EP0741775B1 - Melanges de detergents et de nettoyants s'utilisant dans la plage allant du neutre a l'alcalin - Google Patents

Melanges de detergents et de nettoyants s'utilisant dans la plage allant du neutre a l'alcalin Download PDF

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Publication number
EP0741775B1
EP0741775B1 EP95906343A EP95906343A EP0741775B1 EP 0741775 B1 EP0741775 B1 EP 0741775B1 EP 95906343 A EP95906343 A EP 95906343A EP 95906343 A EP95906343 A EP 95906343A EP 0741775 B1 EP0741775 B1 EP 0741775B1
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Prior art keywords
boric acid
mixtures
detergents
acid esters
contain
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EP95906343A
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German (de)
English (en)
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EP0741775A1 (fr
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Georg Meine
Peter Daute
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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
    • C11D3/166—Organic compounds containing borium

Definitions

  • the invention relates to detergent and / or cleaning agent mixtures in solid or also liquid to pasty form, which in practical use lead to washing liquors with pH values in the neutral to alkaline range when mixed with water.
  • the area of corresponding textile detergents is particularly affected, a particular objective of the teaching according to the invention being to positively influence the washing power compared to enzyme-specific soiling.
  • DE-A 39 16 628 relates to the use of esters of boric acid with selected monofunctional and / or polyfunctional alcohols as a thickening component in aqueous acidic surfactant solutions. Particular emphasis is placed on the alcohol component forming the boric acid ester, primary or secondary alcohols with 8 to 22 carbon atoms, which are alkoxylated with up to 20 mol of one or more alkylene oxides with 2 to 4 carbon atoms.
  • the use of, for example, 0.2 to 10% by weight of such boric acid esters leads to an optimization of the flow and metering behavior of these solutions in acidic aqueous surfactant solutions according to the information in the cited literature reference. At the same time, optically clear and aging-stable aqueous solutions of the type mentioned can be obtained.
  • esters of boric acid and selected alkoxylated longer-chain alcohols particularly in the field of conventional detergents and / or cleaning agents, which adjust neutral to alkaline pH values when they are processed into aqueous washing liquors, important importance.
  • these washing and cleaning agent mixtures usually represent solid combinations of valuable materials, but the use of the boric acid esters defined according to the invention is also helpful in corresponding pasty or liquid washing and cleaning agent mixtures.
  • the invention relates to solid, pasty or liquid detergent and / or cleaning agent formulations, in particular textile detergents, which adjust pH values in the neutral to alkaline range in aqueous mixture and anionic surfactants together with nonionic surfactants and other customary auxiliaries and additives contain.
  • these valuable substance formulations are now characterized in that they contain, in addition to or instead of at least a portion of the nonionic surfactants, boric acid esters of saturated and / or unsaturated monohydric alcohols having 8 to 22 carbon atoms, those with one or more alkylene oxides having 2 to 4 carbon atoms are alkoxylated.
  • the invention relates to the use of esters of boric acid and alkoxylated fatty alcohols with nonionic surfactant character of natural and / or synthetic origin, in addition to or instead of conventional nonionic surfactant compounds in neutral to alkaline washing and cleaning agent mixtures, the blends of anionic and nonionic surfactant compounds together with contain other common valuable and auxiliary materials and are designed in particular for the removal of enzyme-specific impurities.
  • the chemical constitution of the boric acid esters used as additional aids according to the invention can be assigned to the classes of mono-, di- and / or triesters of boric acid, alkoxylated long-chain monofunctional alcohols or corresponding alcohol mixtures being used as the ester-forming alcohol component (s) .
  • Preferred basic building blocks are primary fatty alcohols of natural and / or synthetic origin, which can be straight-chain and / or branched. Corresponding fatty alcohols with 12 to 20 carbon atoms and in particular with 12 to 18 carbon atoms are of particular importance here. These fatty alcohol residues of natural and / or synthetic origin can be aliphatically saturated, but optionally also olefinically 1- and / or poly-olefinically unsaturated. Saturated fatty alcohols and compounds with an olefinic double bond in the fatty alcohol molecule can be of particular importance.
  • the fatty alcohols do not form the boric acid esters defined according to the invention; their lower alkoxylates are the ester-forming alcohol components.
  • the corresponding ethoxylated and / or propoxylated fatty alcohol derivatives are of crucial importance, in particular the E0-modified fatty alcohols are suitable components for the formation of the boric acid esters used according to the invention.
  • the degree of alkoxylation - in particular the average number of E0 units per fatty alcohol molecule - can fluctuate within wide limits and reach, for example, average values in the range up to 40 E0 or even higher.
