EP0710274B1 - High wetting-power detergent - Google Patents
High wetting-power detergent Download PDFInfo
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- EP0710274B1 EP0710274B1 EP94924746A EP94924746A EP0710274B1 EP 0710274 B1 EP0710274 B1 EP 0710274B1 EP 94924746 A EP94924746 A EP 94924746A EP 94924746 A EP94924746 A EP 94924746A EP 0710274 B1 EP0710274 B1 EP 0710274B1
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Classifications
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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
- C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
- C11D1/66—Non-ionic compounds
- C11D1/722—Ethers of polyoxyalkylene glycols having mixed oxyalkylene groups; Polyalkoxylated fatty alcohols or polyalkoxylated alkylaryl alcohols with mixed oxyalkylele groups
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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
- C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
- C11D1/66—Non-ionic compounds
- C11D1/72—Ethers of polyoxyalkylene glycols
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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
- C11D10/00—Compositions of detergents, not provided for by one single preceding group
- C11D10/04—Compositions of detergents, not provided for by one single preceding group based on mixtures of surface-active non-soap compounds and soap
- C11D10/045—Compositions of detergents, not provided for by one single preceding group based on mixtures of surface-active non-soap compounds and soap based on non-ionic surface-active compounds and soap
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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
- C11D3/20—Organic compounds containing oxygen
- C11D3/2075—Carboxylic acids-salts thereof
- C11D3/2079—Monocarboxylic acids-salts thereof
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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
- C11D3/26—Organic compounds containing nitrogen
- C11D3/33—Amino carboxylic acids
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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
- C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
- C11D1/88—Ampholytes; Electroneutral compounds
- C11D1/90—Betaines
Definitions
- the invention relates to powdery, pasty or liquid agents for cleaning and / or degreasing hard surfaces, for example metallic surfaces, but in particular surfaces made of organic polymers, for example paints and coatings, but in particular surfaces made of halogenated polyolefins such as polyvinyl chloride.
- the agent is characterized by a combination of active ingredients consisting of amino acids, carboxylic acids or their salts and nonionic surfactants.
- the agents can be used as industrial cleaners (as neutral cleaners or as alkaline cleaners) as well as for vehicle and company cleaning.
- DE-A-27 12 900 describes a method for cleaning metals by spraying.
- the cleaning is carried out at pH values between 7.5 to 11, preferably 8.5 to 10, with solutions which A) soluble salts, preferably alkanolamine salts of aromatic carboxylic acids and / or branched and / or straight-chain aliphatic carboxylic acids with 6 to 12 C atoms, B) one or more nonionic surfactants, C) one or more surface-active quaternary ammonium compounds.
- A) soluble salts, preferably alkanolamine salts of aromatic carboxylic acids and / or branched and / or straight-chain aliphatic carboxylic acids with 6 to 12 C atoms B) one or more nonionic surfactants, C) one or more surface-active quaternary ammonium compounds.
- GB-A-2 231 580 describes cleaning agents which are particularly intended for the sanitary area. They have pH values between 6.0 and 8.0 and contain: A) 0.1 to 20% by weight of an anionic and / or nonionic surface-active agent, B) hydroxycarboxylic acids or their salts C) amminocarboxylic acids or their salts and D ) 0.1 to 20 wt .-% of an alkylene glycol alkyl ether as a solvent.
- aminocarboxylic acids are not understood to mean free amino acids Have NH 2 groups. Rather, the term aminocarboxylic acid here stands for carboxylic acids with a tertiary amino function, for example nitrilotriacetic acid or ethylenediaminetetraacetic acid.
- DE-A-32 06 350 relates to a liquid detergent mixture which has a suitable viscosity at the time of its use. It is specifically intended as a shampoo. Its main components consist of ammonium alkyl sulfates, alkylenediamine carboxylic acid derivatives and 0.1 to 5% by weight of a carboxylic acid, a salt of the carboxylic acid, an amino acid or one of the salts of the amino acid.
- the carboxylic acid is selected from fatty acids with 1 to 8 carbon atoms, dicarboxylic acids with 2 to 7 carbon atoms, hydroxycarboxylic acids or unsaturated, polybasic carboxylic acids.
- the amino acid is to be selected from neutral amino acids, acidinamino acids, basic amino acids, oxyamino acids, imino acids or sulfur-containing amino acids.
- the amino acids glycine, alanine, valine, leucine, isoleucine, phenylalanine, tryptophanic acid, sarcosine, beta-alanine, gamma-aminobutyric acid, epsilon-aminocaproic acid, glutamic acid, aspartic acid, cysteic acid, homocysteic acid, lysine, ornithine, homo-arginine, are particularly preferred , Tyrosine, threonine, proline, hydroxyproline, cystine, cysteine or methionine.
- WO 92/01 778 discloses a manufacturing process for a detergent powder for textile washing, in which the acid form of an anionic surfactant is continuously neutralized with alkali metal hydroxide.
- This document is related to the present invention by adding an alpha-aminodicarboxylic acid selected from the group consisting of glutamic acid, aspartic acid, aminomalonic acid, aminoadipic acid and 2-amino-2-methylpentanedioic acid or salts thereof.
- Sodium glutamate is particularly preferred.
- Optional components of the detergent mixture are also nonionic, cationic, amphoteric or zwitterionic surfactants.
- These detergents can furthermore contain carboxylates, C 10 -C 18 alkyl monocarboxylates, ie soaps, being particularly mentioned.
- DE-A-19 42 236 describes detergents, washing aids and cleaning agents which have a particularly good dissolving power for protein-containing soiling in that they have sulfur-free, 4-11 carbon atoms and optionally containing a further carboxyl and / or amino group containing amino acids or their salts.
- the preferred amino acids for this are glutamic acid, aspartic acid, histidine, arginine and lysine.
- the detergents also contain protein-splitting enzymes.
- Further constituents of the agents are the usual detergent constituents of detergents, washing aids and cleaning agents, in particular anionic and / or nonionic surfactants and builder substances.
- active ingredients according to the invention described below, consisting of amino acids, certain carboxylic acids and nonionic surfactants, and their special mixing ratios is not anticipated or suggested by this.
- German patent application P 43 19 578.4 of the applicant discloses powdery to granular detergents for textile washing which contain anionic and / or nonionic surfactants as well as zeolite and / or one or more silicates from the group of amorphous and crystalline, layered alkali metal silicates and as a result are characterized in that they additionally contain sulfur-free, 2 to 11 carbon atoms and optionally an additional carboxyl and / or amino group having amino acids and / or their salts.
- the amino acids are preferably selected from glycine, alanine, valine, leucine, isoleucine and their salts.
- These detergents can additionally contain carboxylic acid derivatives in the form of peracids as bleaching agents or soaps as foam inhibitors.
- C12-C24 fatty acid soaps are particularly preferred as soaps.
- These detergents for textile washing therefore contain the typical detergent constituents called zeolite and / or layered alkali silicates.
- German patent application P 43 19 798.1 discloses agents for the mechanical cleaning of dishes, the 1% by weight aqueous solution of which has a pH of 8 to 12, preferably 9 to 11, containing water-soluble builder components and bleaching agents based on oxygen, and thereby characterized in that 0.5 to 60 wt .-%, preferably 10 to 50 wt .-% of one or more amino acids are contained as alkali carriers.
- Alanine, valine, leucine, isoleucine and in particular glycine are mentioned as amino acids. The task of these amino acids and their salts is to serve as readily biodegradable alkali carriers.
- DE-A-19 64 792 also relates - as an additional application to DE-A-19 42 236 cited above - to protein-detergents, washing aids and cleaning agents, the amino acids mentioned in the main application being wholly or partly by sulfur-free amino acids with 2 or 3 carbon atoms or their salts, in particular glycerol, are replaced.
- the usual detergent constituents of detergents as mentioned above in the main application, may be considered as further constituents, including soaps from fatty acids with 10 to 22 carbon atoms and nonionic surfactants.
- DE-A-25 10 245 describes universal household cleaners for all types of hard surfaces which, in addition to anionic surfactants selected from organic surface-active detergent-effective sulfuric acid reaction products, and polypeptides or protein hydrolyzates preferably contain nonionic surfactants.
- the object of the invention is to provide improved cleaning agents for cleaning / degreasing technical surfaces, for example metallic surfaces, but in particular plastic surfaces.
- Surfaces made of non-polar plastics such as those made of polyvinyl chloride (PVC) or polypropylene, can only be cleaned or degreased with great effort because of their comparatively poor wetting behavior.
- PVC polyvinyl chloride
- the formulation that the acids mentioned under a) and b) may be present as such or in the form of their anions means that these acids must be in a water-soluble form, be it that they themselves have sufficient water solubility, that they are contained in the agent in the form of water-soluble salts.
- Particularly suitable as water-soluble salts are the alkali metal salts, preferably the sodium salts, of these acids.
- the anions can be used as ammonium salts or as salts with substituted ammonium ions.
- Alkanolammonium ions are preferably chosen as substituted ammonium ions.
- the naturally occurring alpha-amino acids or amino acid derivatives are generally chiral with respect to the carbon atom carrying the amino group and are in the L form.
- the chiral L-amino acids offer no particular advantage for the technical application according to the invention, they are preferably used as natural or nature-identical active ingredients.
- amino acids in the form of their racemates or in optically active form can be used, for example: glycine, alanine, valine, leucine, isoleucine, phenylalanine, tryptophanic acid, sarcosine, beta-alanine, gamma-aminobutyric acid, epsilon-aminocaproic acid, glutamine, glutamic acid, aspartic acid , Lysine, ornithine, arginine, serine, homoserine, tyrosine, threonine, proline, hydroxyproline, aminomalonic acid, aminoadipic acid and 2-amino-2-methylpentanedioic acid. Particularly good results are obtained with glutamic acid.
- the agents can also contain amino acid precursors which can convert into the amino acids under the conditions of use of the detergent bath.
- amino acid precursors are, for example, oligopeptides or protein hydrolyzates, lactams such as, for example, epsilon-caprolactam or anhydrides of polybasic amino acids.
- the carboxylic acids of group b) can be represented by the general formula (II) R 6 -COOH (II) where R 6 is an aliphatic, linear or branched hydrocarbon radical having 5 to 9 carbon atoms and 0 or a double bond.
- R 6 is an aliphatic, linear or branched hydrocarbon radical having 5 to 9 carbon atoms and 0 or a double bond.
- the saturated carboxylic acids, hexanoic acid (caproic acid), octanoic acid (caprylic acid) and decanoic acid (capric acid) are particularly preferred.
- Branched saturated carboxylic acids in particular 2-ethylhexanoic acid, 3,5,5-trimethylhexanoic acid and 2,2-dimethyloctanoic acid, also offer particular technical advantages.
- the non-ionic surfactants should be selected so that they comply with the legal requirements (detergent law) with regard to their biodegradability. To limit the tendency of the detergent to foam, it is recommended that the cloud points of the nonionic surfactants be below the intended working temperatures of 10 to 70 ° C. The foaming tendency of the cleaning solutions can be further suppressed by adding so-called mixed ethers even at low working temperatures, for example at temperatures between 10 and 25 ° C.
- the mixed ethers which can be used are end-capped ethoxylation products of fatty alcohols of the general formula R'-O- (EO) n -R ", in which R 'is an alkyl or alkenyl radical having 6-18 C atoms, R" is an alkyl radical having 4-8 C atoms and n represent a number from 2-6.
