EP0741775A1 - 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

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Publication number
EP0741775A1
EP0741775A1 EP95906343A EP95906343A EP0741775A1 EP 0741775 A1 EP0741775 A1 EP 0741775A1 EP 95906343 A EP95906343 A EP 95906343A EP 95906343 A EP95906343 A EP 95906343A EP 0741775 A1 EP0741775 A1 EP 0741775A1
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EP
European Patent Office
Prior art keywords
boric acid
washing
mixtures
acid esters
cleaning agent
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
EP95906343A
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German (de)
English (en)
Other versions
EP0741775B1 (fr
Inventor
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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Application filed by Henkel AG and Co KGaA filed Critical Henkel AG and Co KGaA
Publication of EP0741775A1 publication Critical patent/EP0741775A1/fr
Application granted granted Critical
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Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

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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
    • C11D3/16—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 field 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 16628 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 in acidic aqueous surfactant solutions leads to an optimization of the flow and metering behavior of these solutions in accordance with 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, when processed to form an aqueous washing liquor, have a neutral to alkaline pH - Set values that can be important.
  • these detergent 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 detergent and cleaning agent mixtures.
  • the teaching of the invention described below is of particular importance for the field of textile detergents and here in particular for their use in removing enzyme-specific soiling.
  • the invention relates to solid, pasty or liquid detergent and / or cleaning agent formulations, in particular textile detergents which, in aqueous mixture, adjust pH values in the neutral to alkaline range and anionic surfactants together with nonionic surfactants and contain other common auxiliaries and additives.
  • these formulations of valuable substances are now characterized in that, in addition or instead of at least a portion of the non-surfactants, boric acid esters of saturated and / or unsaturated monohydric alcohols containing 8 to 22 carbon atoms, which are combined with one or more alkylene oxides 2 to 4 carbon atoms are alkoxylated.
  • the invention relates to the use of esters of boric acid and alkoxylated fatty alcohols having a 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 mixing of anionic and nonionic surfactant compounds contain together with other usual valuable and auxiliary substances and are especially designed for the removal of enzyme-specific impurities.
  • 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) have been.
  • 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 EO-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 EO units per fatty alcohol molecule - can fluctuate within wide limits and reach, for example, average values in the range up to 40 E0 or above.
  • suitable fatty alcohol derivatives with a lower degree of ethoxylation which is expediently in the range of up to 20 or 25 EO 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 EO 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 niotene surfactants usually used in textile detergents, the specific nature of which in connection with the description of this valuable component in the context of the valuable substance mixtures according to the invention below is discussed in detail.
  • 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.
  • the degree of alkoxylation of the alcoholic components used as a whole to produce the boric acid esters can be the same or different.
  • it should be taken into account here that even in the case of a specific alkoxylation product of a selected fatty alcohol base component, mixtures of substances are used - and are then present as a reaction product - which, in relation to the degree of alkoxylation present in the specific case, only increase via static mean values are labeled.
  • boric acid esters are also generally defined in the sense of the invention using statistical averages. According to the details of DE-A 39 16628 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 form 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 - especially at temperatures above 100 ° C. - with removal of the reaction water.
  • the boric acid esters obtained are generally weakly colored and crystallizing liquid phases on cooling can be comminuted 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, even if they also contrast with the overarching objective of improving the detergency enzyme-specific stains are worn:
  • 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. It has been shown, however, that by using the boric acid esters defined according to the invention, effective improvements in washing performance can be achieved even in the area of cleaning enzyme-specific textile soils concerned, even if the detergents used in today's washing and cleaning agents are also used usual enzyme additives is dispensed with. 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 - possibly even up to for example 60% by weight. Contents of the value and auxiliary mixture of boric acid ester in the range from 1 to 25% by weight are preferred, with 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.
  • Particularly suitable 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.
  • the readily biodegradable alkanesulfonates which are made from C12-