  • suitable fatty alcohol derivatives with a lower degree of ethoxylation which is advantageously in the range up to 20 or 25 E0 units per mole of alcohol, are particularly suitable.
  • Preferred alkoxylated alcohol components forming the boric acid esters are classic representatives of the nonionic surfactants and thus in particular primary alcohols with preferably 9 to 18 carbon atoms and an average of up to 12 to 15 E0 units per mole of alcohol.
  • the alcohol residues of the boric acid esters are derived from corresponding nonionic surfactants based on fatty alcohol and in particular from nonionic surfactants commonly used in textile detergents, the specific nature of which is described in detail below in connection with the description of this valuable component in the context of the valuable substance mixtures according to the invention.
  • the alkoxylated alcohol residues in the boric acid ester can each be based on the same or different fatty alcohols, and the degree of alkoxylation of the alcoholic components used as a whole to produce the boric acid esters can be the same or different.
  • substance mixtures are used in the case of a specific alkoxylation product of a selected fatty alcohol base component - and are then present as a reaction product - which, with regard to the degree of alkoxylation present in the specific case, can only be identified by means of static mean values.
  • boric acid esters are also generally defined in the sense of the invention using statistical averages. According to the details of DE-A 39 16 628 mentioned at the outset, boric acid esters are capable of forming complex esters with 4 ester groups, in addition to their 3 hydroxyl groups available for esterification. It remains to be seen to what extent corresponding ester types can develop in the sense of the invention.
  • the boric acid esters used show molar ratios of the monohydric alcohols to boron in the range from about 1 to 3 and in particular in the range between about 1.5 and 2.5. As indicated, these numerical values are statistical averages.
  • the boric acid esters or ester mixtures used according to the invention can be prepared in a manner known per se by reacting the boric acid and the alkoxylated fatty alcohols or fatty alcohol mixtures in the stoichiometric ratios desired in the presence of acidic catalysts at elevated temperatures, in particular at temperatures above 100 ° C. with removal of the water of reaction.
  • the boric acid esters obtained are generally weakly colored and crystallizing liquid phases on cooling can be shredded in conventional form and are therefore suitable for use in solid as well as in liquid or pasty detergent mixtures.
  • the boric acid esters defined according to the invention as a new active ingredient component in detergent and cleaning agent mixtures known per se for their use in the neutral to alkaline range, the following 3 embodiments can be differentiated from one another if they are also supported by the overarching objective of improving the washing power, in particular with regard to enzyme-specific soiling :
  • the boric acid esters according to the invention can be added to classic detergent formulations which contain wash-active enzymes as an important auxiliary, in particular from the class of proteases, lipases, amylases and / or cellulases.
  • wash-active enzymes as an important auxiliary, in particular from the class of proteases, lipases, amylases and / or cellulases.
  • Such a substitution of the enzyme-based auxiliaries mentioned by the boric acid esters defined according to the invention can be carried out proportionately or completely.
  • the specific embodiment chosen in each individual case determines the amount of the boric acid esters of the definition according to the invention used in the mixture of valuable materials of the respective detergent and cleaning agent.
  • the content of boric acid esters can be in the range from 0.5 to 50% by weight - if appropriate also in excess of, for example, up to 60% by weight. Contents of the valuable and auxiliary mixture of boric acid esters in the range from 1 to 25% by weight are preferred, corresponding contents in the range from about 2 to 15% by weight being particularly important.
  • anionic surfactants and nonionic surfactants are usually used as surfactant components in washing and cleaning agents.
  • the anionic surfactants are preferably used in the form of their alkali metal salts, in particular as sodium or potassium salts.
  • Important anionic surfactants belong to the classes of sulfonates and / or sulfates.
  • sulfonates are sulfonates based on oleochemistry, such as the esters of alpha-sulfo fatty acids, the sulfo group being in its salt form (mono salt), for example the alpha-sulfonated methyl esters of hydrogenated coconut, palm kernel or tallow fatty acids.
  • sulfonates obtained from C 12-18 alkanes, for example by sulfochlorination or sulfoxidation with subsequent hydrolysis or neutralization.
  • the sulfonate group is statistically distributed over the entire carbon chain, with the secondary alkanesulfonates predominating.
  • a disadvantage of alkanesulfonates is that they are obtained from petrochemical raw materials.
  • Suitable sulfate-type surfactants are the sulfuric acid monoesters from primary alcohols of natural and synthetic origin, in particular from fatty alcohols.