- R' is an alkyl or alkenyl radical having 6-18 C atoms
- R" is an alkyl radical having 4-8 C atoms
- n represent a number from 2-6.
- the homolog distribution of the EO chain can be conventional or narrow.
- Corresponding products and their effective amounts used (10-2500 ppm, preferably 50-500 ppm in the ready-to-use cleaning solution) are described in more detail, for example, in the published documents DE-A-37 27 378 and DE-A-39 35 374.
- composition of the agents according to the invention is preferably adjusted so that it contains the amino acids or amino acid derivatives from group a) or their anions in amounts between 0.4 and 4% by weight. and or the carboxylic acids from group b) or their anions in amounts between 2 and 7% by weight and or contain the nonionic surfactants from group c) in amounts between 5 and 10% by weight.
- the cleaners can be formulated as aqueous concentrates, as pumpable pastes or as powders.
- solutions of the constituents according to the invention from groups a), b) and c) are prepared in water in the above-mentioned proportions.
- the aqueous concentrates may contain other auxiliaries customary for cleaners, such as builder substances, further surfactants, polymers and / or complexing agents.
- the auxiliaries mentioned are added in powder form to the active compound combination according to the invention in groups a), b) and c) in such proportions that the total mixture contains the active compounds in groups a), b) and c) in the stated quantitative ranges .
- Pastes contain the active ingredients of groups a), b) and c) in the specified quantity ranges in addition to liquid or solid auxiliaries from the groups mentioned above and enough water to produce a pumpable paste.
- the agents according to the invention fall under the group of neutral cleaners or are alkaline cleaners.
- neutral cleaners are defined as cleaners whose 0.5-2% aqueous solution has a pH in the range of about 6-9.5. At higher pH values, the cleaners are referred to as alkaline cleaners.
- the cleaning solution have demulsifying properties. This means that oily impurities are very easily removed from the surfaces to be degreased, but that these impurities do not form a stable emulsion in the aqueous cleaning solution, but rather - at the working temperature or, if necessary, after temperature adjustment and / or dilution - as an oily phase on the aqueous Float the cleaner. The oil phase can then be easily removed from the cleaning solution, so that the service life of the cleaning bath can be extended considerably.
- the demulsifying properties of the cleaning / degreasing agents according to the invention are particularly evident when diluting the cleaning solutions.
- ammonium compounds of the formula (IV) are suitable as cationic surfactants: suitable which contain one, two or three unsubstituted or hydroxyl-substituted linear or branched carbon chains.
- Ammonium compounds of the general formula R a R b R c R d N + X - are preferably used, in which at least one, preferably two of the radicals R are unsubstituted or optionally substituted by a hydroxyl group with 1-2 carbon atoms and at least one of the remaining radicals R are unsubstituted or optionally substituted by a hydroxyl group in the 2-position straight-chain or branched alkyl groups with at least 10 carbon atoms and the anion X from the group hydroxide, chloride, bromide, sulfate , Nitrate, phosphate, preferably borate, is selected.
- ammonium salts are used as cationic surfactants in which R a and R b are methyl, R c is methyl, 2-hydroxyethyl, benzyl, 2-hydroxydodecyl or 2-hydroxyhexadecyl and R d 2-hydroxydodecyl, 2-hydroxyhexadecyl, lauryl, hexadecyl or stearyl .
- R a R b R c R d N + X - are also used as cationic surfactants, in which R a , R b and R c are (ethylene oxide) n groups, where n is 1-6, R d Is alkyl radical with 10-20 carbon atoms and X are anions from the group carboxylate, in particular benzoate, hydroxide, chloride, bromide, sulfate, nitrate, phosphate, preferably borate.
- Alkylpyridinium salts of the general formula C 5 H 5 N + -RX - are also used as cationic surfactants, in which R is an alkyl radical with 10-20 carbon atoms, preferably with 12-16 carbon atoms, and X anions from the group carboxylate, in particular benzoate, hydroxide, Chloride, bromide, sulfate, nitrate, phosphate, preferably borate.
- nitrogen-containing polymers which can be cationically modified or converted into the corresponding ammonium salts either by protonation or alkylation, generally methylation, of nitrogen are suitable as cationic polymers or cationically modified polymers.
- the degree of cationic modification is different and depends on the neutral starting polymer, on the corresponding acid for protonation or on the corresponding alkylation agent.
- cationic polymers which are used alone or together with cationic surfactants in the composition according to the invention are protonated quaternary acrylamides, N, N-dialkylaminoalkyl acrylates, dialkylamines or vinylpyridine, and methylated quaternary polymers such as polydiallyldimethylammonium chloride or poly-N-methylvinylpyridinium chloride.
- the molecular weights of the cationic polymers used in the agent according to the invention are between 5 ⁇ 10 4 and 5 ⁇ 10 7 , preferably between 7.5 ⁇ 10 4 and 5 ⁇ 10 6 .
- the invention also includes agents which select one or more complexing agents from at least one of the groups d) hydroxypolycarboxylic acids, e) nitrogen-containing mono- or polycarboxylic acids, f) mono- or diphosphonic acids, g) aminophosphonic acids, h) phosphonopolycarboxylic acids, and water-soluble salts Contain sodium, potassium or ammonium salts of the acids of groups d) to h) in amounts with respect to the free acids between 0.01 and 15 wt .-%.
- the agents according to the invention can be used without further alkaline builder substances. For demanding cleaning tasks, however, it is advisable to increase the cleaning effect with alkaline builder substances.
- the builders commonly used for alkaline cleaners are suitable for this.
- the agents according to the invention also include those which contain one or more builder substances selected from at least one of the groups i) mono-, di- or triethanolamine or their cations, k) alkali metal hydroxides, 1) silicates, preferably metasilicates, m) carbonates, n) Oligo- or polycarboxylates, o) ortho- or polyphosphates, p) borates, in amounts between 0.01 and 94.8% by weight, the anions of groups 1) to p) being in the form of their water-soluble salts, preferably ammonium - Or alkali metal salts, in particular as Li, Na or K salts.
- the invention further comprises processes for cleaning and / or degreasing hard surfaces, characterized in that the surfaces are brought into contact with 2 to 50% by weight aqueous solutions of the compositions by dipping or spraying at temperatures between 10 and 70 ° C.
- the expedient concentrations to be set or the dilutions to be selected depend on whether the agents according to the invention are used as powders, as pastes rich in active substances or as more or less highly concentrated aqueous concentrates.
- the preferred procedure is to use 2 to 10% by weight aqueous solutions in the case of powdery compositions, 2 to 15% by weight aqueous solutions when using pasty compositions and 5 to 15% by weight aqueous solutions when using liquid compositions Uses solutions.
- the invention also relates to processes in which the aqueous cleaning solution, in addition to the agents according to the invention, additionally comprises one or more anionic surfactants selected from at least one of the groups q) alkyl sulfates with a linear or branched alkyl radical having 10 to 18 carbon atoms, r) alkyl polyglycol ether sulfates with a linear or branched alkyl radical with 10 to 18 carbon atoms and 1 to 6 -CH 2 -CH 2 -O- groups in the molecule, s) alkylarylsulfonates with an alkylbenzene radical with a linear or branched alkyl group with 7 to 9 carbon atoms in Contains amounts between 0.01 and 3% by weight, the surfactant anions preferably being in the form of the alkali metal salts, in particular the sodium salts.
- the cleaning / degreasing agents and cleaning methods according to the invention can generally be used for the fields of work of industrial cleaners, including vehicle and operational cleaning.
- Their advantage of high wetting power is particularly evident when the surfaces to be degreased are surfaces made from organic polymers. Examples of this are painted surfaces or surfaces made of polycarbonates or polyurethanes.
- the cleaners were formulated as powder products or as liquid aqueous concentrates in deionized water (Examples 1-3). To prepare the degreasing baths, the powders or the concentrates were dissolved or diluted with city water (18 ° German hardness) to the concentrations given in the tables.
- Triethanolamine 18.2 sodium 2.0 2-ethylhexanoic acid 8.5 L-glutamic acid 1.3 Octylphosphonic acid 1.0 Nitrilotri (methylenephosphonic acid) 3.0 Sodium hydroxide 6.5 C 10/12 alcohol mix x 6 EO x 8 PO 7.0 water 52.5
Abstract
Description
Die Erfindung betrifft pulverförmige, pastenförmige oder flüssige Mittel zum Reinigen und/oder Entfetten harter Oberflächen, beispielsweise metallischer Oberflächen, insbesondere aber Oberflächen aus organischen Polymeren, beispielsweise Lacken und Beschichtungen, insbesondere aber Oberflächen aus halogenierten Polyolefinen wie Polyvinylchlorid. Kennzeichen der Mittel ist eine Kombination von Wirkstoffen, bestehend aus Aminosäuren, Carbonsäuren oder jeweils deren Salze sowie nichtionischen Tensiden. Die Mittel können als Industriereiniger (als Neutralreiniger oder als alkalische Reiniger) sowie zur Fahrzeug- und Betriebsreinigung eingesetzt werden.The invention relates to powdery, pasty or liquid agents for cleaning and / or degreasing hard surfaces, for example metallic surfaces, but in particular surfaces made of organic polymers, for example paints and coatings, but in particular surfaces made of halogenated polyolefins such as polyvinyl chloride. The agent is characterized by a combination of active ingredients consisting of amino acids, carboxylic acids or their salts and nonionic surfactants. The agents can be used as industrial cleaners (as neutral cleaners or as alkaline cleaners) as well as for vehicle and company cleaning.
Die DE-A-27 12 900 beschreibt ein Verfahren zur Reinigung von Metallen im Spritzverfahren. Hierbei wird die Reinigung bei pH-Werten zwischen 7,5 bis 11, vorzugsweise 8,5 bis 10, mit Lösungen durchgeführt, die A) lösliche Salze, vorzugsweise Alkanolaminsalze aromatischer Carbonsäuren und/oder verzweigter und/oder geradkettiger aliphatischer Carbonsäuren mit 6 bis 12 C-Atomen, B) ein oder mehrere nichtionogene Tenside, C) ein oder mehrere oberflächenaktive quarternäre Ammoniumverbindungen enthalten. Das Dokument enthält keine Hinweise auf die mögliche Verwendung von Aminosäuren in solchen Reinigern.DE-A-27 12 900 describes a method for cleaning metals by spraying. The cleaning is carried out at pH values between 7.5 to 11, preferably 8.5 to 10, with solutions which A) soluble salts, preferably alkanolamine salts of aromatic carboxylic acids and / or branched and / or straight-chain aliphatic carboxylic acids with 6 to 12 C atoms, B) one or more nonionic surfactants, C) one or more surface-active quaternary ammonium compounds. The document contains no evidence of the possible use of amino acids in such cleaners.
Die GB-A-2 231 580 beschreibt Reinigungsmittel, die besonders für den Sanitärbereich vorgesehen sind. Sie haben pH-Werte zwischen 6,0 und 8,0 und enthalten: A) 0,1 bis 20 Gew.-% eines anionischen und/oder nichtionischen oberflächenaktiven Mittels, B) Hydroxycarbonsäuren oder deren Salze C) Amminocarbonsäuren oder deren Salze und D) 0,1 bis 20 Gew.-% eines Alkylenglycolalkylethers als Lösungsmittel. Aus der Beschreibung geht hervor, daß unter Aminocarbonsäuren keine Aminosäuren verstanden werden, die freie NH2-Gruppierungen aufweisen. Der Begriff Aminocarbonsäure steht hier vielmehr für Carbonsäuren mit tertiärer Aminofunktion, beispielsweise Nitrilotriessigsäure oder Ethylendiamintetraessigsäure.GB-A-2 231 580 describes cleaning agents which are particularly intended for the sanitary area. They have pH values between 6.0 and 8.0 and contain: A) 0.1 to 20% by weight of an anionic and / or nonionic surface-active agent, B) hydroxycarboxylic acids or their salts C) amminocarboxylic acids or their salts and D ) 0.1 to 20 wt .-% of an alkylene glycol alkyl ether as a solvent. The description shows that aminocarboxylic acids are not understood to mean free amino acids Have NH 2 groups. Rather, the term aminocarboxylic acid here stands for carboxylic acids with a tertiary amino function, for example nitrilotriacetic acid or ethylenediaminetetraacetic acid.
