Classifications

• • 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
  • C11D3/0005—Other compounding ingredients characterised by their effect
  • C11D3/0026—Low foaming or foam regulating compositions
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01D—SEPARATION
  • B01D19/00—Degasification of liquids
  • B01D19/02—Foam dispersion or prevention
  • B01D19/04—Foam dispersion or prevention by addition of chemical substances
  • B01D19/0404—Foam dispersion or prevention by addition of chemical substances characterised by the nature of the chemical substance
• • 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
  • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
  • C11D1/02—Anionic compounds
  • C11D1/04—Carboxylic acids or salts thereof
• • 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
  • C11D3/20—Organic compounds containing oxygen
  • C11D3/2096—Heterocyclic compounds

Definitions

• non-ionic detergent substances especially those based on polyglycol ethers, have a lowfoaming power.
• the foam-inhibiting properties of these compounds are often not sufficiently adequate to reduce the foam formation of such washing and cleaning agents which contain highly foaming tensides of the sulfate or sulfonate type.
• the effect of these fatty acids is, however, limited to tensides of the sulfonate type and depends, in addition, upon the hardness of the water used for the preparation of the cleaning solution.
• the silicones widely used as foam inhibitors are less suitable for washing and cleansing agents since they may have a hydrophobizing effect on the cleaned objects and can be removed only with difiiculty from the substrate.
• An object of the present invention is to provide washing, rinsing and cleaning agents which, compared with the known agents, have an improved anti-foaming action independent of the nature and composition of the foaming compounds as well as of the hardness of the water, have no negative effect on the cleaning action of the agents or on the usefulness of the cleaned substrate, are effective in "ice small concentrations and overcome the disadvantages of the prior art.
• J-R: I h O- 0 wherein R and R are members having 8 to 30 carbon atoms selected from the group consisting of alkyl, alkenyl, alkylcycloalkyl and alkylphenyl, and R and R are members selected from the group consisting of hydrogen and hydrocarbonyls having 1 to 30 carbon atoms selected from the group consisting of alkyl, alkenyl, alkylcycloalkyl and alkylphenyl, (2) at least one saponification product of said dimer ketene of the formula wherein R R R and R have the above assigned values and X represents
• the invention therefore, comprises low-foaming washing, rinsing and cleaning agents which are characterized in that they contain (a) from 90% to 99.9% of at least one compound having a cleaning or complexing action, and (b) from 0.1% to 10% by weight of at least one foam-inhibiting compound of the Formula I and its saponification product of the Formula II R2 COOK (II) wherein R and R represent hydrocarbon radicals with 8 to 30 carbon atoms and R and R represent hydrogen or hydrocarbon radicals with 1 to 30 carbon atoms, and X represents a cation.
• the cation X is from the class of alkali metals, alkaline earth metals, the ammonium and of the organic ammonium bases.
• the radicals R and R or R and R can be identical or different, straight-chain or branched, saturated or unsaturated, or also cycloaliphatic or alkylaromatic.
• R, and R are straight-chain, saturated or singly unsaturated hydrocarbon radicals such as alkyls and alkenyls with 12 to 22 carbon atoms.
• the radicals R and R are hydrogen, and X is an alkali metal such as sodium or potassium.
• carboxylic acid chlorides or bromides of the formula 3 R CHR COHal or R CHR COHal in which Hal represents chlorine or bromine.
• carboxylic acid halides are derived from aliphatic, cycloaliphatic, or alkylaromatic carboxylic acids, particularly from fatty acids of natural or synthetic origin.
• lauric myristic, palmitic, stearic, arachic, behenic, lignoceric, palmitoleic, and oleic acid, or their mixtures occurring in natural fats, such as coconut, tallow, rape oil, palm kernel, soybean oil, cottonseed oil, peanut oil, or olive oil fatty acids or their hydrogenation products.
• synthetic fatty acids and fatty acid mixtures obtainable by paraflin oxidation, ethylene polymerization, or oxosynthesis can be utilized in the form of their halides.