  • Suitable fatty alcohols are the sulfuric acid monoesters of the C 12-18 fatty alcohols, such as lauryl, myristyl, cetyl alcohol or stearyl alcohol, and the fatty alcohol mixtures obtained from coconut oil, palm and palm kernel oil, which additionally contain fractions of unsaturated alcohols, for example oleyl alcohol can.
  • Mixtures in which the proportion of the alkyl radicals is 50 to 70% by weight on C 12 , 18 to 30% by weight on C 14 , 5 to 15% by weight on C 16 , are preferred 3% by weight on C 10 and less than 10% by weight on C 18 are distributed.
  • the proportion of fatty alkyl sulfates in the active ingredient mixture can be, for example, 1 to 20% by weight and in particular 3 to 15% by weight.
  • anionic surfactants are sulfonated fatty acid glycerol esters. This includes the monoesters, diesters and triesters, as well as their mixtures, as are obtained in the production by esterification by a monoglycerol with 1 to 3 moles of fatty acid or in the transesterification of triglycerides with 0.3 to 2 moles of glycerol.
  • Preferred sulfated fatty acid glycerol esters are the sulfonation products of saturated fatty acids having 6 to 22 carbon atoms, for example caproic acid, caprylic acid, capric acid, myristic acid, lauric acid, palmitic acid, stearic acid or behenic acid.
  • fats and oils that is to say natural mixtures of different fatty acid glycerol esters
  • suitable feedstocks are palm oil, palm kernel oil, palm stearin, olive oil, turnip oil, coriander oil, sunflower oil, cottonseed oil, peanut oil, linseed oil, lard oil or lard. Due to their high natural content of saturated fatty acids, it has proven to be particularly advantageous to start from coconut oil, palm kernel oil or beef tallow.
  • the sulfonation of the saturated fatty acids with 6 to 22 carbon atoms or the mixtures of fatty acid glycerol esters with iodine numbers less than 5, which contain fatty acids with 6 to 22 carbon atoms, is preferably carried out by reaction with gaseous sulfur trioxide and subsequent neutralization with aqueous bases, as described in international patent application W0 -A-91/09009.
  • the sulfonation products are a complex mixture which contains mono-, di- and triglyceride sulfonates with alpha and / or internal sulfonic acid grouping.
  • sulfonated fatty acid salts glyceride sulfates, glycerine sulfates, glycerin and soaps are formed. If one starts from the sulfonation of saturated fatty acids or hardened fatty acid glycerol ester mixtures, the proportion of the alpha-sulfonated fatty acid disalts can, depending on the procedure, be up to about 60% by weight.
  • Suitable anionic surfactants are the salts of alkylsulfosuccinic acid, which are also referred to as sulfosuccinates or as sulfosuccinic acid esters and which are monoesters and / or diesters of sulfosuccinic acid with alcohols, preferably fatty alcohols, and in particular ethoxylated fatty alcohols.
  • alcohols preferably fatty alcohols, and in particular ethoxylated fatty alcohols.
  • Sulfosuccinates whose fatty alcohol residues are derived from ethoxylated fatty alcohols with a restricted homolog distribution can be particularly preferred.
  • Suitable anionic surfactants are, in particular, soaps, preferably in amounts of 3 to 25% by weight, in particular in amounts of 5 to 20% by weight.
  • Saturated fatty acid soaps are suitable, such as the salts of lauric acid, myristic acid, palmitic acid or stearic acid, and in particular soap mixtures derived from natural fatty acids, for example coconut, palm kernel or tallow fatty acids.
  • Salts of saturated and unsaturated fatty acids with C 12-18 chain lengths in the form of their mixtures are particularly suitable.
  • a preferably used soap mixture is formed from sodium oleate and the sodium salts of the saturated C 12-16 fatty acid mixtures.
  • the proportion of C 12-14 fatty acids in the saturated component is advantageously at least 60% by weight, preferably at least 75% by weight (calculated as fatty acid). Suitable for this purpose are, for example, coconut fatty acids, from which the portions with 10 and fewer carbon atoms are largely separated.
  • the preferred nonionic surfactants are liquid ethoxylated and / or propoxylated, with preference for the ethoxylated fatty alcohols, in particular primary alcohols with preferably 9 to 18 carbon atoms and average 1 to 12 moles of ethylene oxide (E0) are used per mole of alcohol, in which the alcohol radical may be linear or methyl-branched in the 2-position, or may contain linear and methyl-branched radicals in the mixture, as are usually present in oxo alcohol radicals.
  • alcohol ethoxylates are preferred which have an average of 2 to 8 E0.
  • the preferred ethoxylated alcohols include, for example, in particular C 12-14 alcohols with 3 E0 or 4 E0, C 9-11 alcohol with 7 E0, C 13-15 alcohols with 3 E0, 5 E0, 7 E0 or 8 E0, C 12-18 alcohols with 3 E0, 5 E0 or 7 E0 and mixtures thereof, such as mixtures of C 12-14 alcohol with 3 E0 and C 12-18 alcohol with 5 E0.
  • the degrees of ethoxylation given represent statistical averages, which can be an integer or a fraction for a specific product.
  • Preferred alcohol ethoxylates have a restricted homolog distribution (narrow range ethoxylates, NRE).
  • the content of liquid nonionic surfactants in the detergents and cleaning agents is, for example, 15 to 65% by weight, but, as stated above, in one embodiment it can also be completely or partially replaced by the boric acid esters based on nonionic surfactants defined according to the invention.