DE-A-32 06 350 bezieht sich auf eine flüssige Reinigungsmittelmischung, die zum Zeitpunkt ihres Gebrauchs eine passende Viskosität aufweist. Sie ist speziell als Haarwaschmittel vorgesehen. Ihre Hauptkomponenten bestehen aus Ammoniumalkylsulfaten, Alkylendiamincarbonsäurederivaten sowie 0,1 bis 5 Gew.-% einer Carbonsäure, einem Salz der Carbonsäure, einer Aminosäure oder einem der Salz der Aminosäure. Die Carbonsäure ist ausgewählt aus Fettsäuren mit 1 bis 8 Kohlenstoffatomen, Dicarbonsäuren mit 2 bis 7 Kohlenstoffatomen, Hydroxycarbonsäuren oder ungesättigten, mehrbasischen Carbonsäuren. Die Aminosäure ist auszuwählen aus neutralen Aminosäuren, Acidinaminosäuren, basischen Aminosäuren, Oxyaminosäuren, Iminosäuren oder schwefelhaltigen Aminosäuren. Besonders bevorzugt werden die Aminosäuren Glycin, Alanin, Valin, Leucin, Isoleucin, Phenylalanin, Tryptophansäure, Sarcosin, beta-Alanin, gamma-Aminobuttersäure, epsilon-Aminocapronsäure, Glutaminsäure, Asparaginsäure, Cysteinsäure, Homocysteinsäure, Lysin, Ornithin, Arginin, Serin, Homoserin, Tyrosin, Threonin, Prolin, Hydroxyprolin, Cystin, Cystein oder Methionin.DE-A-32 06 350 relates to a liquid detergent mixture which has a suitable viscosity at the time of its use. It is specifically intended as a shampoo. Its main components consist of ammonium alkyl sulfates, alkylenediamine carboxylic acid derivatives and 0.1 to 5% by weight of a carboxylic acid, a salt of the carboxylic acid, an amino acid or one of the salts of the amino acid. The carboxylic acid is selected from fatty acids with 1 to 8 carbon atoms, dicarboxylic acids with 2 to 7 carbon atoms, hydroxycarboxylic acids or unsaturated, polybasic carboxylic acids. The amino acid is to be selected from neutral amino acids, acidinamino acids, basic amino acids, oxyamino acids, imino acids or sulfur-containing amino acids. The amino acids glycine, alanine, valine, leucine, isoleucine, phenylalanine, tryptophanic acid, sarcosine, beta-alanine, gamma-aminobutyric acid, epsilon-aminocaproic acid, glutamic acid, aspartic acid, cysteic acid, homocysteic acid, lysine, ornithine, homo-arginine, are particularly preferred , Tyrosine, threonine, proline, hydroxyproline, cystine, cysteine or methionine.
WO 92/01 778 offenbart einen Herstellprozeß für ein Waschmittelpulver zur Textilwäsche, bei dem die Säureform eines anionischen Tensids mit Alkalimetallhydroxid kontinuierlich neutralisiert wird. Bezug zur vorliegenden Erfindung erhält dieses Dokument dadurch, daß eine alpha-Aminodicarbonsäure zugegeben wird, die ausgewählt ist aus der Gruppe Glutaminsäure, Asparaginsäure, Aminomalonsäure, Aminoadipinsäure und 2-Amino-2-methyl-pentandisäure oder deren Salze. Natriumglutamat ist besonders bevorzugt. Fakultative Bestandteile der Waschmittelmischung sind weiterhin nichtionische, kationische, amphotere oder zwitterionische Tenside. Weiterhin können diese Waschmittel Carboxylate enthalten, wobei C10-C18 Alkylmonocarboxylate, d.h. Seifen, besonders genannt werden.WO 92/01 778 discloses a manufacturing process for a detergent powder for textile washing, in which the acid form of an anionic surfactant is continuously neutralized with alkali metal hydroxide. This document is related to the present invention by adding an alpha-aminodicarboxylic acid selected from the group consisting of glutamic acid, aspartic acid, aminomalonic acid, aminoadipic acid and 2-amino-2-methylpentanedioic acid or salts thereof. Sodium glutamate is particularly preferred. Optional components of the detergent mixture are also nonionic, cationic, amphoteric or zwitterionic surfactants. These detergents can furthermore contain carboxylates, C 10 -C 18 alkyl monocarboxylates, ie soaps, being particularly mentioned.
In der DE-A-19 42 236 werden Wasch-, Waschhilfs- und Reinigungsmittel beschrieben, die dadurch ein besonders gutes Lösevermögen für eiweißhaltige Anschmutzungen aufweisen, daß sie schwefelfreie, 4-11 Kohlenstoffatome und gegebenenfalls eine weitere Carboxyl- und/oder Aminogruppe aufweisende Aminosäuren bzw. deren Salze enthalten. Die hierfür bevorzugten Aminosäuren sind Glutaminsäure, Asparaginsäure, Histidin, Arginin und Lysin. Dabei ist es bevorzugt, daß die Waschmittel außerdem eiweißspaltende Enzyme enthalten. Weitere Bestandteile der Mittel sind die üblichen, reinigend wirkenden Bestandteile von Wasch-, Waschhilfs- und Reinigungsmittel, insbesondere anionische und/oder nichtionische Tenside sowie Buildersubstanzen. Die im folgenden beschriebene erfindungsgemäße Wirkstoffkombination aus Aminosäuren, bestimmten Carbonsäuren und nichtionischen Tensiden sowie deren spezielle Mischungsverhältnisse wird hierdurch nicht vorweggenommen oder nahegelegt.DE-A-19 42 236 describes detergents, washing aids and cleaning agents which have a particularly good dissolving power for protein-containing soiling in that they have sulfur-free, 4-11 carbon atoms and optionally containing a further carboxyl and / or amino group containing amino acids or their salts. The preferred amino acids for this are glutamic acid, aspartic acid, histidine, arginine and lysine. It is preferred that the detergents also contain protein-splitting enzymes. Further constituents of the agents are the usual detergent constituents of detergents, washing aids and cleaning agents, in particular anionic and / or nonionic surfactants and builder substances. The combination of active ingredients according to the invention described below, consisting of amino acids, certain carboxylic acids and nonionic surfactants, and their special mixing ratios is not anticipated or suggested by this.
Aus der deutschen Patentanmeldung P 43 19 578.4 der Anmelderin sind pulverförmige bis granulare Waschmittel für die Textilwäsche bekannt, welche anionische und/oder nichtionische Tenside sowie Zeolith und/oder ein oder mehrere Silicate aus der Gruppe der amorphen und kristallinen, schichtförmigen Alkalisilicate enthalten und die dadurch gekennzeichnet sind, daß sie zusätzlich schwefelfreie, 2 bis 11 Kohlenstoffatome und gegebenenfalls eine weitere Carboxyl- und/oder Aminogruppe aufweisende Aminosäuren und/ oder deren Salze enthalten. Vorzugsweise sind die Aminosäuren ausgewählt aus Glycin, Alanin, Valin, Leucin, Isoleucin sowie deren Salzen. Diese Waschmittel können zusätzlich Carbonsäurederivate in Form von Persäuren als Bleichmittel oder von Seifen als Schaumdämpfer enthalten. Als Seifen sind insbesondere die C12-C24-Fettsäureseifen bevorzugt. Diese Waschmittel für die Textilwäsche enthalten also die als Builder bezeichneten typischen Waschmittelbestandteile Zeolith und/oder schichtförmige Alkalisilicate.German patent application P 43 19 578.4 of the applicant discloses powdery to granular detergents for textile washing which contain anionic and / or nonionic surfactants as well as zeolite and / or one or more silicates from the group of amorphous and crystalline, layered alkali metal silicates and as a result are characterized in that they additionally contain sulfur-free, 2 to 11 carbon atoms and optionally an additional carboxyl and / or amino group having amino acids and / or their salts. The amino acids are preferably selected from glycine, alanine, valine, leucine, isoleucine and their salts. These detergents can additionally contain carboxylic acid derivatives in the form of peracids as bleaching agents or soaps as foam inhibitors. C12-C24 fatty acid soaps are particularly preferred as soaps. These detergents for textile washing therefore contain the typical detergent constituents called zeolite and / or layered alkali silicates.
Die deutsche Patentanmeldung P 43 19 798.1 offenbart Mittel zum maschinellen Reinigen von Geschirr, dessen 1 gew.-%ige wäßrige Lösung einen pH-Wert von 8 bis 12, vorzugsweise 9 bis 11, aufweist, enthaltend wasserlösliche Builderkomponenten und Bleichmittel auf Sauerstoffbasis, und dadurch gekennzeichnet, daß als Alkaliträger 0,5 bis 60 Gew.-%, vorzugsweise 10 bis 50 Gew.-% einer oder mehrerer Aminosäuren enthalten sind. Als Aminosäuren werden Alanin, Valin, Leucin, Isoleucin und insbesondere Glycin genannt. Die Aufgabe dieser Aminosäuren und ihrer Salze besteht darin, als biologisch gut abbaubare Alkaliträger zu dienen.German patent application P 43 19 798.1 discloses agents for the mechanical cleaning of dishes, the 1% by weight aqueous solution of which has a pH of 8 to 12, preferably 9 to 11, containing water-soluble builder components and bleaching agents based on oxygen, and thereby characterized in that 0.5 to 60 wt .-%, preferably 10 to 50 wt .-% of one or more amino acids are contained as alkali carriers. Alanine, valine, leucine, isoleucine and in particular glycine are mentioned as amino acids. The task of these amino acids and their salts is to serve as readily biodegradable alkali carriers.
Die DE-A-19 64 792 betrifft - als Zusatzanmeldung zu der vorstehend zitierten DE-A-19 42 236 - gleichfalls eiweißlösende Wasch-, Waschhilfs- und Reinigungsmittel, wobei die in der Hauptanmeldung genannten Aminosäuren vollständig oder teilweise durch schwefelfreie Aminosäuren mit 2 oder 3 C-Atomen oder deren Salzen, insbesondere Glycerin, ersetzt sind. Als weitere Bestandteile kommen neben Enzymen die wie vorstehend in der Hauptanmeldung genannten üblichen reinigend wirkenden Bestandteile von Waschmitteln in Frage, darunter Seifen von Fettsäuren mit 10 bis 22 C-Atomen und nichtionischen Tensiden.DE-A-19 64 792 also relates - as an additional application to DE-A-19 42 236 cited above - to protein-detergents, washing aids and cleaning agents, the amino acids mentioned in the main application being wholly or partly by sulfur-free amino acids with 2 or 3 carbon atoms or their salts, in particular glycerol, are replaced. In addition to enzymes, the usual detergent constituents of detergents, as mentioned above in the main application, may be considered as further constituents, including soaps from fatty acids with 10 to 22 carbon atoms and nonionic surfactants.