• alkylcycloalkenoic acid halides and alkyl benzoic acid halides may be employed such as dodecylcyclohexylacetyl chloride and octylphenylacetyl chloride.
• ketenes are obtained in a known manner by dehydrochlorination, which ketenes dimerize spontaneously to give compounds of Formula I.
• the saponification products, according to Formula II, which are in equilibrium with the enol form, according to Formula III H OX (III) are obtained from the dimer ketenes by alkaline saponification.
• the saponification of the dimer ketenes, according to Formula I can be carried out before or during the preparation of the agents, according to the invention, or in their application. It is promoted by the use of higher temperatures and by the presence of alkaline reacting substances. Thus, for instance, on heating of an alkaline washing liquor at temperatures above 70 to 80 C., a more or less complete saponificatioon of the dimer ketene may ocur.
• the compounds, according to Formula I are particularly effec tive in the temperature range from 50 C. to 80 C., whereas their alkaline saponification products are effective in the range from 70 C. to 100 C.
• the foam-inhibiting effect of the partially saponified dimer ketenes or the mixtures of dimer ketenes and their saponification products extends over a broad temperature range.
• the alkali metal salts of the saponification products, according to the Formula II, are, in addition, surface active and may have a favorable influence upon the washing and cleansing power of the agents.
• foam inhibitors of Formula I and/or II in which the radicals R to R have different constitutions or a different number of carbon atoms can be used advantageously.
• the foaming behavior can be adjusted to the respective requirements within a temperature range of from 30 C. to 100 C.
• the washing, rinsing and cleaning compositions of the invention are low-foaming rinsing, washing and cleaning compositions comprising (a) from 90% to 99.9% by weight of at least one active compound selected from the group consisting of cleaning compounds and complexing compounds, and (b) from 0.1% to by weight of a foam inhibitor selected from the grou consisting of (1) at least one dimer ketene of the formula wherein R and R are members having 8 to 30 carbon atoms selected from the group consisting of alkyl, alkenyl, alkylcycloalkyl and alkylphenyl, and R and R are members selected from the group consisting of hydrogen and hydrocarbonyls having 1 to 30 carbon atoms selected from the group consisting of alkyl, alkenyl, alkylcycloalkyl and alkylphenyl, and (2) at least one saponification product of said dimer ketene of the formula wherein R R R and R have the above assigned values and X represents a member selected from the
• foam inhibitors to be used depend upon the amount of foaming or detergent substance present in the final composition and/or on the substrate to be cleaned as well as upon the magnitude of the desired effect.
• concentrations applied extend from 0.1% to 10%, preferably from 0.2% to 5% by weight, based on the solid composition. It is, of course, possible to work With still larger amounts, for instance, up to 25% by Weight and more. This, however, is not required in the practice.
• the foam inhibitors can be mixed with the other washing, cleansing and descaling agents in a conventional manner and can be processed together with them, for example, spray dried or granulated, or they can be converted by other known processes to solid, liquid or pasty mixtures.
• the foam inhibitors can also be mixed in molten or dissolved form with the other ingredients, present as powders or granules, or be sprayed or granulated on them.
• ingredients which are present in amounts from to 99.9%,, preferably to 99.8% by weight, consist of at least one Washing, bleaching, or complexing compound, such as anionic, non-ionic, amphoteric or cationic surface-active compounds, polymeric phosphates, complexing agents, as well as other non-surface-active builders, oxygen-containing bleaching agents and other ingredients customarily present in such agents.
• Washing, bleaching, or complexing compound such as anionic, non-ionic, amphoteric or cationic surface-active compounds, polymeric phosphates, complexing agents, as well as other non-surface-active builders, oxygen-containing bleaching agents and other ingredients customarily present in such agents.
• the washing and cleansing agents can also contain anionic basic detergent substances of the sulfonate or sulfate type.
