ferments or yeasts, such as pepsin, pancreatin, trypsin, papain, catalase and diastase. Preferably, enzymic substances obtained from strains of bacteria or fungi, such as Bacillus subtilis and Streptomyces griseus, are used which are relatively stable towards alkalis, percompounds and anionic detergent substances and even at temperatures between 45. and 70 C are not appreciably inactivated. Their relatively great stability towards oxidizing agents possibly is due to their low content of free sulfliydryl groups.
The enzymes represent a valuable addition to the agents of the invention, since they are already active at temperatures at which the dialkyldisulfimides have not yet developed their full activity. On the other hand, the disulfimides are completely stable towards strongly alkaline or active chlorine-containing compounds even at temperatures above 70 C. while most of the known enzymes are already inactivated to a considerable extent under the said conditions. This is of special advantage in that the amount of enzymes required can be considerably reduced by the use of the cheaper dialkyldisulfimides.
The agents according to the invention may contain further detergent substances, oxygenor chlorine-containing bleaching agents and the usual additives, depending on the purpose for which they are to be used.
Among the surface-active basic detergent substances which may be contained in the agents of the invention, weakly foaming compounds are of primary importance for all fields of application in which the development of foam is to be completely or largely excluded. These are especially the non-ionic polyglycol ether derivatives of alcohols, fatty acids and alllv kylphenols which contain 3 to 30 glycol ether groups and 8 to 20 carbon atoms in the hydrocarbon residue. Polyglycol ether derivatives in which the number of ethylene glycol ether groups amounts to to and the hydrocarbon residues are derived from straight-chain primary alcohols with 12 to 18 carbon atoms or from alkylphenols with a straight chain alkyl chain containing 6 to 14 carbon atoms, are specially suitable. By adding 3 to 15 mols of propylene oxide on to the lastnamed polyethyleneglycol ethers or by conversion into the acetals, washing agents are obtained which are marked by a specially low degree of foaming.
Further suitable non-ionic basic detergent substances are the water-soluble adducts containing to 250 ethylene glycol ether groups and 10 to 100 propylene glycol ether groups of polyethylene oxide to polypropylene glycol, ethylenediamine-polypropylene glycol and alkylpolypropylene glycol with l to 10 carbon atoms in the alkyl chain. The said compounds usually contain 1 to 5 ethylene glycol units per propylene glycol unit.
Washing and cleaning agents in which the development of foam is not harmful or is desirable, may contain anionic basic detergent substances detergent the sulfonate or sulfate type. Examples of such basic detergent substances are olefinsulfonates such as are obtained, for example, by sulfonation of primary or secondary aliphatic monoolefins with gaseous sulfur trioxide and subsequent alkaline or acid hydrolysis, and also alkylsulfonates such as are obtainable from n-alkanes by sulfochlorination or sulfoxidation and subsequent hydrolysis or neutralization or by addition of a bisulfite to olefins. In addition, alkylbenzenesulfonates, a-sulfo-fatty acid esters, primary and secondary alkyl sulfates and the sulfates of ethoxylated or propoxylated alcohols are suitable. Further compounds of this class which if desired may be present in the washing agents are the higher molecular weight sulfated partial ethers and partial esters of polyhydric alcohols, such as the alkali metal salts of the monoalkyl ethers or the mono-fatty acid esters of glycerine monosulfuric acid ester or, 1,2- dihydroxypropanesulfonic acid. Sulfates of ethoxylated or propoxylated fatty acid amides and alkylphenols as well as fatty acid taurides and fatty acid isothionates are also suitable.
in addition to the said basic detergent substances of the sulfonate and sulfate type, the agents may also contain alkali metal soaps of higher fatty acids, ampholytes such as alkylbetaines and alkylsulfobetaines and nonionic surface-active compounds of the amine oxide and sulfoxide type.
The anionic basic detergent substances may be present in the form of the sodium, potassium and ammonium salts as well as salts of organic bases as, for example, mono-, dior triethanolamine. Provided the said vdetergent compounds have an aliphatic hydrocarbon residue, this should preferably have a straight-chain and contain 8 to 22 carbon atoms. In compounds with araliphatic hydrocarbon residues, the preferably unbranched alkyl chains should contain an average of 6 to 16 carbon atoms.