In der DE-A-25 10 245 werden Universal-Haushaltsreiniger für alle Arten harter Oberflächen beschrieben, die neben anionischen Tensiden, ausgewählt aus organischen oberflächenaktiven Detergens-wirksamen Schwefelsäure-Reaktionsprodukten, und Polypeptiden oder Proteinhydrolysaten bevorzugt nichtionische Tenside enthalten.DE-A-25 10 245 describes universal household cleaners for all types of hard surfaces which, in addition to anionic surfactants selected from organic surface-active detergent-effective sulfuric acid reaction products, and polypeptides or protein hydrolyzates preferably contain nonionic surfactants.
Der Erfindung liegt die Aufgabe zugrunde, verbesserte Reinigungsmittel zum Reinigen/Entfetten technischer Oberflächen, beispielsweise metallischer Oberflächen, insbesondere aber von Kunststoffoberflächen zur Verfügung zu stellen. Oberflächen aus unpolaren Kunststoffen, wie beispielsweise solche aus Polyvinylchlorid (PVC) oder aus Polypropylen, sind wegen ihres vergleichsweise schlechten Benetzungsverhaltens nur mit besonderem Aufwand zu reinigen oder zu entfetten. In der Technik besteht daher ein Bedarf nach verbesserten Reinigungsmitteln, die sich durch eine erhöhte Benetzungsfähigkeit gegenüber unpolaren Kunststoffen auszeichnen. Es ist die Aufgabe der vorliegenden Erfindung, solche verbesserten technischen Reinigungs-/ Entfettungsmittel zur Verfügung zu stellen.The object of the invention is to provide improved cleaning agents for cleaning / degreasing technical surfaces, for example metallic surfaces, but in particular plastic surfaces. Surfaces made of non-polar plastics, such as those made of polyvinyl chloride (PVC) or polypropylene, can only be cleaned or degreased with great effort because of their comparatively poor wetting behavior. There is therefore a need in the art for improved cleaning agents which are distinguished by an increased wetting ability compared to non-polar plastics. It is the object of the present invention to provide such improved technical cleaning / degreasing agents.
Diese Aufgabe wird gelöst durch pulverförmige, pastenförmige oder flüssige Mittel zum Reinigen und/oder Entfetten harter Oberflächen, enthaltend
- a) 0,2 bis 12 Gew.-% einer oder mehrerer aliphatischer oder aromatischer Monoamino- oder Diaminomono- oder -dicarbonsäuren oder Monoaminodicarbonsäuremonoamiden der allgemeinen Formel (I)
- a und b unabhängig voneinander ganze Zahlen von 0 bis 6 bedeuten,
- R1 an jedem C-Atom unabhängig voneinander H, OH, CH3 oder C2H5 bedeuten kann,
- R2 an jedem C-Atom unabhängig voneinander H, CH3 oder C2H5 bedeuten kann,
- R3 für H, CH3 oder C2H5 steht,
- R4 an jedem C-Atom unabhängig voneinander H, OH, CH3 oder C2H5 bedeuten kann,
- R5 an jedem C-Atom unabhängig voneinander H, CH3 oder C2H5 bedeuten kann und
- X Wasserstoff, einen homo- oder heterozyclischen Rest, vorzugsweise Phenyl, C(O)OH oder C(O)NH2 und unter der Bedingung, daß b > 0 ist, zusätzlich NH2, NH-C(=NH)-NH2, NH-C(=O)-NH2 bedeutet,
- b) 1 bis 12 Gew.-% einer oder mehrerer Carbonsäuren, die der allgemeinen Formel (II)
R6-COOH (II)
entsprechen, wobei R6 für einen aliphatischen, linearen oder verzweigten Kohlenwasserstoffrest mit 5 bis 9 Kohlenstoffatomen und 0 oder einer Doppelbindung oder für eine R7-C6H4-C(O)-CH=CH- Gruppe steht, in der R7 einen linearen oder verzweigten Alkylrest mit 8 bis 14 Kohlenstoffatomen bedeutet, oder deren Anionen, - c) 4 bis 15 Gew.-% eines oder mehrerer nichtionischer Tenside, ausgewählt aus der Gruppe der ethoxylierten und/oder der ethoxylierten und propoxylierten Fettalkohole der allgemeinen Formel (III)
R8-O-(EO)x-(PO)y-H (III)
wobei- R8 einen linearen oder verzweigten Alkylrest mit 6 bis 14 C-Atomen,
- x eine Zahl im Bereich von 2 bis 10 und
- y eine Zahl im Bereich von 0 bis 8 bedeuten,
- EO für eine -CH2-CH2-O- Gruppe und
- PO für eine -CH(CH3)-CH2-O- Gruppe stehen, und
- a) 0.2 to 12% by weight of one or more aliphatic or aromatic monoamino or diaminomono or dicarboxylic acids or monoaminodicarboxylic acid monoamides of the general formula (I)
- a and b independently of one another are integers from 0 to 6,
- R 1 on each C atom can independently be H, OH, CH 3 or C 2 H 5 ,
- R 2 on each C atom can independently be H, CH 3 or C 2 H 5 ,
- R 3 represents H, CH 3 or C 2 H 5 ,
- R 4 on each C atom can independently denote H, OH, CH 3 or C 2 H 5 ,
- R 5 on each C atom independently of one another can denote H, CH 3 or C 2 H 5 and
- X is hydrogen, a homo- or heterocyclic radical, preferably phenyl, C (O) OH or C (O) NH 2 and, provided that b> 0, additionally NH 2 , NH-C (= NH) -NH 2 , NH-C (= O) -NH 2 means
- b) 1 to 12% by weight of one or more carboxylic acids which have the general formula (II)
R 6 -COOH (II)
correspond, where R 6 is an aliphatic, linear or branched hydrocarbon radical having 5 to 9 carbon atoms and 0 or a double bond or an R 7 -C 6 H 4 -C (O) -CH = CH group, in which R 7 represents a linear or branched alkyl radical having 8 to 14 carbon atoms, or their anions, - c) 4 to 15% by weight of one or more nonionic surfactants selected from the group of ethoxylated and / or ethoxylated and propoxylated fatty alcohols of the general formula (III)
R 8 -O- (EO) x - (PO) y -H (III)
in which- R 8 is a linear or branched alkyl radical having 6 to 14 carbon atoms,
- x is a number in the range from 2 to 10 and
- y is a number in the range from 0 to 8,
- EO for a -CH 2 -CH 2 -O- group
- PO stands for a -CH (CH 3 ) -CH 2 -O- group, and
Die Formulierung, daß die unter a) und b) genannten Säuren als solche oder in Form ihrer Anionen vorhanden sein können, bedeutet, daß diese Säuren in einer wasserlöslichen Form vorliegen müssen, sei es, daß sie selbst eine ausreichende Wasserlöslichkeit aufweisen, sei es, daß sie in Form wasserlöslicher Salze in dem Mittel enthalten sind. Als wasserlösliche Salze sind insbesondere die Alkalimetallsalze, vorzugsweise die Natriumsalze, dieser Säuren geeignet. Außerdem können die Anionen als Ammoniumsalze oder als Salze mit substituierten Ammoniumionen eingesetzt werden. Als substituierte Ammoniumionen werden vorzugsweise Alkanolammoniumionen gewählt.The formulation that the acids mentioned under a) and b) may be present as such or in the form of their anions means that these acids must be in a water-soluble form, be it that they themselves have sufficient water solubility, that they are contained in the agent in the form of water-soluble salts. Particularly suitable as water-soluble salts are the alkali metal salts, preferably the sodium salts, of these acids. In addition, the anions can be used as ammonium salts or as salts with substituted ammonium ions. Alkanolammonium ions are preferably chosen as substituted ammonium ions.
Bevorzugt werden unverzweigte Aminosäuren der Formel (I) oder ihrer Derivate eingesetzt, also solche Verbindungen, bei denen die Reste R1 bis R5 jeweils Wasserstoff bedeuten. Wegen ihres verbreiteten natürlichen Vorkommens, beispielsweise in Proteinen, und ihrer leichten Verfügbarkeit, beispielsweise in Form von Proteinhydrolysaten, werden vorzugsweise alpha-Aminosäuren verwendet. Solche alpha-Aminosäuren werden in der Formel (I) dadurch symbolisiert, daß der Index a = 0 ist. Unter den möglichen alpha-Aminosäuren werden wiederum solche bevorzugt ausgewählt, die an dem die Aminogruppe tragenden Kohlenstoffatom nicht verzweigt sind, bei denen also in der Formel (I) der Rest R3 Wasserstoff bedeutet.Unbranched amino acids of the formula (I) or their derivatives are preferably used, that is to say those compounds in which the radicals R 1 to R 5 are each hydrogen. Because of their widespread natural occurrence, for example in proteins, and their easy availability, for example in the form of protein hydrolyzates, alpha-amino acids are preferably used. Such alpha-amino acids are symbolized in formula (I) in that the index a = 0. From the possible alpha-amino acids, those are in turn preferably selected which are not branched on the carbon atom carrying the amino group and in which the radical R 3 in the formula (I) is hydrogen.
Die natürlich vorkommenden alpha-Aminosäuren oder Aminosäurederivate sind in der Regel bezüglich des die Aminogruppe tragenden Kohlenstoffatoms chiral und liegen in der L-Form vor. Obwohl für den erfindungsgemäßen technischen Einsatzzweck die chiralen L-Aminosäuren keinen besonderen Vorteil bieten, werden sie als natürliche oder naturidentische Wirkstoffe bevorzugt eingesetzt.The naturally occurring alpha-amino acids or amino acid derivatives are generally chiral with respect to the carbon atom carrying the amino group and are in the L form. Although the chiral L-amino acids offer no particular advantage for the technical application according to the invention, they are preferably used as natural or nature-identical active ingredients.
Als Aminosäuren können demnach in Form ihrer Racemate oder in optisch aktiver Form beispielsweise Verwendung finden: Glycin, Alanin, Valin, Leucin, Isoleucin, Phenylalanin, Tryptophansäure, Sarcosin, beta-Alanin, gamma-Aminobuttersäure, epsilon-Aminocapronsäure, Glutamin, Glutaminsäure, Asparaginsäure, Lysin, Ornithin, Arginin, Serin, Homoserin, Tyrosin, Threonin, Prolin, Hydroxyprolin, Aminomalonsäure, Aminoadipinsäure und 2-Amino-2-methyl-pentandisäure. Besonders gute Ergebnisse werden mit Glutaminsäure erhalten.Accordingly, amino acids in the form of their racemates or in optically active form can be used, for example: glycine, alanine, valine, leucine, isoleucine, phenylalanine, tryptophanic acid, sarcosine, beta-alanine, gamma-aminobutyric acid, epsilon-aminocaproic acid, glutamine, glutamic acid, aspartic acid , Lysine, ornithine, arginine, serine, homoserine, tyrosine, threonine, proline, hydroxyproline, aminomalonic acid, aminoadipic acid and 2-amino-2-methylpentanedioic acid. Particularly good results are obtained with glutamic acid.
Anstelle der Aminosäuren oder ihrer Salze können die Mittel auch Aminosäuren-Vorläufer enthalten, die sich unter den Anwendungsbedingungen des Reinigerbades in die Aminosäuren umwandeln können. Solche Aminosäuren-Vorläufer sind beispielsweise Oligopeptide oder Proteinhydrolysate, Lactame wie beispielsweise epsilon-Caprolactam oder Anhydride mehrbasischer Aminosäuren.Instead of the amino acids or their salts, the agents can also contain amino acid precursors which can convert into the amino acids under the conditions of use of the detergent bath. Such amino acid precursors are, for example, oligopeptides or protein hydrolyzates, lactams such as, for example, epsilon-caprolactam or anhydrides of polybasic amino acids.