  • nonionic surfactants are, for example, tallow fatty alcohols with 11 E0, 14 E0 or 25 E0.
  • alkoxylated alcohols with up to 80 E0 preferably tallow fatty alcohol with 40 E0 or polyethylene glycols, preferably with a relative molecular weight between 200 and 600, in a mixture with other nonionic surfactants can be used.
  • mixtures of materials according to the invention are, in particular, inorganic and / or organic builder substances, alkali carbonates and alkali silicates, optical brighteners, bleaching agents, graying inhibitors and, if appropriate, foam inhibitors, bleach activators, enzymes, textile-softening substances, colorants and fragrances, and neutral salts such as sulfates and / or chlorides in the form their sodium or potassium salts.
  • inorganic and / or organic builder substances alkali carbonates and alkali silicates, optical brighteners, bleaching agents, graying inhibitors and, if appropriate, foam inhibitors, bleach activators, enzymes, textile-softening substances, colorants and fragrances, and neutral salts such as sulfates and / or chlorides in the form their sodium or potassium salts.
  • Suitable inorganic builder substances are, for example, zeolites, phosphates and layered silicates.
  • the finely crystalline, synthetic and bound water-containing zeolite used is preferably zeolite NaA in detergent quality.
  • zeolite NaX and mixtures of NaA and NaX are also suitable.
  • the zeolite can be used as a spray-dried powder or as an undried stabilized suspension that is still moist from its production.
  • Suitable zeolites have an average particle size of less than 10 ⁇ m (volume distribution; measurement method: Coulter Counter) and preferably contain 18 to 22, in particular 20 to 22% by weight of bound water.
  • Suitable substitutes or partial substitutes for the zeolite are layer silicates of natural and synthetic origin.
  • Layered silicates of this type are known, for example, from patent applications DE-B-23 34 899, EP-A-0 026 529 and DE-A-35 26 405. Their usability is not limited to a special composition or structural formula.
  • Suitable substitutes or partial substitutes for phosphates or zeolites are in particular also crystalline layered sodium silicates of the general formula NaNSi x O 2x + 1 .yH 2 O, where M is sodium or hydrogen, x is a number from 1.9 to 4 and y is a number from 0 to 20 and preferred values for x are 2, 3 or 4.
  • Such crystalline layered silicates are described, for example, in European patent application EP-A-01 64 514.
  • Preferred crystalline layered silicates are those in which M is sodium and x is 2 or 3.
  • both beta and delta sodium silicates Na 2 Si 2 O 5 .yH 2 O are preferred.
  • Usable Organic builders are, for example, the polycarboxylic acids preferably used in the form of their sodium salts, such as citric acid, adipic acid, succinic acid, glutaric acid, tartaric acid, sugar acids, aminocarboxylic acids, nitrilotriacetic acid (NTA), and mixtures of these.
  • Preferred salts are the salts of polycarboxylic acids such as citric acid, adipic acid, succinic acid, glutaric acid, tartaric acid, sugar acids and mixtures of these.
  • Suitable polymeric polycarboxylates are, for example, the sodium salts of polyacrylic acid or polymethacrylic acid, for example those with a relative molecular weight of 800 to 150,000 (based on acid).
  • Suitable copolymeric polycarboxylates are, in particular, those of acrylic acid with methacrylic acid and of acrylic acid or methacrylic acid with maleic acid. Copolymers of acrylic acid with maleic acid which contain 50 to 90% by weight of acrylic acid and 50 to 10% by weight of maleic acid have proven to be particularly suitable.
  • Their relative molecular weight, based on free acids is generally 5,000 to 200,000, preferably 10,000 to 120,000 and in particular 50,000 to 100,000.
  • biodegradable terpolymers for example those which contain salts of acrylic acid and maleic acid as well as vinyl alcohol or vinyl alcohol derivatives as monomers or those which contain salts of acrylic acid and 2-alkylallylsulfonic acid and sugar derivatives as monomers.
  • polyacetals which can be obtained by reacting dialdehydes with polyolcarboxylic acids which have 5 to 7 carbon atoms and at least 3 hydroxyl groups, see, for example, EP-A-0 280 223.
  • water-soluble inorganic salts such as bicarbonates, carbonates, amorphous silicates or mixtures of these.
  • alkali carbonates and amorphous alkali disilicate especially sodium silicate with a molar ratio Na 2 O: SiO 2 of 1: 1 to 1: 4.5, preferably of 1: 2 to 1: 3.5, are used.
  • the sodium carbonate content of the mixtures of valuable substances can be, for example, up to 20% by weight, preferably between 2 and 5% by weight.
  • the content of sodium silicate is generally up to 10% by weight and preferably between 2 and 8% by weight.
  • bleaching agents which serve as bleaching agents and supply H 2 O 2 in water
  • sodium perborate tetrahydrate and sodium perborate monohydrate are of particular importance.
  • Further bleaching agents which can be used are, for example, sodium percarbonate, peroxypyrophosphates, citrate perhydrates and H 2 O 2 -producing peracid salts or peracids, such as perbenzoates, peroxophthalates, diperazelaic acid or diperdodecanedioic acid.
  • bleach activators can be incorporated into the preparations.
  • these are N-acyl or O-acyl compounds which form organic peracids with H 2 O 2 , preferably N, N'-tetraacylated diamines, such as tetraacetylethylene diamine, carboxylic acid anhydrides and esters of polyols such as glucose pentaacetate.