Increases in activity, for example, an improved washing power or a reduced foaming power, can be obtained in many cases by a suitable combination of different surface-active basic detergent substances or builder salts. Such improvements are possible, for example, by combinations of anionic with nonionic and/or amphoteric compounds, by combinations of different anionic compounds with one another, by combinations of different nonionic compounds with one another and by mixing basic detergent substances of the same type which differ with respect to the number of carbon atoms or the number and position of double bonds or the branching of chains in the hydrocarbon residue. Mixtures of inorganic and organic builder salt components with a synergistic action may also be used or combined with the above-mentioned mixtures.
The agents may also contain oxygen-yielding or active chlorine-containing bleaching agents, such as alkali metal perborates, alkali metal percarbonates, alkali metal perphosphates, urea perhydrate, alkali metal hypochlorites,
clflorinated trisodium phosphates and chlorinated cyanuric acid or its alkali metal salts, and bleaching agent activators and stabilizers, such as magnesium silicate.
Further suitable components of the mixture are greying inhibitors such as sodium cellulose glycollate, disinfecting and freshening agents, fillers, e.g., urea, abrasives, dyestuffs and perfumes as well as optical brighteners, for example, of the diaminostilbenedisulfonic acid type according to the following formula 1 in which X and Y have the following meanings: NH Nil-CH NH--CH CH,OH,
N(CH CH OH) morpholino, dimethylmorpholino, NHC H,,, NHC l-l SO l-l, OCH and Cl, while X and Y may be the same or different. Compounds in which X represents an anilino group and Y a diethanolamino or morpholino group are particularly suitable.
Further, optical brighteners of the diarylpyrazo-line type according to the following formula may be present:
I Ar
In this formula, R represents a hydrogen atom or an alkyl or aryl residue which, if desired, may be substituted, Ar and Ar represent aryl residues such as phenyl, diphenyl or naphthyl, which may carry further substituents such as hydroxy, alkoxy, hydroxyalkyl, amino, alkylamino, acylamino, carboxyl, sulfonic acid and sulfonamide groups or halogen atoms.
l,3-dia.rylpyrazolines in which R represents a hydrogen atom are preferably used.
Agents which are intended for use in drum washing machines or automatic dishwashing machines may contain in addition known anti-foaming agents, for example, saturated fatty acids or their alkali metal soaps with 20 to 24 carbon atoms or triazine derivatives, which are obtainable by reaction of 1 mol of cyanuric chloride with 2 to 3 mols of an aliphatic, straight-chain, branched or cyclic primary monoamine or by propoxylation or butoxylation of melamine.
The washing and cleaning agents may be present in liquid, pasty or solid forms, for example, pulverulent, granulated or lump form. Liquid preparations may contain solvents miscible with water, especially ethanol and isopropanol, and solution aids such as the alkali metal salts of benzene-, toluene-,
' xyleneor ethylbenzene-sulfonic acids. To increase the foaming power and to improve the compatibility with the skin, alkylolamides', such as fatty acid monoand di-ethanolamides, may be added.
The preparation of the agents according to the invention may be carried out in the usual way by mixing, granulating or spray drying. When enzymes are used, it is advisable to mix these with nonionic basic detergent substances and possibly perfumes or to disperse them in the melt of a salt containing water of crystallization, for example, Glaubers salt, and then to unite this mixture with the remaining power constituents. The enzymes are thereby cemented with the usual powder particles, so that the mixtures do not tend to form dust or to ether g p 1 separate into their components, 50 I 95 percent of pentasodium triphosphate,
The mixtures of the invention, therefore, may have the fol- 1 to 40 P' of Sodium Silicate -z 2 111 I0 lowing comptosition, and the figllowing compositions, in weight 5 5 p f -f i il g percent, are aged on a wateree recipe; 0 percent 0 potassium 1C oroisocyanurate.