Die Carbonsäuren der Gruppe b) lassen sich darstellen durch die allgemeine Formel (II)
R6-COOH (II)
wobei R6 für einen aliphatischen, linearen oder verzweigten Kohlenwasserstoffrest mit 5 bis 9 Kohlenstoffatomen und 0 oder einer Doppelbindung steht. Insbesondere bevorzugt sind die gesättigten Carbonsäuren, Hexansäure (Capronsäure), Octansäure (Caprylsäure) und Decansäure (Caprinsäure). Besondere technische Vorteile bieten auch verzweigte gesättigte Carbonsäuren, insbesondere 2-Ethylhexansäure, 3,5,5-Trimethylhexansäure sowie 2,2-Dimethyloctansäure.The carboxylic acids of group b) can be represented by the general formula (II)
R 6 -COOH (II)
where R 6 is an aliphatic, linear or branched hydrocarbon radical having 5 to 9 carbon atoms and 0 or a double bond. The saturated carboxylic acids, hexanoic acid (caproic acid), octanoic acid (caprylic acid) and decanoic acid (capric acid) are particularly preferred. Branched saturated carboxylic acids, in particular 2-ethylhexanoic acid, 3,5,5-trimethylhexanoic acid and 2,2-dimethyloctanoic acid, also offer particular technical advantages.
Weiterhin können als Carbonsäuren der allgemeinen Formel (II) solche stehen, bei denen R6 für eine R7-C6H4-C(O)-CH=CH- Gruppe steht, in der R7 einen linearen oder verzweigten Alkylrest mit 8 bis 14 Kohlenstoffatomen bedeutet.Further carboxylic acids of the general formula (II) are those in which R 6 is an R 7 -C 6 H 4 -C (O) -CH = CH group, in which R 7 is a linear or branched alkyl radical having 8 means up to 14 carbon atoms.
Die nichtionischen Tenside der Gruppe c) sind ausgewählt aus der Gruppe der ethoxylierten und/oder der ethoxylierten und propoxylierten Fettalkohole der allgemeinen Formel (III)
R8-O-(EO)x-(PO)y-H (III)
wobei
- R8
- einen linearen oder verzweigten Alkylrest mit 6 bis 14 C-Atomen, vorzugsweise 8 bis 12 C-Atomen und insbesondere 8 C-Atomen,
- x
- eine Zahl im Bereich von 2 bis 10 und
- y
- eine Zahl im Bereich von 0 bis 8 bedeuten und
- EO
- für eine -CH2-CH2-O- Gruppe und
- PO
- für eine -CH(CH3)-CH2-O- Gruppe stehen.
R 8 -O- (EO) x - (PO) y -H (III)
in which
- R 8
- a linear or branched alkyl radical having 6 to 14 carbon atoms, preferably 8 to 12 carbon atoms and in particular 8 carbon atoms,
- x
- a number in the range from 2 to 10 and
- y
- represent a number in the range from 0 to 8 and
- EO
- for a -CH 2 -CH 2 -O- and
- PO
- represent a -CH (CH 3 ) -CH 2 -O- group.
Dabei sind die nichtionischen Tenside so auszuwählen, daß sie den gesetzlichen Bestimmungen (Waschmittelgesetz) bezüglich ihrer biologischen Abbaubarkeit genügen. Um die Schaumneigung der Reiniger zu begrenzen, ist es empfehlenswert, daß die Trübungspunkte der Niotenside unterhalb der beabsichtigten Arbeitstemperaturen von 10 bis 70 °C liegen. Die Schaumneigung der Reinigerlösungen kann durch Zusätze sogenannter Mischether auch bei tiefen Arbeitstemperaturen, beispielsweise bei Temperaturen zwischen 10 und 25 °C, weiter unterdrückt werden. Die verwendbaren Mischether stellen endgruppenverschlossene Ethoxylierungsprodukte von Fettalkoholen der allgemeinen Formel R'-O-(EO)n-R" dar, in der R' einen Alkyl- oder Alkenylrest mit 6-18 C-Atomen, R" einen Alkylrest mit 4-8 C-Atomen und n eine Zahl von 2-6 bedeuten. Die Homologenverteilung der EO-Kette kann konventionell oder eingeengt sein. Entsprechende Produkte und deren wirksame Einsatzmengen (10-2500 ppm, vorzugsweise 50-500 ppm in der gebrauchsfertigen Reinigerlösung) sind beispielsweise in den Offenlegungsschriften DE-A-37 27 378 und DE-A-39 35 374 näher beschrieben.The non-ionic surfactants should be selected so that they comply with the legal requirements (detergent law) with regard to their biodegradability. To limit the tendency of the detergent to foam, it is recommended that the cloud points of the nonionic surfactants be below the intended working temperatures of 10 to 70 ° C. The foaming tendency of the cleaning solutions can be further suppressed by adding so-called mixed ethers even at low working temperatures, for example at temperatures between 10 and 25 ° C. The mixed ethers which can be used are end-capped ethoxylation products of fatty alcohols of the general formula R'-O- (EO) n -R ", in which R 'is an alkyl or alkenyl radical having 6-18 C atoms, R" is an alkyl radical having 4-8 C atoms and n represent a number from 2-6. The homolog distribution of the EO chain can be conventional or narrow. Corresponding products and their effective amounts used (10-2500 ppm, preferably 50-500 ppm in the ready-to-use cleaning solution) are described in more detail, for example, in the published documents DE-A-37 27 378 and DE-A-39 35 374.
Vorzugsweise stellt man die Zusammensetzung der erfindungsgemäßen Mittel so ein, daß sie die Aminosäuren oder Aminosäurederivate aus der Gruppe a) oder deren Anionen in Mengen zwischen 0,4 und 4 Gew.-%
und/oder
die Carbonsäuren aus der Gruppe b) oder deren Anionen in Mengen zwischen 2 und 7 Gew.-%
und/oder
die nichtionischen Tenside aus der Gruppe c) in Mengen zwischen 5 und 10 Gew.-% enthalten.The composition of the agents according to the invention is preferably adjusted so that it contains the amino acids or amino acid derivatives from group a) or their anions in amounts between 0.4 and 4% by weight.
and or
the carboxylic acids from group b) or their anions in amounts between 2 and 7% by weight
and or
contain the nonionic surfactants from group c) in amounts between 5 and 10% by weight.
Je nach vorgesehener Anbietungsform können die Reiniger als wäßrige Konzentrate, als pumpfähige Pasten oder als Pulver formuliert werden. Bei wäßrigen Konzentraten stellt man im einfachsten Fall Lösungen der erfindungsgemäßen Bestandteile aus den Gruppen a), b) und c) in den oben genannten Anteilsbereichen in Wasser her. Daneben können die wäßrigen Konzentrate jedoch weitere für Reiniger übliche Hilfsstoffe wie beispielsweise Buildersubstanzen, weitere Tenside, Polymere und/oder Komplexbildner enthalten.Depending on the intended form of supply, the cleaners can be formulated as aqueous concentrates, as pumpable pastes or as powders. In the simplest case, in the case of aqueous concentrates, solutions of the constituents according to the invention from groups a), b) and c) are prepared in water in the above-mentioned proportions. In addition, however, the aqueous concentrates may contain other auxiliaries customary for cleaners, such as builder substances, further surfactants, polymers and / or complexing agents.
Bei der Formulierung als Pulver setzt man die genannten Hilfsstoffe in Pulverform der erfindungsgemäßen Wirkstoffkombination der Gruppen a), b) und c) in solchen Anteilen zu, daß die Gesamtmischung die Wirkstoffe der Gruppen a), b) und c) in den angegebenen Mengenbereichen enthält.When formulated as a powder, the auxiliaries mentioned are added in powder form to the active compound combination according to the invention in groups a), b) and c) in such proportions that the total mixture contains the active compounds in groups a), b) and c) in the stated quantitative ranges .
Pasten enthalten die Wirkstoffe der Gruppen a), b) und c) in den angegebenen Mengenbereichen neben flüssigen oder festen Hilfsstoffen aus den vorstehend genannten Gruppen und so viel Wasser, daß eine pumpfähige Paste entsteht.Pastes contain the active ingredients of groups a), b) and c) in the specified quantity ranges in addition to liquid or solid auxiliaries from the groups mentioned above and enough water to produce a pumpable paste.
Je nach Ab- oder Anwesenheit von in wäßriger Lösung stark alkalisch reagierenden Wirk- oder Hilfsstoffen fallen die erfindungsgemäßen Mittel unter die Gruppe der Neutralreiniger oder stellen alkalische Reiniger dar.Depending on the absence or presence of active substances or auxiliaries which react strongly alkaline in aqueous solution, the agents according to the invention fall under the group of neutral cleaners or are alkaline cleaners.
Neutralreiniger sind gemäß Römpp Chemie Lexikon definiert als Reiniger, deren 0,5-2%-ige wäßrige Lösung einen pH-Wert im Bereich von etwa 6-9,5 aufweist. Bei höheren pH-Werten werden die Reiniger als alkalische Reiniger bezeichnet.According to Römpp Chemie Lexikon, neutral cleaners are defined as cleaners whose 0.5-2% aqueous solution has a pH in the range of about 6-9.5. At higher pH values, the cleaners are referred to as alkaline cleaners.
Bei vielen technischen Anwendungen ist es wünschenswert, daß die Reinigerlösung demulgierende Eigenschaften aufweist. Dies bedeutet, daß ölige Verunreinigungen von den zu entfettenden Flächen zwar sehr leicht abgelöst werden, daß diese Verunreinigungen jedoch in der wäßrigen Reinigerlösung keine stabile Emulsion bilden, sondern - bei der Arbeitstemperatur oder gegebenenfalls nach Temperaturanpassung und/oder Verdünnung - als ölige Phase auf dem wäßrigen Reiniger aufschwimmen. Die Ölphase kann dann leicht von der Reinigerlösung abgezogen werden, so daß sich die Standzeit des Reinigerbades beträchtlich verlängern läßt. Die demulgierenden Eigenschaften der erfindungsgemäßen Reinigungs-/Entfettungsmittel zeigen sich insbesondere beim Verdünnen der Reinigerlösungen. Im Falle des Einschleppens selbstemulgierender, anionische Emulgatoren enthaltender Öle werden sie dadurch erhalten bzw. verbessert, daß die Mittel kationische Tenside, Betaine und/oder kationisch modifizierte Polymere in Mengen zwischen 0,01 und 3 Gew.-% enthalten.In many technical applications it is desirable that the cleaning solution have demulsifying properties. This means that oily impurities are very easily removed from the surfaces to be degreased, but that these impurities do not form a stable emulsion in the aqueous cleaning solution, but rather - at the working temperature or, if necessary, after temperature adjustment and / or dilution - as an oily phase on the aqueous Float the cleaner. The oil phase can then be easily removed from the cleaning solution, so that the service life of the cleaning bath can be extended considerably. The demulsifying properties of the cleaning / degreasing agents according to the invention are particularly evident when diluting the cleaning solutions. In the case of the introduction of self-emulsifying oils containing anionic emulsifiers, they are obtained or improved by the fact that the agents contain cationic surfactants, betaines and / or cationically modified polymers in amounts between 0.01 and 3% by weight.