  • Graying inhibitors have the task of keeping the dirt detached from the fibers suspended in the liquor and thus preventing graying.
  • Water-soluble colloids are suitable for this, for example the water-soluble salts of polymeric carboxylic acids, glue, gelatin, salts of ether carboxylic acids or ether sulfonic acids of starch or cellulose or salts of acidic sulfuric acid esters of cellulose or starch.
  • Water-soluble polyamides containing acidic groups are also suitable for this purpose.
  • Soluble starch preparations and starch products other than those mentioned above can also be used, for example degraded starch, aldehyde starches, etc.
  • Polyvinylpyrrolidone can also be used.
  • cellulose ethers such as carboxymethyl cellulose, methyl cellulose, hydroxyalkyl cellulose and mixed ethers are preferred.
  • Suitable foam inhibitors are, for example, soaps of natural or synthetic origin, which have a high proportion of C 18-24 fatty acids.
  • Suitable non-surfactant-like foam inhibitors are, for example, organopolysiloxanes and their mixtures with microfine, optionally silanized silica, and also paraffins, waxes, microcrystalline waxes and their mixtures with silanized silica or bistearylethylenediamide. Mixtures of different foam inhibitors are also used with advantages.
  • the foam inhibitors are preferably bound to a granular water-soluble or dispersible carrier substance.
  • Enzymes from the classes of proteases, lipases, amylases, cellulases or mixtures thereof are possible. Enzymes obtained from bacterial strains or fungi such as Bacillus subtilis, Bacillus licheniformis and Streptomyces griseus are particularly suitable. Proteases of the subtilisin type and in particular proteases which are obtained from Bacillus lentus are preferably used.
  • Enzyme mixtures for example of protease and amylase or protease and lipase or protease and cellulase or of cellulase and lipase or of protease, amylase and lipase or protease, lipase and cellulase, but in particular mixtures containing cellulase, are of particular interest.
  • (Per) oxidases have also proven to be suitable in some cases.
  • the enzymes can be adsorbed on carriers and / or embedded in coating substances in order to protect them against premature decomposition.
  • the salts of polyphosphonic acids preferably the neutral reacting sodium salts of, for example, 1-hydroxyethane-1,1-diphosphonate and diethylenetriaminepentamethylenephosphonate and in particular 1-hydroxyethane-1,1-diphosphonic acid come in as stabilizers, in particular for per-compounds and - in the conventional sense also for enzymes Consideration.
  • Sodium formate for example, can also be used as a stabilizer.
  • Derivatives of diaminostilbenedisulfonic acid or its alkali metal salts can be used as optical brighteners. Suitable are, for example, salts of 4,4'-bis (2-anilino-4-morpholino-1,3,5-triazinyl-6-amino) stilbene-2,2'-disulfonic acid or compounds of the same structure which are used instead of morpholino Group carry a diethanolamino group, a methylamino group, an anilino group or a 2-methoxyethlamino group. Brighteners of the substituted diphenylstyryl type may also be present. Mixtures of the aforementioned brighteners can also be used. Together with the brighteners, small amounts of dye are often added, in particular the blue dye Tinolux (R) (commercial product of Ciba-Geigy), also used.
  • R blue dye Tinolux
  • Preferred alcohols are ethanol, 1,2-propanediol, glycerol and mixtures thereof.
  • the compositions contain, for example, 2 to 20% by weight and in particular 5 to 15% by weight of ethanol or any mixture of ethanol and 1,2-propanediol or in particular of ethanol and glycerol.
  • the detergents according to the invention in liquid to pasty form either in addition to the mono- and / or polyfunctional alcohols having 1 to 6 carbon atoms or also exclusively polyethylene glycol with a relative Molecular mass between 200 and 2,000, preferably up to 600, in particular contained in amounts of about 2 to 17 wt .-%.
  • Hashing agent preparations in liquid to pasty form can be aqueous or essentially water-free agents.
  • “essentially water-free” means that the agent preferably contains no free water that is not bound as crystal water or in a comparable form. In some cases, small amounts of free water are tolerable, especially in amounts up to 5% by weight.
  • Preferred essentially water-free detergents in liquid to pasty form contain 20 to 65% by weight of liquid nonionic surfactants and water in amounts of 0 to 5% by weight.
  • anionic surfactants mentioned and, for example, bleaches, thickeners, builders, inorganic salts, foam inhibitors, enzymes, optical brighteners, and colorants and fragrances, as described, for example, in international patent application WO-A-92/02610, may be present as further ingredients .
  • peroxy bleaching agents sodium perborate tetrahydrate and sodium perborate monohydrate are of particular importance.
  • Further bleaching agents are, for example, H 2 O 2 , peroxy carbonate, citrate perhydrates and H 2 O 2 -producing peracid salts of peracids such as perbenzoates, peroxyphthalates or diperoxydodecanedioic acid.
  • thickeners for example, hardened castor oil, salts of long-chain fatty acids, preferably in amounts of 0 to 5% by weight and in particular in amounts of 0.5 to 2% by weight - for example sodium, potassium, aluminum, magnesium - and titanium stearates or the sodium and / or potassium salts of behenic acid, alkyl glycosides as described in German patent applications DE 40 26 809, DE 40 26 471 and DE 41 02 502 and further polymeric compounds are used.