  • Alkanes can be obtained, for example, by sulfochlorination or sulfoxidation with subsequent hydrolysis or neutralization.
  • the sulfonate group is statistically distributed over the entire carbon chain, the secondary alkanesulfonates predominating.
  • Suitable surfactants of the sulfate type 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 1-10 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 also contain proportions of unsaturated alcohols For example, oleyl alcohol.
  • the proportion of the alkyl radicals is 50 to 70% by weight on C12, 18 to 30% by weight on C14, 5 to 15% by weight on Cjß, less than 3% by weight. % on C10 and less than 10% by weight on Ci ⁇ .
  • 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. These include the monoesters, diesters and triesters, and also their mixtures, as obtained in the preparation by esterification by a monoglycerol with 1 to 3 mol of fatty acid or in the transesterification of triglycerides with 0.3 to 2 mols of glycerol become.
  • Preferred sulfated fatty acid glycerol esters are the sulfonation products of saturated fatty acids with 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. Because of 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 WO-A-91/09009 is specified.
  • the sulfonation products are a complex mixture containing mono-, di- and triglyceride sulfonates with alpha and / or internal sulfonic acid grouping.
  • Sulfonated fatty acid salts glyceride sulfates, glycerol sulfates, glycerol and soaps are formed as by-products. If one starts from the sulfonation of saturated fatty acids or hardened fatty acid glyceryl ester mixtures, the proportion of the alpha-sulfonated fatty acid disalts can be up to about 60% by weight, depending on the procedure.
  • 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 Ci2-18 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 Ci2-i6 _rT fatty acid mixtures.
  • the proportion of Ci2_i4 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, preferably ethoxylated fatty alcohols, in particular primary alcohols with preferably 9 to 18 carbon atoms and On average, 1 to 12 moles of ethylene oxide (EO) are used per mole of alcohol, in which the alcohol radical can be linear or methyl-branched in the 2-position, or can contain linear and methyl-branched radicals in the mixture, as are usually present in oxo alcohol radicals.
  • EO ethylene oxide
  • alcohol ethoxylates are preferred which have an average of 2 to 8 EO.
  • the preferred ethoxylated alcohols include, for example, in particular Ci2-14 alcohols with 3 EO or 4 EO, Cg_n alcohol with 7 EO, Ci3_i5 alcohols with 3 EO, 5 EO, 7 EO or 8 EO, Ci2-i8 alcohols with 3 EO, 5 EO or 7 EO and mixtures of these such as mixtures of Ci2-14 alcohol with 3 EO and Ci2-i8 alcohol with 5 EO.
  • 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 can - as stated above - in one embodiment also in whole or in part by the boric acid esters defined according to the invention based on nonionic surfactants to be replaced.
  • nonionic surfactants are, for example, tallow fatty alcohols with 11 EO, 14 EO or 25 EO.
  • alkoxylated alcohols with up to 80 EO preferably tallow fatty alcohol with 40 EO or polyethylene glycols, preferably with a relative molecular weight between 200 and 600, can also be used
  • Mixture with other nonionic surfactants can be used.
  • customary ingredients of the 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 of their sodium or potassium salts.
  • Suitable inorganic builder substances are, for example, zeolites, phosphates and layered silicates.
  • the fine 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 suspension stabilized while 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-2334899, EP-A-0026 529 and DE-A-3526405. 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 NaMSi x ⁇ 2 ⁇ + ⁇ * yH2 ⁇ , 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 sheet silicates are described, for example, in European patent application EP-A-01 64514.
  • Preferred crystalline layered silicates are those in which M represents sodium and x assumes the values 2 or 3.
  • both beta and delta sodium silicates Na2S ⁇ ' 2 ⁇ 5 * yH2 ⁇ are preferred.
  • Custom Bare 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, amino carboxylic 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 thereof.
  • 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 and 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-0280223.
  • customary ingredients of the class of detergents and cleaning agents in solid form which are concerned according to the invention are 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 a2 ⁇ : Si ⁇ 2 of 1: 1 to 1: 4.5, preferably from 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 natriu sili- Kat is generally up to 10 wt .-% and preferably between 2 and 8 wt .-%.
  • 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 peracid salts or peracids providing H2O2, such as perbenzoates, peroxophthalates, diperazelaic acid or diperdodecanedioic acid.
  • bleach activators can be incorporated into the preparations.
  • Examples include N-acyl or O-acyl compounds which form organic peracids with H2O2, 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 fiber suspended in the liquor and thus preventing graying.
  • Water-soluble colloids of mostly organic nature 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 ether are preferred.
  • Suitable foam inhibitors are, for example, soaps of natural or synthetic origin, which have a high proportion of Ci8-24 fatty acids.
  • Suitable non-surfactant-like foam inhibitors are, for example, organopolysiloxanes and their mixtures with microfine, optionally siliconized 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 proteins 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 stabilizers in particular for per-compounds and - in a conventional sense also - for enzymes are the salts of polyphosphonic acids, preferably the neutral sodium salts of, for example, 1-hydroxyethane-1,1-diphosphonate and diethylene triamine pentamethylene phosphonate and in particular l-hydroxyethane-l, l- diphosphonic acid into consideration.