0.5 to 25 percent, preferably 1 to 15 percent of dialkyldisull -t g t ifi g and i l g agent] 1f d fi id or i l o percen o e so mm s t o i-n-octy -su imi e,
to 90 percent, preferably 20 to 60 percent, of inorganic to 10 Percent sulfonate basic detergent,
and/or organic builders, O to 10 percent of alkylpolyglycol ether sulfate (C -C 0 to 40 percent, preferably 1 to 20 percent, of at least one 10 y ethyleneglycol ether g p compound from the class of anionic, nonionic and 0 I0 30 percent of neutral or acid potassium amphoteric surface-active compounds. pyrophosphate,
0 to 50 percent, preferably 1 to 30 percent, of a bleaching g l f Pg n f' lrli i-ifoamingigentl:l h l l l h agent, especially per-compounds and their mixtures with 0 P 0 y 3C1 Y 61168 W 6! er bleaching agent activators or stabilizers, and active- Condensate l0 18 y acid, 1 to 10 eihyleneglycol chlorine-containing compounds, ether g p 0 to 5 percent, preferably 0. l to 2.5 percent of enzymes, 0 to 10 percent of solution aid from the class of alkali metal 0 to 20 percent, preferably 1 to 12 percent, of other washing Salts of benzene q or y lf acid,
agent components such as greying inhibitors, anti-foam- 20 0 to 10 F of orga-mc Solvent from the Class of za ing agents, skin-protecting agents, biocides, optical alcohols and ethei: alcohols, brighteners, solution aids, and dyestuffs and perfumes. 0 to 1 Percent of Optical bnghtenel'r Some compositions of the invention are given below which Remanidel' water, perfmfler dyestuffs, preservatlveshave proved panicularly good in practice. The invention is not Soaking and pre'washmg agent:
1 to 5 percent of the sodium salt of di-n-octyldisulfimide,
0 to 5 percent of sulfonate basic detergent substances,
0 to 3 percent of alkylpolyglycol ether (C C alkyl) or alkylphenolpolyglycol ether (C C, alkyl) with 5 to 12 ethyleneglycol ether groups,
restricted to the following mixtures. However, on the contrary, these can be varied in a number of ways and/or can be supplemented by the additives mentioned in the specification. The sulfate and sulfonate basic detergent substances and soaps are generally used as the sodium salts. When liquid preparations are concerned, the anionic detergent substances g 23 percent g gg h may advantageously be used in the form of the mono-, dior to percent 0 so um mp osphate and its mixtures with sodium pyrophosphate,
tri-ethanolammonium salts.
COMPOSlTlONS l. Pulverulcnt, weakly foaming washing agent:
1 to 5 percent of water glass, 0 to 5 percent of magnesium silicate, O to 5 percent of enzyme.
1 to l 5 percent of the sodium salt of di-n-octyldisulfimide, The following examples are illustrative of the practice of the l to l5 percent ofsulfonate basic detergent substances from invention without being limitative in any respect.
the class of alkylbenzenesulfonates, olefin-sulfonates and EXAMPLES n'alkanesulfmmesv A cotton fabric soiled with 14 percent blood-protein stan- O to 5 Pement of y p y y ether 12-' m or 40 dardized EMPA-ferment pollution) was washed in a paddle P i p y y ether a l4 y Wlth 5 to stirrer washing machine, the washing liquor being heated from 10 ethyleneglycol ether p 20 to 50 C. in a period of 20 minutes and then kept for a 0 5 Pemem um Soap, further 10 minutes at 50 C. The proportion by weight of texto 50 Percent of a Condensed alkali metal Phosphate tiles to washing liquor was 1:10, the hardness of the tap water from the class of PY tri'phoiiphmesr was 16 German hardness and the concentration of the wash- 0 to 20 Percent ofmP1X'forming agents from the class of ing agent mixtures, utilized in the following table, was 5 gm alkali metal salts of aminopolycarboxylic acids, aminoalper liter, The percentage brightening was determined kylenepolyphosphonic acids and y y photometrically. The brightening of the soiled fabrics was 14 kanephosphonic acids, percent. 1 I0 5 p e OfYSOdiUm Silicate, In the Table I the comparative experiments are denoted by tO percent Of an inorganic salt from the class Of car- A B and C and the examples according to the invention bonates, bicarbonates, borates, sulfates and chlorides of b Th numerical values h that the agents accordalkali m ing to the invention have an improved dirt-loosening action, 0.5 to 4 percefll of magnesium Silicate, especially in combination with enzymes.