  • the latter include the mixture components already mentioned, such as polyvinylpyrrolidone, urethanes and the salts of polymeric polycarboxylates.
  • Polymethacrylates and in particular copolymers of acrylic acid with maleic acid are also suitable water-soluble polyacrylates which are crosslinked, for example, with about 1% of a polyallyl ether of sucrose and which have a relative molecular weight above one million. Examples of these are the polymers obtainable under the name Carbopol (R) 940 and 941.
  • the crosslinked polyacrylates are preferably used in amounts not exceeding 2% by weight, preferably in amounts of up to 1% by weight.
  • the water-containing liquid to pasty detergents are preferably free from peroxy bleaching agents. They preferably contain 5 to 35% by weight and in particular 10 to 35% by weight of nonionic surfactants and 20 to 55% by weight and in particular 25 to 45% by weight of water.
  • liquid to pasty compositions contain 10 to 20% by weight of ethoxylated fatty alcohols, preferably a primary C 12-18 fatty alcohol with an average of 1 to 12 moles of ethylene oxide per mole of alcohol.
  • Liquid to pasty concentrates containing 20 to 35% by weight of nonionic surfactants, in particular 22 to 32% by weight of a primary C 12-18 fatty alcohol with an average of 1 to 12 moles of ethylene oxide per mole of fatty alcohol, 28 to 40 are particularly preferred % By weight of water and 5 to 17% by weight of mono- and / or polyfunctional alcohols containing 2 to 4 carbon atoms.
  • the agents can additionally contain about 5 to 20% by weight of a partially esterified copolymer, as described in European patent application 367 049.
  • These partially esterified polymers are obtained by copolymerizing (a) at least one C 4-28 olefin or mixtures of at least one C 4-28 olefin with up to 20 mol% of C 1-28 alkyl vinyl ethers and (b) ethylenically unsaturated dicarboxylic acid anhydrides with 4 to 8 carbon atoms in a molar ratio of 1: 1 to copolymers with K values from 6 to 100 and subsequent partial esterification of the copolymers with reaction products such as C 1-13 alcohols, C 8-22 fatty acids, C 1-12 alkylphenols, secondary C 2-30 amines or mixtures thereof with at least one C 2-4 alkylene oxide or tetrahydrofuran and hydrolysis of the anhydride groups of the copolymers to give carboxyl groups, the partial esterification of the copolymers being carried out to such an extent that 5 to 50% of the carboxyl groups of the Copolymers are esterified.
  • Preferred copolymers contain maleic anhydride as the ethylenically unsaturated dicarboxylic acid anhydride.
  • the partially esterified copolymers can either in Form of the free acid or preferably in partially or completely neutralized form.
  • the copolymers are advantageously used in the form of an aqueous solution, in particular in the form of a 40 to 50% strength by weight solution.
  • the use of these partially esterified copolymers gives concentrated aqueous liquid detergents which are flowable under the sole influence of gravity and without the action of other shear forces.
  • the concentrated aqueous liquid detergents preferably contain partially esterified copolymers in amounts of up to 15% by weight and in particular in amounts of 5 to 12% by weight.
  • the pH of the concentrated, flowable washing and cleaning agents which are particularly preferred according to the invention is generally 7 to 10.5, preferably 7 to 9.5 and in particular 7 to 8.5. Higher pH values, for example above 9, can be set by using small amounts of sodium hydroxide solution or alkaline salts, such as sodium carbonate or sodium silicate.
  • the liquid detergents according to the invention generally have viscosities between 150 and 10,000 mPas (Brookfield viscometer, spindle 1, 20 revolutions per minute, 20 ° C.). Viscosities of between 150 and 5,000 mPas are preferred for the essentially water-free agents.
  • the viscosity of the aqueous compositions is preferably below 2,000 mPas and is in particular between 150 and 1,000 mPas.
  • liquid supply forms for detergents and cleaning agents discussed last can also contain the additives that are usually used, for example salts of polycarboxylic acids or polyphosphonic acids, optical brighteners, enzymes, enzyme stabilizers, small amounts of neutral filler salts, and also dyes and fragrances, opacifiers or pearlescent agents.
  • additives for example salts of polycarboxylic acids or polyphosphonic acids, optical brighteners, enzymes, enzyme stabilizers, small amounts of neutral filler salts, and also dyes and fragrances, opacifiers or pearlescent agents.
  • Anionic surfactant commercial product "Sulfopon K 35" from the applicant (aqueous pasty preparation based on C 12-18 fatty alcohol sulfate with a predominant content of sodium lauryl sulfate)
  • Distilled fatty acids Commercial product "Edenor K 12-18" from the applicant (by far the predominant proportion of fatty acids in the C 12-18 range with a content of approx. 10% by weight of olefinically unsaturated acids)
  • Nonionic surfactant compound as previously stated (“Dehydol LT 7")
  • the recipes for the 3 detergents WM I to III used are as follows: Table I (Numerical values in% by weight) WM I WM II WM III Sulfopon K 35 5 5 5 Edenor K 12-18 5 5 5 KOH 1.2 1.2 1.2 Ethanol 5 5 5 5 Dehydol LT 7 15 0 15 Nio-boric acid ester 0 15 1.5 water rest rest rest;