• alkylbenzene sulfonates for example, dodecylbenzene sulfonate are suitable, also olefin sulfonates, such as, for example, are obtained by sulfonation of primary and secondarl aliphatic monoolefins with gaseous sulfur trioxide and subsequent alkaline or acidic hydrolysis, as well as alkylsulfonates obtainable from nalkanes by sulfochlorination or sulfoxidation and subsequent hydrolysis or neutralization, or by addition of hisulfite to olefins.
• oz-SlllfOfflttY acid esters are also suitable.
• Other compounds of this class which can be optionally present in the washing composition are the higher molecular weight sulfated partial ethers and partial esters of polyhydric alcohols, such as the alkali metal salts of the monoalkylethers or mono fatty esters of the glycerine monosulfuric acid esters, or 1,2-dihydroxy-propanesulfonic acid.
• sulfates of ethoxylated or propoxylated fatty amides and alkylphenols are well as fatty acid taurides and fatty acid isothionates are suitable.
• alkyl betaines and particularly alkyl sulfobetaines are suitable, for example, 3-(N,N-dimethyl-N-alkylammonium)-propane-l-sulfonate and 3-(N,N-dimethyl-N-alkylammonium)-2-hydroxypropane-l-sulfonate.
• the anionic basic detergent ingredients can 'be present in the form of their alkali metal salts such as the sodium and potassium, and ammonium salt, as well as salts of organic bases, such as mono-, diand tri-ethanolamine.
• alkali metal salts such as the sodium and potassium, and ammonium salt
• organic bases such as mono-, diand tri-ethanolamine.
• anionic and amphoteric compounds have an aliphatic hydrocarbon radical, the latter should preferably be straight-chained and should have from 8 to 22 carbon atoms.
• araliphatic hydrocarbon radicals such as alkylphenyl radicals, the preferred straight alkyl chains contain an average of from 6 to 16 carbon atoms.
• non-ionic surface-active basic detergent ingredients primarily suitable are the polyglycolether derivatives of alcohols, fatty acids and alkylphenols which contain 3 to 30 glycol ether groups and 8 to 20 carbon atoms in the hydrocarbon radical.
• Particularly suitable are polyoxyethyleneglycolether derivatives in which the number of oxyethylene groups is 5 to 15 and whose hydrocarbon radicals are derived from straight-chain primary alcohols with 12 to 18 carbon atoms, or from alkylphenols with a straight-chain alkyl chain of 6 to 14 carbon atoms.
• non-ionic basic detergent ingredients are the water-soluble polyethylene oxide adducts, containing 20 to 250 ethyleneglycolether groups and to 100 propyleneglycolether groups adducted to polypropylene glycol, ethylenediamine-polypropyleneglycol and alkylenepolypropyleneglycol with 1 to 10 carbon atoms in the alkylene chain.
• the compounds utilized usually contain 1 to 5 oxyethylene units per oxypropylene unit.
• non-ionic compounds are those of the amine oxide and sulfoxide types, which, if necessary can be ethoxylated.
• suitable components of the mixture include neutral salts, such as sodium sulfate and sodium chloride as well as compounds regulating the pH value, such as the bicarbonates, carbonates, borates and hydroxides of the alkali metals, such as sodium or potassium, and acids such as lactic acid and citric acid.
• the amount of alkalinereacting substances including the alkali metal silicates and phosphates should be such that the pH of a liquor utilizable for mechanical dishwashing machines and descaling of textiles, service pipes, washing machines and hot water heaters, amounts to 9 to 14, and in laundry machines for coarse washing, 9 to 12, and for fine washing, 6 to 9.
• the cleaning compositions of the invention may also contain oxygen-yielding or active chlorine-containing bleaching agents such as hydrogen peroxide, alkali metal perborates, alkali metal precarbonates, alkali metal perphosphates, urea perhydrate, alkali metal persulfate, alkali metal hypochlorites, chlorinated trisodium phosphate and chlorinated cyanuric acid and its alkali metal salts as well as bleaching agent activators and stabilizers such as magnesium silicate.