TABLE I Examples in parts by weight Comparison 1 2 3 4 5 A B C Components of the washing agent:
Na-di-ll-octyldisnlfimido 10 10 10 5 15 ()loyl alcohol polyglycol other (10 othylone-glycol other groups) 5 5 5 3 lontasotlium triphosphate. 45 45 l5 45 -15 45 45 15 Sodium sulfate 45 44. 5 1U 39. 5 41] 5-1. 5 50 Enzynm O. 5 0.5 0. 5 lorcont brightening 48 8 48 7 51 49 38 1 47.1 43 l 10 to 35 Percent of Sodium Perborate tetrahydrate, The following examples 6 to 10 where conducted according 0 to 5 P of enzymes, to the foregoing examples, while the washing period at 50 C 5 Percent ofami'foaming agent, was extended to 30 minutes. The washing compositions con- 0.05 to 1 percent of an optical brightener i d f 0.5 to 3 percent of sodium cellulose glycollate. 10 percent Na-dialkyldisulfimide 2. Dishwashing agent for automatic machines: 45 percent pentasodium triphosphate 0.5 to 3 percent of the sodium salt of di-n-octyl-disulfimide, 45 percent sodium sulfate 0 to 3 percent of alkylpolyglycol ether (C, C,,,alkyl) or The structure of the dialkyldisulfimides utilized in the experialkylphenolpolyglycol ether (C,,C, alkyl) with 5 to ments and the percentage brightening of the rinsed fabrics are 30 ethylene glycol ether and 5 to 30 propylene glycol 7 shown in the table II.
TABLE [I Ex. Dialkyldisulfimide Brightening 6 Na-di-n'octyldisulfimide 53.5 7 Na-n-hexyl-n-oetyldisulfimide 3.6 8 Na-n-octyl-n-decyldisulfimide 53 .7 9 Na-n-hcptyl-n-octyldisulfimide 54.2 H) Nu-n-hcptyl-n-decyldinulfimide 5 3 .8
The preceding specific embodiments are illustrative of the practice of the invention. It is to be understood, however, that other expedients known to those skilled in the art may be employed without departing from the spirit of the invention.
We claim:
1. A composition for washing, rinsing and soaking consisting essentially of (a) at least one compound selected from the group consisting of (l) dialkyldisulfimide having straightchain alkyls with 6 to 10 carbon atoms and (2) alkali metal salts, ammonium salts and lower alkylamine and lower alkanolamine salts of said dialkyldisulfimide and (b) at least one builder salt selected from the group consisting of alkali metal and ammonium polyphosphates, alkali metal silicates and alkali metal and ammonium salts of aminopolycarboxylic acids and polyphosphonic acids, wherein said components (a) and (b) are present in amounts offrom 05:99.5 to 1:3 by weight.
2. The composition of claim 1 wherein said dialkyldisulfimide is a salt of di-n-octyldisulfimide selected from the group consisting of the alkali metal salt, ammonium salt and lower alkylamine and lower alkanolamine salts.
3. A protein-solubilizing composition for washing, rinsing and soaking consisting essentially of:
a. from 0.5 to 25 percent by weight of at least one compound selected from the group consisting of l) dialkyldisulfimide having straight-chain alkyls with 6 to l0 carbon atoms and 2) alkali metal salts, ammonium salts and lower alkylamine and lower alkanolamine salts of said dialkyldisulfimide,
b. from l0 to 90 percent by weight of at least one builder salt selected from the group consisting of alkali metal and ammonium polyphosphates, alkali metal silicates, and alkali metal and ammonium salts of aminopolycarboxylic acids and polyphosphonic acids,
c. from 0 to percent by weight of neutral salts,
d. from 0 to 40 percent by weight of at least one compound selected from the group consisting of anionic, non-ionic and amphoteric surface-active detergent substances,
e. from 0 to 50 percent by weight of bleaching agents,
f, from O to 5 percent by weight of enzymes,
g. from O to 3 percent by weight of greying inhibitors,
h. from 0 to 5 percent by weight of antifoaming agents,
i. from O to 1 percent by weight of optical brighteners $32 3? UNITED STA'iES rgrrmr 02mm; r QERTH ICATE 0F CQRRECTiQN Eatec'i Inv fit h) DIETER WALTER et el It is certified that error appears in the above-identifiedpatent and that said Letters Patent are hereby corrected as shown below:
F Patent Appln, k Y
Col. Line Page Line 3 22 7 13 Please delete detergent" (second occurrence) and insert of 8 es Claim 5 of e Claim 3 Amend. "A" After "i. from O to 1% by weight of optical b righteners," the'following phrase should be inserted wherein the percentages are based on a water-free composition and total 100% by weight Signed and sealed this 29th de ty of May 1973 (SEAL) Attest:
EDWARD M.FLETCHER,JR. ROBERT GOTTSCHALK Attes'ting Officer Commissioner of Patents

Claims (2)

  1. 2. The composition of claim 1 wherein said dialkyldisulfimide is a salt of di-n-octyldisulfimide selected from the group consisting of the alkali metal salt, ammonium salt and lower alkylamine and lower alkanolamine salts.