Als kationische Tenside sind solche Ammoniumverbindungen der Formel (IV)
Insbesondere werden als Kationtenside Ammoniumsalze verwendet, in denen Ra und Rb Methyl, Rc Methyl, 2-Hydroxyethyl, Benzyl, 2-Hydroxydodecyl oder 2-Hydroxyhexadecyl und Rd 2-Hydroxydodecyl, 2-Hydroxyhexadecyl, Lauryl, Hexadecyl oder Stearyl sind.In particular, ammonium salts are used as cationic surfactants in which R a and R b are methyl, R c is methyl, 2-hydroxyethyl, benzyl, 2-hydroxydodecyl or 2-hydroxyhexadecyl and R d 2-hydroxydodecyl, 2-hydroxyhexadecyl, lauryl, hexadecyl or stearyl .
Weiterhin werden als Kationtenside Verbindungen der allgemeinen Formel RaRbRcRdN+X- eingesetzt, in der Ra, Rb und Rc (Ethylenoxid)n-Gruppen sind, wobei n 1-6 bedeutet, Rd ein Alkylrest mit 10-20 Kohlenstoffatomen ist und X Anionen aus der Gruppe Carboxylat, insbesondere Benzoat, Hydroxid, Chlorid, Bromid, Sulfat, Nitrat, Phosphat, vorzugsweise Borat, sind.Compounds of the general formula R a R b R c R d N + X - are also used as cationic surfactants, in which R a , R b and R c are (ethylene oxide) n groups, where n is 1-6, R d Is alkyl radical with 10-20 carbon atoms and X are anions from the group carboxylate, in particular benzoate, hydroxide, chloride, bromide, sulfate, nitrate, phosphate, preferably borate.
Als Kationtenside werden auch Alkylpyridiniumsalze der allgemeinen Formel C5H5N+-RX- verwendet, in der R ein Alkylrest mit 10-20 Kohlenstoffatomen, vorzugsweise mit 12-16 Kohlenstoffatomen, und X Anionen aus der Gruppe Carboxylat, insbesondere Benzoat, Hydroxid, Chlorid, Bromid, Sulfat, Nitrat, Phosphat, vorzugsweise Borat, sind.Alkylpyridinium salts of the general formula C 5 H 5 N + -RX - are also used as cationic surfactants, in which R is an alkyl radical with 10-20 carbon atoms, preferably with 12-16 carbon atoms, and X anions from the group carboxylate, in particular benzoate, hydroxide, Chloride, bromide, sulfate, nitrate, phosphate, preferably borate.
Als kationische Polymere bzw. kationisch modifizierte Polymere kommen prinzipiell alle stickstoffhaltigen Polymere in Betracht, die entweder durch Protonierung oder Alkylierung, in der Regel Methylierung, des Stickstoffs kationisch modifiziert bzw. in die entsprechenden Ammoniumsalze überführt werden können. Der kationische Modifizierungsgrad ist dabei unterschiedlich und hängt ab vom neutralen Ausgangspolymeren, von der entsprechenden Säure zur Protonierung bzw. von dem entsprechenden Alkylierungsagenz.In principle, all nitrogen-containing polymers which can be cationically modified or converted into the corresponding ammonium salts either by protonation or alkylation, generally methylation, of nitrogen are suitable as cationic polymers or cationically modified polymers. The degree of cationic modification is different and depends on the neutral starting polymer, on the corresponding acid for protonation or on the corresponding alkylation agent.
Beispielhaft für kationische Polymere, die im erfindungsgemäßen Mittel allein oder zusammen mit Kationtensiden eingesetzt werden, sind protonierte quartäre Acrylamide, N,N-Dialkylaminoalkylacrylate, Dialkylamine oder Vinylpyridin, sowie methylierte quartäre Polymere wie Polydiallyldimethylammoniumchlorid oder Poly-N-methylvinylpyridiniumchlorid.Examples of cationic polymers which are used alone or together with cationic surfactants in the composition according to the invention are protonated quaternary acrylamides, N, N-dialkylaminoalkyl acrylates, dialkylamines or vinylpyridine, and methylated quaternary polymers such as polydiallyldimethylammonium chloride or poly-N-methylvinylpyridinium chloride.
Die Molekulargewichte der im erfindungsgemäßen Mittel verwendeten kationischen Polymere liegen zwischen 5 x 104 und 5 x 107, vorzugsweise zwischen 7,5 x 104 und 5 x 106. Bevorzugt werden protoniertes Polyethylenimin (25 % AS), methyliertes Polyethylenimin (25 % AS) oder protoniertes N,N-Dimethylaminoethylacrylat-acrylamid-copolymerisat (100 % AS) verwendet (AS = Aktivsubstanz).The molecular weights of the cationic polymers used in the agent according to the invention are between 5 × 10 4 and 5 × 10 7 , preferably between 7.5 × 10 4 and 5 × 10 6 . Protonated polyethyleneimine (25% AS), methylated polyethyleneimine (25% AS) or protonated N, N-dimethylaminoethyl acrylate-acrylamide copolymer (100% AS) are preferably used (AS = active substance).
Durch Zugabe geeigneter Komplexbildner läßt sich die Leistungsfähigkeit der erfindungsgemäßen Mittel bei Ansatz in hartem Wasser oder bei der Anwendung auf Oberflächen, die metallhaltige Verunreinigungen aufweisen, weiter verbessern. Demgemäß umfaßt die Erfindung auch Mittel, die einen oder mehrere Komplexbildner ausgewählt aus mindestens einer der Gruppen d) Hydroxypolycarbonsäuren, e) stickstoffhaltige Mono- oder Polycarbonsäuren, f) Mono- oder Diphosphonsäuren, g) Aminophosphonsäuren, h) Phosphonopolycarbonsäuren, sowie wasserlösliche Salze, vorzugsweise Natrium-, Kaliumoder Ammoniumsalze der Säuren der Gruppen d) bis h) in Mengen bezüglich der freien Säuren zwischen 0,01 und 15 Gew.-% enthalten.By adding suitable complexing agents, the performance of the agents according to the invention can be further improved when prepared in hard water or when used on surfaces which have metal-containing impurities. Accordingly, the invention also includes agents which select one or more complexing agents from at least one of the groups d) hydroxypolycarboxylic acids, e) nitrogen-containing mono- or polycarboxylic acids, f) mono- or diphosphonic acids, g) aminophosphonic acids, h) phosphonopolycarboxylic acids, and water-soluble salts Contain sodium, potassium or ammonium salts of the acids of groups d) to h) in amounts with respect to the free acids between 0.01 and 15 wt .-%.
Geeignete Komplexbildner sind in großer Anzahl bekannt. Sie können unterschiedlichen chemischen Gruppen angehören. Vorzugsweise werden einzeln oder im Gemisch miteinander eingesetzt:
- d) Hydroxypolycarbonsäuren wie Weinsäure und Zitronensäure,
- e) stickstoffhaltige Mono- oder Polycarbonsäuren wie Ethylendiamintetraessigsäure (EDTA), N-Hydroxyethylethylendiamintriessigsäure, Diethylentriaminpentaessigsäure, Hydroxyethyliminodiessigsäure, Nitridodiessigsäure-3-propionsäure, Isoserindiessigsäure, N,N-Di-(β-hydroxyethyl)-glycin, N-(1,2-Dicarboxy-2-hydroxyethyl)-glycin, N-(1,2-Dicarboxy-2-hydroxyethyl)-asparaginsäure oder Nitrilotriessigsäure (NTA),
- f) Monophosphonsäuren mit 1 bis 10 C-Atomen, geminale Diphosphonsäuren wie 1-Hydroxyethan-1,1-diphosphonsäure (HEDP), deren höhere Homologe mit bis zu 8 Kohlenstoffatomen sowie Hydroxy- oder Aminogruppen-haltige Derivate hiervon und 1-Aminoethan-1,1-diphosphonsäure, deren höhere Homologe mit bis zu 8 Kohlenstoffatomen sowie Hydroxy- oder Aminogruppen-haltige Derivate hiervon,
- g) Aminophosphonsäuren wie Ethylendiamintetra(methylenphosphonsäure), Diethylentriaminpenta(methylenphosphonsäure) oder Nitrilotri(methylenphosphonsäure) sowie
- h) Phosphonopolycarbonsäuren wie 2-Phosphonobutan-1,2,4-tricarbonsäure.
- d) hydroxypolycarboxylic acids such as tartaric acid and citric acid,
- e) nitrogen-containing mono- or polycarboxylic acids such as ethylenediaminetetraacetic acid (EDTA), N-hydroxyethylethylenediaminetriacetic acid, diethylenetriaminepentaacetic acid, hydroxyethyliminodiacetic acid, nitridodiacetic acid-3-propionic acid, isoserinediacetic acid, N, N-di- (β-hydroxyethyl) -glycine Dicarboxy-2-hydroxyethyl) glycine, N- (1,2-dicarboxy-2-hydroxyethyl) aspartic acid or nitrilotriacetic acid (NTA),
- f) monophosphonic acids with 1 to 10 carbon atoms, geminal diphosphonic acids such as 1-hydroxyethane-1,1-diphosphonic acid (HEDP), their higher homologues with up to 8 carbon atoms, and derivatives thereof containing hydroxy or amino groups and 1-aminoethane-1 , 1-diphosphonic acid, its higher homologues with up to 8 carbon atoms and hydroxyl or amino group-containing Derivatives thereof,
- g) aminophosphonic acids such as ethylenediaminetetra (methylenephosphonic acid), diethylenetriaminepenta (methylenephosphonic acid) or nitrilotri (methylenephosphonic acid) and
- h) phosphonopolycarboxylic acids such as 2-phosphonobutane-1,2,4-tricarboxylic acid.
Die erfindungsgemäßen Mittel können ohne weitere, alkalische, Buildersubstanzen eingesetzt werden. Für anspruchsvolle Reinigungsaufgaben ist es jedoch empfehlenswert, die Reinigungswirkung durch alkalische Buildersubstanzen zu steigern. Hierfür sind die für alkalische Reiniger üblicherweise verwendeten Buildersubstanzen geeignet. Demnach umfassen die erfindungsgemäßen Mittel auch solche, die eine oder mehrere Buildersubstanzen, ausgewählt aus mindestens einer der Gruppen i) Mono-, Di- oder Triethanolamin oder deren Kationen, k) Alkalimetallhydroxide, 1) Silicate, vorzugsweise Metasilicate, m) Carbonate, n) Oligo- oder Polycarboxylate, o) Ortho- oder Polyphosphate, p) Borate, in Mengen zwischen 0,01 und 94,8 Gew.-% enthalten, wobei die Anionen der Gruppen 1) bis p) in Form ihrer wasserlöslichen Salze, vorzugsweise Ammonium- oder Alkalimetallsalze, insbesondere als Li-, Na- oder K-Salze vorliegen.The agents according to the invention can be used without further alkaline builder substances. For demanding cleaning tasks, however, it is advisable to increase the cleaning effect with alkaline builder substances. The builders commonly used for alkaline cleaners are suitable for this. Accordingly, the agents according to the invention also include those which contain one or more builder substances selected from at least one of the groups i) mono-, di- or triethanolamine or their cations, k) alkali metal hydroxides, 1) silicates, preferably metasilicates, m) carbonates, n) Oligo- or polycarboxylates, o) ortho- or polyphosphates, p) borates, in amounts between 0.01 and 94.8% by weight, the anions of groups 1) to p) being in the form of their water-soluble salts, preferably ammonium - Or alkali metal salts, in particular as Li, Na or K salts.