• oxygen-yielding or active chlorine-containing bleaching agents such as hydrogen peroxide, alkali metal perborates, alkali metal precarbonates, alkali metal perphosphates, urea perhydrate, alkali metal persulfate, alkali metal hypochlorites, chlorinated trisodium phosphate and chlorinated cyanuric acid and its alkali metal salts as well as bleaching agent activators and stabilizers such as magnesium silicate.
• optical brighteners for cellulosic fibers for example, those of the diaminostilbene-disulfonic acid type according to the following formula in which X and Y represent the following: NH -NHCH -NHCH --CH OH,
• optical brighteners of the diarylpyrazoline type according to the following formula may be present:
• Ar and Ar' represent 'aryl residues, such as phenyl, diphenyl or naphthyl, which may carry further substituents such as hydroxy, alkoxy, hydroxylalkyl, amino, alkylamino, acylamino, carboxyl, sulfonic acid and sulfonamide groups or halogen atoms.
• 1,3-diarylpyrazolines are preferably used in which Ar is p-sulfonamidophenyl and Ar is p-chlorophenyl.
• whiteners suitable for the brightening of other types of fibers may be present, for example, such as of the type of naphthotriazolestilbene sulfonates, ethylene-bis-benzimidazoles, ethylene-bis-benzoxazoles, thiophene-bis-benzoxazoles, dialkylaminocoumarins, and cyanoanthracenes.
• These brighteners or their mixtures can be present in the washing composition in amounts from 0.01% to 1.5% by weight, preferably from 0.1% to 1% by weight.
• suitable mixture ingredients are anti-greying compounds, such as sodium celluloseglycolate, as well as the water-soluble alkali metal salts of synthetic polymers which contain free carboxylic groups.
• anti-greying compounds such as sodium celluloseglycolate
• water-soluble alkali metal salts of synthetic polymers which contain free carboxylic groups include polyesters or the polyamides of triand tetra-carboxylic acids and dihydric alcohols or diamines, also polymeric acrylic, methacrylic, maleic, fumaric, itaconic, citraconic and aconitic acids, as well as the mixed polymerizates of the above-named unsaturated carboxylic acids or their mixed polymerizates with olefins.
• Washing agents for washing textiles may also contain restoring additives, for example, fatty acid amides of diamines or hydroxyalkyldiamines.
• the washing and cleaning compositions of the invention may also contain enzymes from the class of the proteases, lipases and amylases, which may be obtained from animal and vegetable origin, for example, from digestive ferments or yeasts, such as pepsin, pancreatin, t-rypsin, papai n, catalase and diastase.
• enzymes from the class of the proteases, lipases and amylases which may be obtained from animal and vegetable origin, for example, from digestive ferments or yeasts, such as pepsin, pancreatin, t-rypsin, papai n, catalase and diastase.
• enzymic active substances are obtained from strains of bacteria or fungi, such as Bacillus subtilz's and Streptomyces griseus, which substances are relatively stable towards alkalis, per-compounds and anionic detergent substances and are not appreciably inactivated even at temperatures between 45 C. and 70 C.
• the washing and cleaning agents may be present in liquid, pasty or solid form, for example, pulverulent, granulated or lump form.
• liquid preparations may contain solvents miscible with water, especially ethanol and isopropanol, as well as solution aids such as the alkali metal salts of benzene-, toluene-, xyleneor ethylbenzenesulfonic acids.
• Skin protecting substances such as fatty acid monoand dialkylolamides may be added to the ring and cleaning agents intended for manual use.
• compositions of the invention may also contain dyes and perfumes, bacteriacides, restoring compounds as well as fillers such as urea.