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Claims (11)

  1. Formulations de produits de lavage et/ou de nettoyage solides, pâteuses ou liquides, en particulier des produits de lavage pour textiles, qui ajustent les valeurs de pH en mélange aqueux dans la plage neutre à alcaline, et qui renferment des agents tensioactifs anioniques conjointement à des agents tensioactifs non ioniques et à d'autres adjuvants et additifs usuels,
    caractérisées en ce qu'
    elles renferment en supplément ou à la place d'au moins une fraction des agents tensioactif non ioniques, un ester d'acide borique d'alcools monovalents saturés et/ou non saturés ayant de 8 à 22 atomes de carbone qui sont alcoxylés avec un ou plusieurs oxydes d'alkylène ayant de 2 à 4 atomes de carbone.
  2. Produits de lavage et/ou de nettoyage selon la revendication 1,
    caractérisés en ce qu'
    ils renferment des mono-, di- et/ou triesters d'acide borique avec des radicaux d'alcools gras alcoxylés, de préférence avec 1,5 à 2,5 (valeur moyenne statistique) radicaux d'alcools gras correspondants dans la molécule.
  3. Produits de lavage et/ou de nettoyage selon les revendications 1 et 2,
    caractérisés en ce que
    les radicaux alcools des esters d'acide borique dérivent des agents tensioactifs non ioniques correspondants à base d'alcools gras, en particulier des agents tensioactifs non ioniques mis en oeuvre habituellement dans les produits de lavage pour articles textiles qui sont substitués en particulier avec jusqu'à 25 radicaux d'oxyde d'alkylène (valeur moyenne statistique).
  4. Produits de lavage et/ou de nettoyage selon les revendications 1 à 3,
    caractérisés en ce qu'
    ils renferment les esters d'acide borique en quantités allant de 0,5 à 50 % en poids, de préférence de 1 à 25 % en poids, à chaque fois rapporté au mélange de substances de valeur, tandis que les teneurs dans la plage de 2 à 15 % en poids peuvent être particulièrement préférées.
  5. Produits de lavage et/ou de nettoyage selon les revendications 1 à 4,
    caractérisés en ce que
    les esters d'acide borique dérivent d'alcools gras primaires, ayant de 12 à 22 atomes de carbone, de préférence de 12 à 18 atomes de carbone qui sont alcoxylés avec jusqu'à 20 mol d'OE ec/ou d'OP.
  6. Produits de lavage et/ou de nettoyage selon les revendications 1 à 5,
    caractérisés en ce qu'
    ils renferment des esters d'acide borique d'alcools gras éthoxylés au moins d'une manière prédominante, d'origine naturelle et/ou synthétique avec de préférence de 2 à 10 unités d'OE (valeur moyenne) par molécule d'alcool gras.
  7. Produits de lavage et/ou de nettoyage selon les revendications 1 à 6,
    caractérisés en ce que
    les esters d'acide borique viennent à l'utilisation dans des agents pour le traitement d'impuretés spécifiques d'enzyme et par là en particulier en ajoutant simultanément des protéases, des lipases, des cellulases et/ou des amylases.
  8. Utilisation d'esters d'acide borique et d'alcools gras alcoxylés ayant un caractère d'agent tensioactif non ionique, d'origine naturelle et/ou synthétique, à côté de ou à la place de composés tensioactifs non ioniques usuels dans des mélanges de produits de lavage et/ou de nettoyage ajustés d'une manière neutre à alcaline, qui renferment des mélanges de composés tensioactifs anioniques et non ioniques conjointement avec d'autres substances de valeur et des adjuvants usuels et sont en particulier disponibles pour l'élimination d'impuretés spécifiques d'enzyme.
  9. Utilisation selon la revendication 8,
    caractérisée en ce que
    des esters d'acide borique avec en moyenne de 1 à 3 radicaux d'alcools gras éthoxylés dans la molécule sont utilisés, qui dérivent de préférence d'alcools gras ou de mélanges d'alcools correspondants ayant de 12 à 22 atomes de carbone, en particulier de 12 à 18 atomes de C.
  10. Utilisation selon les revendications 8 et 9,
    caractérisée en ce qu'
    on ajoute les esters d'acide borique aux produits de lavage pour textiles qui renferment des enzymes actives pour le lavage ou sont mélangés aux mélanges de produits de lavage pour textiles sans ajout d'enzyme en vue de renforcer leur action de nettoyage par rapport aux salissures spécifiques d'un enzyme.
  11. Utilisation selon les revendications 8 à 10,
    caractérisée en ce qu'
    on utilise conjointement les esters d'acide borique dans des préparations pour produits de lavage liquides.
EP95906343A 1994-02-02 1995-01-24 Melanges de detergents et de nettoyants s'utilisant dans la plage allant du neutre a l'alcalin Expired - Lifetime EP0741775B1 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
DE4403146A DE4403146A1 (de) 1994-02-02 1994-02-02 Wasch- und Reinigungsmittelgemische für den Einsatz im neutralen bis alkalischen Bereich
DE4403146 1994-02-02
PCT/EP1995/000240 WO1995021235A1 (fr) 1994-02-02 1995-01-24 Melanges de detergents et de nettoyants s'utilisant dans la plage allant du neutre a l'alcalin