  2. 3. A protein-solubilizing composition for washing, rinsing and soaking consisting essentially of: a. from 0.5 to 25 percent by weight of at least one compound selected from the group consisting of (1) dialkyldisulfimide having straight-chain alkyls with 6 to 10 carbon atoms and (2) alkali metal salts, ammonium salts and lower alkylamine and lower alkanolamine salts of said dialkyldisulfimide, b. from 10 to 90 percent by weight of at least one builder salt selected from the group consisting of alkali metal and ammonium polyphosphates, alkali metal silicates, and alkali metal and ammonium salts of aminopolycarboxylic acids and polyphosphonic acids, c. from 0 to 80 percent by weight of neutral salts, d. from 0 to 40 percent by weight of at least one compound selected from the group consisting of anionic, non-ionic and amphoteric surface-active detergent substances, e. from 0 to 50 percent by weight of bleaching agents, f. from 0 to 5 percent by weight of enzymes, g. from 0 to 3 percent by weight of greying inhibitors, h. from 0 to 5 percent by weight of antifoaming agents, i. from 0 to 1 percent by weight of optical brighteners
US853498A 1968-09-26 1969-08-27 Protein solubilizing washing rinsing and soaking compositions Expired - Lifetime US3673096A (en)

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DE19681792617 DE1792617A1 (en) 1968-09-26 1968-09-26 Protein dissolving detergent, dish washing detergent and soaking agent

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JP (1) JPS4818923B1 (en)
AT (1) AT306202B (en)
BE (1) BE739386A (en)
CH (1) CH493624A (en)
DE (1) DE1792617A1 (en)
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Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2292997A (en) * 1938-08-03 1942-08-11 Unichem Chemikalien Handels A Cadillary-active sulphonic acid imides
US2698304A (en) * 1950-02-06 1954-12-28 Bohme Fettchemie Gmbh Emulsifier compositon
US3066104A (en) * 1958-02-10 1962-11-27 Diamond Alkali Co Heavy duty liquid synthetic detergent composition
US3321497A (en) * 1963-10-07 1967-05-23 Monsanto Co Compositions of matter
US3451935A (en) * 1966-04-25 1969-06-24 Procter & Gamble Granular enzyme-containing laundry composition

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2292997A (en) * 1938-08-03 1942-08-11 Unichem Chemikalien Handels A Cadillary-active sulphonic acid imides
US2698304A (en) * 1950-02-06 1954-12-28 Bohme Fettchemie Gmbh Emulsifier compositon
US3066104A (en) * 1958-02-10 1962-11-27 Diamond Alkali Co Heavy duty liquid synthetic detergent composition
US3321497A (en) * 1963-10-07 1967-05-23 Monsanto Co Compositions of matter
US3451935A (en) * 1966-04-25 1969-06-24 Procter & Gamble Granular enzyme-containing laundry composition

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DE1792617A1 (en) 1971-11-18
NL6913022A (en) 1970-04-01
JPS4818923B1 (en) 1973-06-09
AT306202B (en) 1973-03-26
BE739386A (en) 1970-03-25
CH493624A (en) 1970-07-15
FR2018958A1 (en) 1970-06-26

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