  • Sodium formate for example, can also be used as a stabilizer.
  • Derivatives of diaminostilbenedisulfonic acid or their alkali metal salts can be used as optical brighteners. Suitable are, for example, salts of 4,4'-bis (2-anilino-4-morpholino-l, 3,5-triazinyl-6-amino) stilbene-2,2'-disulfonic acid or compounds of similar structure which are used instead of morpholino Group carry a diethanolamino group, a methylamino group, 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 coloring S toffzu accounts, particularly the blue dye Tinolu ⁇ (R) (commercial product of Ciba-Geigy) used concomitantly.
  • R blue dye Tinolu ⁇
  • 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 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 .-%.
  • Detergent preparations in liquid to pasty form can be aqueous or essentially water-free agents.
  • “essentially anhydrous” 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 also colorants and fragrances can be contained as further ingredients, as described, for example, in the international patent application message W0-A-92/02610 are described.
  • the compounds which serve as peroxy bleaching agents and supply H2O2 in water the sodium perborate tetrahydrate and the sodium perborate monohydrate are of particular importance.
  • Other bleaching agents are, for example, H2O2, peroxycarbonate, citrate perhydrates and H2O2-providing peracidic salts of peracids such as perbenzoates, peroxyphthalates or diperoxydodecanedioic acid.
  • thickeners which can be used are 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 4026809, DE 4026471 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 1-6 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 1-5 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 367049.
  • These partially esterified polymers are obtained by copolymerizing (a) at least one C4_28 ⁇ 01efin or mixtures of at least one C4_28 ⁇ 01efin with up to 20 mol% of C ⁇ _28-alkyl vinyl ethers and (b) ethylenically unsaturated dicarboxylic acid anhydrides with 4 to 8 carbon atoms in a molar ratio 1: 1 to copolymers with K values from 6 to 100 and subsequent partial esterification of the copolymers with reaction products such as C ⁇ _i3 alcohols, C8_22 ⁇ ' : Ettklare, C ⁇ _i2 ⁇ alkylphenols, secondary C2-30 _Am in en or their mixtures with at least a C2-4-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
  • 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 Pas (Brookfield viscometer, spindle 1, 20 revolutions per minute, 20 ° C.). Viscosities 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.
  • the liquid supply forms for detergents and cleaning agents discussed last can also include 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 colorants and fragrances, opacifiers or pearlescent agents tel, included.
  • additives for example salts of polycarboxylic acids or polyphosphonic acids, optical brighteners, enzymes, enzyme stabilizers, small amounts of neutral filler salts, and also colorants and fragrances, opacifiers or pearlescent agents tel, included.
  • Detergent I liquid detergent according to usual practice (state of the art)
  • WM II Detergent II
  • the formulation of WM I is modified in such a way that instead of the nonionic surfactant content, an amount of nonionic surfactant boric acid ester in the sense of the definition according to the invention is used.
  • WM III Detergent III
  • the nonionic surfactant boric acid ester as defined by the invention according to the definition of the invention is mixed in a limited amount (10% by weight, based on the free nonionic surfactant content) as an additional component into the detergent components from WM I used in the same proportions.
  • Anionic surfactant commercial product "Sulfopon K 35" from the applicant (aqueous-pasty preparation based on C 1-10 fatty alcohol sulfate with 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 range C12-I8 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 individually the following:
  • the comparison of the numerical values shows in the predominant number of the washing results to be compared with one another the increased remission values of the washing results achieved with detergent types II and III according to the invention. It is particularly interesting that this tendency is also evident in the enzyme-free detergent formulations, although in absolute terms the washing results achieved here - predictably - are lower than when enzymes are also used.

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  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Wood Science & Technology (AREA)
  • Organic Chemistry (AREA)
  • Detergent Compositions (AREA)
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
DE4403146 1994-02-02
DE4403146A DE4403146A1 (de) 1994-02-02 1994-02-02 Wasch- und Reinigungsmittelgemische für den Einsatz im neutralen bis alkalischen Bereich
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 true EP0741775A1 (fr) 1996-11-13
EP0741775B1 EP0741775B1 (fr) 1997-10-29

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Application Number Title Priority Date Filing Date
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)

Families Citing this family (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

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See references of WO9521235A1 *

Also Published As

Publication number Publication date
ATE159754T1 (de) 1997-11-15
WO1995021235A1 (fr) 1995-08-10
DE59500911D1 (de) 1997-12-04
ES2110313T3 (es) 1998-02-01
EP0741775B1 (fr) 1997-10-29
DE4403146A1 (de) 1995-08-03

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