Publications (2)

Publication Number Publication Date
EP0741775A1 EP0741775A1 (fr) 1996-11-13
EP0741775B1 true EP0741775B1 (fr) 1997-10-29

Family

ID=6509280

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EP95906343A Expired - Lifetime EP0741775B1 (fr) 1994-02-02 1995-01-24 Melanges de detergents et de nettoyants s'utilisant dans la plage allant du neutre a l'alcalin

Country Status (5)

Country Link
EP (1) EP0741775B1 (fr)
AT (1) ATE159754T1 (fr)
DE (2) DE4403146A1 (fr)
ES (1) ES2110313T3 (fr)
WO (1) WO1995021235A1 (fr)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE10057670C1 (de) * 2000-11-21 2002-03-14 Siemens Ag Antennenelement

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB1053196A (fr) * 1964-06-30
DE3916628A1 (de) * 1989-05-22 1990-11-29 Henkel Kgaa Verdickungsmittel fuer waessrige tensidloesungen
US5171875A (en) * 1991-01-11 1992-12-15 Lce Partnership Beta branched borate esters

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE10057670C1 (de) * 2000-11-21 2002-03-14 Siemens Ag Antennenelement

Also Published As

Publication number Publication date
ATE159754T1 (de) 1997-11-15
ES2110313T3 (es) 1998-02-01
DE4403146A1 (de) 1995-08-03
EP0741775A1 (fr) 1996-11-13
WO1995021235A1 (fr) 1995-08-10
DE59500911D1 (de) 1997-12-04

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