Weiterhin umfaßt die Erfindung Verfahren zur Reinigung und/oder Entfettung harter Oberflächen, dadurch gekennzeichnet, daß man die Oberflächen mit 2 bis 50 gew.-%igen wäßrigen Lösungen der Mittel durch Tauchen oder Spritzen bei Temperaturen zwischen 10 und 70 °C in Kontakt bringt.The invention further comprises processes for cleaning and / or degreasing hard surfaces, characterized in that the surfaces are brought into contact with 2 to 50% by weight aqueous solutions of the compositions by dipping or spraying at temperatures between 10 and 70 ° C.
Dabei hängen die zweckmäßigerweise einzustellenden Konzentrationen bzw. die zu wählenden Verdünnungen davon ab, ob die erfindungsgemäßen Mittel als Pulver, als wirkstoffreiche Pasten, oder als mehr oder weniger stark konzentrierte wäßrige Konzentrate eingesetzt werden. Vorzugsweise geht man so vor, daß man bei pulverförmigen Mitteln 2 bis 10 gew.-%ige wäßrige Lösungen, bei Verwendung pastenförmiger Mittel 2 bis 15 gew.-%ige wäßrige Lösungen und bei Verwendung flüssiger Mittel 5 bis 15 gew.-%ige wäßrige Lösungen einsetzt.The expedient concentrations to be set or the dilutions to be selected depend on whether the agents according to the invention are used as powders, as pastes rich in active substances or as more or less highly concentrated aqueous concentrates. The preferred procedure is to use 2 to 10% by weight aqueous solutions in the case of powdery compositions, 2 to 15% by weight aqueous solutions when using pasty compositions and 5 to 15% by weight aqueous solutions when using liquid compositions Uses solutions.
Bei technischen Reinigern ist es bekannt, die nichtionischen Tenside mit anionischen Tensiden zu kombinieren. Demnach liegen im Rahmen der vorliegenden Erfindung auch Verfahren, bei denen die wäßrige Reinigungslösung neben den erfindungsgemäßen Mitteln noch zusätzlich ein oder mehrere anionische Tenside ausgewählt aus mindestens einer der Gruppen q) Alkylsulfate mit einem linearen oder verzweigten Alkylrest mit 10 bis 18 C-Atomen, r) Alkyl-polyglykolether-sulfate mit einem linearen oder verzweigten Alkylrest mit 10 bis 18 C-Atomen und 1 bis 6 -CH2-CH2-O- Gruppen im Molekül, s) Alkylarylsulfonate mit einem Alkylbenzolrest mit einer linearen oder verzweigten Alkylgruppe mit 7 bis 9 C-Atomen in Mengen zwischen 0,01 und 3 Gew.-% enthält, wobei die Tensidanionen vorzugsweise in Form der Alkalimetallsalze, insbesondere der Natriumsalze vorliegen.In technical cleaners, it is known to combine the nonionic surfactants with anionic surfactants. Accordingly, are within the scope of the present The invention also relates to processes in which the aqueous cleaning solution, in addition to the agents according to the invention, additionally comprises one or more anionic surfactants selected from at least one of the groups q) alkyl sulfates with a linear or branched alkyl radical having 10 to 18 carbon atoms, r) alkyl polyglycol ether sulfates with a linear or branched alkyl radical with 10 to 18 carbon atoms and 1 to 6 -CH 2 -CH 2 -O- groups in the molecule, s) alkylarylsulfonates with an alkylbenzene radical with a linear or branched alkyl group with 7 to 9 carbon atoms in Contains amounts between 0.01 and 3% by weight, the surfactant anions preferably being in the form of the alkali metal salts, in particular the sodium salts.
Die erfindungsgemäßen Reinigungs-/Entfettungsmittel und Reinigungsverfahren lassen sich allgemein für die Arbeitsgebiete der Industriereiniger, einschließlich der Fahrzeug- und Betriebsreinigung, verwenden. Ihr Vorzug des hohen Benetzungsvermögens zeigt sich insbesondere dann, wenn es sich bei den zu entfettenden Oberflächen um Oberflächen aus organischen Polymeren handelt. Beispielhaft hierfür sind lackierte Oberflächen oder Oberflächen aus Polycarbonaten oder Polyurethanen. Besonders zu nennen sind weiterhin Oberflächen aus unpolaren Kunststoffen wie beispielsweise aus Polyolefinen und vorzugsweise Oberflächen aus halogenierten Polyolefinen und insbesondere Polyvinylchlorid.The cleaning / degreasing agents and cleaning methods according to the invention can generally be used for the fields of work of industrial cleaners, including vehicle and operational cleaning. Their advantage of high wetting power is particularly evident when the surfaces to be degreased are surfaces made from organic polymers. Examples of this are painted surfaces or surfaces made of polycarbonates or polyurethanes. Surfaces made of non-polar plastics, such as polyolefins, and preferably surfaces made of halogenated polyolefins, and in particular polyvinyl chloride, should also be mentioned in particular.
Die Reiniger wurden als Pulverprodukt oder als flüssige wäßrige Konzentrate in vollentsalztem Wasser formuliert (Beispiele 1-3). Zum Ansetzen der Entfettungsbäder wurden die Pulver bzw. die Konzentrate mit Stadtwasser (18° Deutsche Härte) auf die in den Tabellen angegebenen Konzentrationen gelöst bzw. verdünnt.The cleaners were formulated as powder products or as liquid aqueous concentrates in deionized water (Examples 1-3). To prepare the degreasing baths, the powders or the concentrates were dissolved or diluted with city water (18 ° German hardness) to the concentrations given in the tables.
Die Reinigungs-/Entfettungswirkung der erfindungsgemäßen Mittel und von Vergleichsformulierungen wurde an Platten aus PVC (=Polyvinylchlorid) überprüft. Hierzu wurden die Probeplatten zunächst mit einem handelsüblichen Reiniger gereinigt und anschließend mit einem mineralischen Testöl beölt. Die beölten PVC-Platten wurden bei Raumtemperatur in Reinigerlösungen gemäß den Tabellen 1 bis 3 gehängt und die Zeit bis zur vollständigen Benetzung beurteilt. Die für jede Formulierungsgruppe (= jede Tabelle) jeweils kürzeste Zeit wurde = 100 % gesetzt und die längeren Benetzungszeiten hierauf bezogen. Wenn nach maximal 4 Stunden Beobachtungszeit noch keine vollständige Benetzung eingetreten war, wurde der Versuch abgebrochen. Solche Fälle sind in den Tabellen mit "---" gekennzeichnet.The cleaning / degreasing effect of the agents according to the invention and of comparison formulations was checked on PVC (= polyvinyl chloride) sheets. For this purpose, the sample plates were first cleaned with a commercially available cleaner and then oiled with a mineral test oil. The oiled PVC sheets were hung at room temperature in cleaning solutions according to Tables 1 to 3 and the time until complete wetting was assessed. The shortest time for each formulation group (= each table) was set = 100% and the longer wetting times related to this. If no complete wetting had occurred after a maximum of 4 hours of observation, the experiment was stopped. Such cases are marked in the tables with "---".
Die nach diesen Versuchen als am schnellsten benetzende Formulierungen identifizierten Beispiele aus jeder Gruppe, die Beispiele 4, 8 und 12 sowie entsprechende Aminosäure-freie Vergleichsbeispiele wurden hinsichtlich ihrer Benetzungszeiten unter verschiedenen Applikationsbedingungen relativ zueinander geprüft. Dabei wurde die kürzeste Benetzungszeit = 100 % gesetzt. Die Ergebnisse zeigt Tabelle 4.The formulations from each group identified as the fastest wetting formulations after these experiments, Examples 4, 8 and 12 and corresponding amino acid-free comparative examples were tested relative to one another with regard to their wetting times under different application conditions. The shortest wetting time = 100%. The results are shown in Table 4.
Es wurden erfindungsgemäße Reinigungs-/Entfettungsmittel mit folgender Zusammensetzung hergestellt (in Gew.-%):Cleaning / degreasing agents according to the invention were produced with the following composition (in% by weight):
Claims (16)
- Powder-form, paste-form or liquid formulations for cleaning and/or degreasing hard surfaces which containa) 0.2 to 12% by weight of one or more aliphatic or aromatic monoamino-or diaminomonocarboxylic or dicarboxylic acids or monoaminodicarboxylic acid monoamides corresponding to general formula (I):a and b independently of one another are integers of 0 to 6,R1 at each carbon atom independently of one another may represent H, OH, CH3 or C2H5,R2 at each carbon atom independently of one another may represent H, CH3 or C2H5,R3 is H, CH3 or C2H5,R4 at each carbon atom independently of one another may represent H, OH, CH3 or C2H5,R5 at each carbon atom independently of one another may represent H, CH3 or C2H5, andX is hydrogen, a homocyclic or heterocyclic group, preferably phenyl, C(O)OH or C(O)NH2 and - with the proviso that b > 0 - also represents NH2, NH-C(=NH)-NH2, NH-C(=O)-NH2,or anions thereof,b) 1 to 12% by weight of one or more carboxylic acids corresponding to general formula (II):
R6-COOH (II)
in which R6 is an aliphatic, linear or branched hydrocarbon radical containing 5 to 9 carbon atoms and 0 or 1 double bond or an R7-C6H4-C(O)-CH=CH- group, where R7 is a linear or branched C8-14 alkyl radical, or anions thereof,c) 4 to 15% by weight of one or more nonionic surfactants selected from the group of ethoxylated and/or ethoxylated and propoxylated fatty alcohols corresponding to general formula (III):the balance to 100% by weight consisting of water and/or auxiliaries, preferably selected from builders, other surfactants, polymers and complexing agents.
R8-O-(EO)x-(PO)y-H (III)
in whichR8 is a linear or branched alkyl radical containing 6 to 14 carbon atoms,x is a number of 2 to 10,y is a number of 0 to 8,EO is a -CH2-CH2-O- group andPO is a -CH(CH3)-CH2-O- group, - Formulations as claimed in claim 1, characterized in that, in the general formula (I) of the amino acids or amino acid derivatives of group a), R1, R2, R3, R4 and R5 each represent hydrogen.
- Formulations as claimed in one or both of claims 1 and 2, characterized in that, in general formula (I), a = 0.
- Formulations as claimed in claim 3, characterized in that, in general formula (I), R3 is hydrogen.
- Formulations as claimed in one or more of claims 1 to 4, characterized in that the amino acids or amino acid derivatives corresponding to general formula (I) are chiral in relation to the carbon atom bearing the amino group and are preferably present in the L form.
- Formulations as claimed in one or more of claims 1 to 5, characterized in that oligopeptides, protein hydrolyzates, lactams or anhydrides of polybasic amino acids are used as the amino acid derivatives of amino acids corresponding to general formula (I).
- Formulations as claimed in one or more of claims 1 to 6, characterized in that they containthe amino acids or amino acid derivatives from group a) or anions thereof in quantities of 0.4 to 4% by weightand/orthe carboxylic acids from group b) or anions thereof in quantities of 2 to 7% by weightand/orthe nonionic surfactants from group c) in quantities of 5 to 10% by weight.
- Formulations as claimed in one or more of claims 1 to 7, characterized in that they contain cationic surfactants, betaines and/or cationically modified polymers in quantities of 0.01 to 3% by weight.