• Textile softener compositions according to the invention contain primarily alkali metal polyphosphates, such as sodium or potassium polyphosphates, for example, pentasodium triphosphate, hexasodium tetraphosphate and their mixtures with polyphosphates of the formula where n represents a whole number from to 20 and also sodium or potassium metaphosphates, such as sodium trimetaphosphate, sodium tetrametaphosphate, and sodium polymetaphosphates of the formula (NaPO where m represents a whole number from 5 to 30.
• alkali metal polyphosphates such as sodium or potassium polyphosphates, for example, pentasodium triphosphate, hexasodium tetraphosphate and their mixtures with polyphosphates of the formula where n represents a whole number from to 20 and also sodium or potassium metaphosphates, such as sodium trimetaphosphate, sodium tetrametaphosphate, and sodium polymetaphosphates of the formula (NaPO
• the condensed phosphates may optionally be completely or partially replaced by complexing agents from the class of aminopolycarboxylic acids, alkanediphosphonic acids, hydroxyalkanediphosphonic acids, and aminoalkanepolyphosphonic acids, or their alkali metal salts.
• washing, cleansing and softening compositions may optionally contain other known foam inhibitors, such as saturated fatty acids with 20 to 24 carbon atoms or their alkali metal salts, paraflins, higher molecular weight fatty acid esters or triglycerides, or trialkylmelamines. Such additions may often have a synergistic effect.
• foam inhibitors such as saturated fatty acids with 20 to 24 carbon atoms or their alkali metal salts, paraflins, higher molecular weight fatty acid esters or triglycerides, or trialkylmelamines.
• the surface-active compounds can consist of up to 100%, preferably from 5% to 70%, of compounds of the sulfonate and/or sulfate type, up to 100%, preferably from 5% to 40% of non-ionic compounds of the polyglycolether type and up to 100%, preferably from 10% to 50%, of soaps.
• the builder salts can consist of up to 100%, preferably to 95%, of alkali metal triphosphates and their mixtures with alkali metal pyrophosphates, up to 100%, preferably 5% to 50%, of an alkali metal salt of a complexing compound from the class of polyphosphonic acids, nitrilotriacetic acid, ethylenediaminetetraacetic acid and their alkali metal salts, and up to 100%, preferably from 5% to 75%, of at least one compound of the class of alkali metal silicates, alkali metal carbonates and alkali metal borates.
• auxiliary and supplementary washing agent compounds belong in addition to the optical brighteners, especially enzymes which can be present in an amount of up to 5%, preferably from 0.2% to 3%, and the additional anti-greying compounds which can be present in an amount of up to 5%, preferably from 0.2% to 3%.
• the sulfate and sulfonate basic surface-active washing components and soaps are generally used as the sodium salts although other alkali metal salts may be employed. If liquid preparations are used, the anionic detergent substances may advantageously be used in the form of the mono-, dior triethanolammonium salts.
• alkylpolyglycolethers C to C -alkyl
• alkylphenolpolyglycolethers C to C -alkyl
• an inorganic salt from the class of the carbonates, bicarbonates, borates, sulfates and chlorides of alkali metals.
• EXAMPLES 1 to 28 The washing agents listed in Table II were used. The numerical data is in percent by weight.
• the sulfonate washing ingredients and the soaps were used as sodium salts.
• the a-sulfo fatty esters are methyl ester of a hydrogenated tallow fatty acid, sulfonated in the a-position to the ester group. The abbreviations are:
• NTA Sodium nitrilotriacetate
• EDTA Sodium ethylenediaminetetraacetate
• CMC Sodium salt of carboxymethylcellulose
• EO Ethylene oxide groups
• Low-foaming rinsing, washing and cleaning compositions consisting essentially of (A) from 90% to 99.9% by Weight of active compounds selected from the group consisting of cleaning compounds and complexing compounds, said active compounds being from to 40% of at least one surface-active compound selected from the group consisting of anionic, non-ionic and amphoteric surface-active compounds from 10% to 100% of at least one builder component selected from the group consisting of non-surface-active cleaning builder salts and complexing builder salts, and from 0 to 50% of an activeoxygen per compound, and (B) from 0.1% to 10% by weight of a foam inhibitor selected from the group consisting of (1) at least one dimer ketene of the formula I t-r wherein R and R are members having 8 to 30 carbon atoms selected from the group consisting of alkyl, alkenyl, alkylcycloalkyl and alkylphenyl, and R and R are members selected from the group consisting of hydrogen and hydrocarbonyls having 1 to 30 carbon atoms
• foam inhibitor is said saponification product of saide dimer ketene and its enol.
• foam inhibitor is a mixture of said dimer ketene and said saponification product of said dimer ketene and its enol.
• R and R represent members selected from the group consisting of alkyl having from 12 to 22 carbon atoms and alkenyl having from 12 to 22 carbon atoms, R and R are hydrogen and X is a cation selected from the group consisting of sodium and potassium.
• said ingredient A contains from 1% to 40% by weight of said ingredient A of at least one surface-active compound selected from the group consisting of anionic, non-ionic and amphoteric surfaceactive compounds, from to 80% by weight of said ingredient A of builder compounds selected from the 12 group consisting of non-surface-active cleaning builder salts and complexing builder salts, and from 10% to 50% by Weight of said ingredient A of an active-oxygen percompound.
• said at least one surfaceactive compound consists of from 25% to by Weight of surface-active sulfonates and sulfates, from 5% to 40% of non-ionic polyglycolethers and from 10% to 50% of soap.
• the low-foaming rinsing, washing and cleaning compositions of claim 7 wherein said builder compounds consist of from 25 to 95% of alkali metal triphosphates and their mixtures with alkali metal pyrophosphates, from 5% to 50% of an alkali metal salt of a complexing compound selected from the group consisting of polyphosphonic acids, nitrotriacetic acid and ethylenediaminetetraacetic acid, and from 5% to of at least one compound selected from the group consisting of alkali metal silicates, alkali metal carbonates and alkali metal borates.
• a complexing compound selected from the group consisting of polyphosphonic acids, nitrotriacetic acid and ethylenediaminetetraacetic acid
• the low-foaming rinsing, washing and cleaning compositions of claim 7 having a further content of from 0.2% to 3% by weight of said ingredient A of enzymes selected from the group consisting of proteases, lipeases and amylases.
• the low-foaming rinsing, washing and cleaning compositions of claim 7 having a further content of from 0.2% to 3% by Weight of said ingredient A of greying inhibitors.
• the low-foaming rinsing, washing and cleaning compositions of claim 7 having a further content of from 0.01% to 1.5% by weight of said ingredient A of optical brighteners.
• the low-foaming rinsing, washing and cleaning compositions of claim 7 having a further content of from 0 to 5% by weight of said ingredient A of foam inhibitors selected from the group consisting of saturated fatty acids having 20 to 24 carbon atoms and their alkali metal salts, parafiins, triglycerides of fatty acids and trialkylmelamines.
• said ingredient A consists of cleaning and complexing compounds selected from the group consisting of polyphosphates of the formula (n+2)' n an+1) and metaphosphates of the formula wherein Me represents a metal ion selected from the group consisting of sodium and potassium, n represents an integer from 3 to 20 and m represents an integer from 5 to 30, sodium nitrilotriacetate, potassium nitrilotriacetate, sodium ethylenediaminetetraacetate and potassium ethylenediaminetetraacetate.

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• 1969
  • 1969-12-31 DE DE19691965639 patent/DE1965639A1/de active Pending
• 1970
  • 1970-11-26 NL NL7017315A patent/NL7017315A/xx unknown
  • 1970-12-09 US US96672A patent/US3703469A/en not_active Expired - Lifetime
  • 1970-12-29 BE BE760960A patent/BE760960A/xx unknown
  • 1970-12-30 AT AT1175370A patent/AT305477B/de active
  • 1970-12-30 FR FR707047229A patent/FR2072148B1/fr not_active Expired

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