- Formulations as claimed in one or more of claims 1 to 8, characterized in that they contain one or more complexing agents selected from at least one of the groups d) hydroxypolycarboxylic acids, e) nitrogen-containing mono-or polycarboxylic acids, f) mono- or diphosphonic acids, g) aminophosphonic acids, h) phosphonopolycarboxylic acids and also water-soluble salts, preferably sodium, potassium or ammonium salts, of the acids of groups d) to h) in quantities based on the free acids of 0.01 to 15% by weight.
- Formulations as claimed in one or more of claims 1 to 9, characterized in that they contain one or more builders selected from at least one of the groups i) mono-, di- or triethanolamine or cations thereof, k) alkali metal hydroxides, I) silicates, preferably metasilicates, m) carbonates, n) oligo- or polycarboxylates, o) ortho or polyphosphates, p) borates in quantities of 0.01 to 94.8% by weight, the anions of groups I) to p) being present in the form of their water-soluble salts, preferably ammonium or alkali metal salts, more particularly as Li, Na or K salts.
- Formulations as claimed in one or more of claims 1 to 10, characterized in that they additionally contain 0.05 to 14.5% by weight of mixed ethers corresponding to the general formula R'-O-(EO)n-R", where R' is a C6-18 alkyl or alkenyl radical, R" is a C4-8 alkyl radical and n is a number of 2 to 6.
- Formulations as claimed in one or more of claims 1 to 11, characterized in that the amino acid of group a) is glutamic acid.
- A process for cleaning and/or degreasing hard surfaces, characterized in that the surfaces are contacted with 2 to 50% by weight aqueous solutions of the formulations claimed in one or more of claims 1 to 12 by immersion or spraying at temperatures of 10 to 70°C.
- A process as claimed in claim 13, characterized in that 2 to 10% by weight aqueous solutions are used in the case of powders, 2 to 15% by weight aqueous solutions are used in the case of pastes and 5 to 15% by weight aqueous solutions are used in the case of liquid formulations.
- A process as claimed in one or both of claims 13 and 14, characterized in that the aqueous cleaning solution additionally contains one or more anionic surfactants selected from at least one of the groups q) alkyl sulfates with a linear or branched C10-18 alkyl group, r) alkyl polyglycol ether sulfates with a linear or branched C10-18 alkyl group and 1 to 6 -CH2-CH2-O- groups in the molecule, s) alkylaryl sulfonates with an alkyl benzene group containing a linear or branched C7-9 alkyl group in quantities of 0.01 to 3% by weight, the surfactant anions preferably being present in the form of alkali metal salts, more particularly sodium salts.
- A process as claimed in one or more of claims 13 to 15, characterized in that the surfaces are surfaces of organic polymers, preferably painted surfaces and/or surfaces of polycarbonates, polyurethanes, polyolefins, halogenated polyolefins, more particularly polyvinyl chloride.
Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE4324396 | 1993-07-21 | ||
DE4324396A DE4324396A1 (en) | 1993-07-21 | 1993-07-21 | Detergents with high wettability |
PCT/EP1994/002285 WO1995003389A1 (en) | 1993-07-21 | 1994-07-12 | High wetting-power detergent |
Publications (2)
Publication Number | Publication Date |
---|---|
EP0710274A1 EP0710274A1 (en) | 1996-05-08 |
EP0710274B1 true EP0710274B1 (en) | 1997-10-01 |
Family
ID=6493315
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP94924746A Expired - Lifetime EP0710274B1 (en) | 1993-07-21 | 1994-07-12 | High wetting-power detergent |
Country Status (7)
Country | Link |
---|---|
US (1) | US5935920A (en) |
EP (1) | EP0710274B1 (en) |
AT (1) | ATE158813T1 (en) |
DE (2) | DE4324396A1 (en) |
DK (1) | DK0710274T3 (en) |
ES (1) | ES2109012T3 (en) |
WO (1) | WO1995003389A1 (en) |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP3156475B1 (en) | 2015-10-16 | 2018-06-06 | Hans Georg Hagleitner | Liquid cleaning concentrate |
Families Citing this family (20)
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DE19719606C2 (en) * | 1997-05-09 | 1999-02-18 | Henkel Kgaa | Solid preparations |
DE19842053A1 (en) * | 1998-09-15 | 2000-03-23 | Bayer Ag | Use of polyaspartic acids in cleaning formulations with an abrasive effect |
US6428814B1 (en) * | 1999-10-08 | 2002-08-06 | Elan Pharma International Ltd. | Bioadhesive nanoparticulate compositions having cationic surface stabilizers |
US6559116B1 (en) | 1999-09-27 | 2003-05-06 | The Procter & Gamble Company | Antimicrobial compositions for hard surfaces |
DE10007323A1 (en) * | 2000-02-17 | 2001-08-23 | Bode Chemie Gmbh & Co Kg | Detergent for medical instruments |
US6514458B1 (en) * | 2000-02-25 | 2003-02-04 | Ge Betz, Inc. | Method for removing microbes from surfaces |
WO2001062091A1 (en) * | 2000-02-25 | 2001-08-30 | Betzdearborn Inc. | Method for enhancing biocidal activity |
DE102004057623A1 (en) | 2004-11-29 | 2006-06-01 | Henkel Kgaa | Aqueous cleaning agent concentrate, useful for cleaning oil- and/or fat- polluted metallic surfaces, comprises water, glycol ether and/or non-ionic surfactant, polyethylenimine and cationic surfactant |
DE102006018216B4 (en) | 2006-04-18 | 2008-09-25 | Chemetall Gmbh | Process for the demulsifying cleaning of metallic surfaces |
US8093200B2 (en) | 2007-02-15 | 2012-01-10 | Ecolab Usa Inc. | Fast dissolving solid detergent |
DE102007000501A1 (en) * | 2007-10-15 | 2009-04-16 | Chemetall Gmbh | Cleaning composition for metallic surfaces |
EP2138437A1 (en) | 2008-06-27 | 2009-12-30 | Kba-Giori S.A. | Inspection system for inspecting the quality of printed sheets |
EP2305785A1 (en) | 2009-10-02 | 2011-04-06 | Unilever N.V. | Use of a carboxylic or amino compound as cleaning aid for hard surfaces and method of cleaning such hard surfaces |
US8389463B2 (en) * | 2009-11-09 | 2013-03-05 | Ecolab Usa Inc. | Enhanced dispensing of solid compositions |
CN102770522B (en) * | 2010-02-23 | 2014-03-19 | 狮王株式会社 | Metal cleaner |
US20130096045A1 (en) * | 2011-10-12 | 2013-04-18 | Ecolab Usa Inc. | Moderately alkaline cleaning compositions for proteinaceous and fatty soil removal at low temperatures |
WO2014095617A1 (en) * | 2012-12-20 | 2014-06-26 | Unilever Plc | Stain removal compositions |
CN108137459B (en) | 2015-10-07 | 2021-06-18 | 海名斯精细化工公司 | Wetting and antifoam agents |
MA46044A (en) * | 2016-08-25 | 2019-07-03 | Ecolab Usa Inc | CLEANING COMPOSITIONS CONSISTING OF AN AMINO ACID AND THEIR METHODS OF USE |
WO2022018779A2 (en) * | 2020-07-19 | 2022-01-27 | University Of Petra | Safe foaming liquid composition for personal care |
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DE1942236A1 (en) * | 1969-08-20 | 1971-03-04 | Henkel & Cie Gmbh | Enzymatic washing agents and detergents |
DE1964792A1 (en) * | 1969-12-24 | 1971-07-01 | Henkel & Cie Gmbh | Protein removing washing agents contg amino - acids |
FR2264085B1 (en) * | 1974-03-15 | 1976-12-17 | Procter & Gamble Europ | |
DE2712900C2 (en) * | 1977-03-24 | 1986-04-10 | Henkel KGaA, 4000 Düsseldorf | Process for cleaning metals by spraying |
US4412943A (en) * | 1981-02-23 | 1983-11-01 | Kao Soap Co., Ltd. | Liquid detergent composition |
JPS6115815A (en) * | 1984-06-29 | 1986-01-23 | Lion Corp | Cosmetic for hair |
DE3727378A1 (en) * | 1987-08-17 | 1989-03-02 | Henkel Kgaa | FOAM-PRESSING ADDITIVES IN LOW-FOAM CLEANING AGENTS |
JPH0299599A (en) * | 1988-10-07 | 1990-04-11 | Sumitomo Light Metal Ind Ltd | Cleaning agent for aluminum heat-exchanger for air-conditioning |
JPH0699703B2 (en) * | 1989-05-12 | 1994-12-07 | 花王株式会社 | Liquid cleaning composition for bathroom |
DE3935374A1 (en) * | 1989-10-24 | 1991-04-25 | Henkel Kgaa | ALKYLPOLYETHYLENGLYKOLETHER AS FOAM-PRESSING ADDITIVES FOR CLEANERS |
US5066425A (en) * | 1990-07-16 | 1991-11-19 | The Procter & Gamble Company | Formation of high active detergent particles |
JP3170724B2 (en) * | 1992-03-11 | 2001-05-28 | 味の素株式会社 | Detergent composition |
DE4319578A1 (en) * | 1993-06-14 | 1994-12-15 | Henkel Kgaa | Detergent containing amino acids and / or their salts |
DE4319798A1 (en) * | 1993-06-15 | 1994-12-22 | Henkel Kgaa | Dishwashing detergent with reduced tendency to scale up |
US5573702A (en) * | 1993-11-22 | 1996-11-12 | Colgate-Palmolive Co. | Liquid cleaning compositions with grease release agent |
BR9408124A (en) * | 1993-11-22 | 1997-08-05 | Colgate Palmolive Co | Microemulsion composition cleaning composition for hard surfaces for all purposes liquid detergent for light duty and liquid detergent composition |
US5486307A (en) * | 1993-11-22 | 1996-01-23 | Colgate-Palmolive Co. | Liquid cleaning compositions with grease release agent |
US5415813A (en) * | 1993-11-22 | 1995-05-16 | Colgate-Palmolive Company | Liquid hard surface cleaning composition with grease release agent |
-
1993
- 1993-07-21 DE DE4324396A patent/DE4324396A1/en not_active Withdrawn
-
1994
- 1994-07-12 DE DE59404229T patent/DE59404229D1/en not_active Expired - Fee Related
- 1994-07-12 US US08/583,083 patent/US5935920A/en not_active Expired - Fee Related
- 1994-07-12 EP EP94924746A patent/EP0710274B1/en not_active Expired - Lifetime
- 1994-07-12 WO PCT/EP1994/002285 patent/WO1995003389A1/en active IP Right Grant
- 1994-07-12 AT AT94924746T patent/ATE158813T1/en not_active IP Right Cessation
- 1994-07-12 DK DK94924746.4T patent/DK0710274T3/en active
- 1994-07-12 ES ES94924746T patent/ES2109012T3/en not_active Expired - Lifetime
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP3156475B1 (en) | 2015-10-16 | 2018-06-06 | Hans Georg Hagleitner | Liquid cleaning concentrate |
Also Published As
Publication number | Publication date |
---|---|
ATE158813T1 (en) | 1997-10-15 |
WO1995003389A1 (en) | 1995-02-02 |
DE4324396A1 (en) | 1995-01-26 |
ES2109012T3 (en) | 1998-01-01 |
DE59404229D1 (en) | 1997-11-06 |
DK0710274T3 (en) | 1998-05-11 |
EP0710274A1 (en) | 1996-05-08 |
US5935920A (en) | 1999-08-10 |
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