EP0710274A1

EP0710274A1 - High wetting-power detergent

Info

Publication number: EP0710274A1
Application number: EP94924746A
Authority: EP
Inventors: Juergen Geke; Friedbert Zetzsche
Original assignee: Henkel AG and Co KGaA
Current assignee: Henkel AG and Co KGaA
Priority date: 1993-07-21
Filing date: 1994-07-12
Publication date: 1996-05-08
Anticipated expiration: 2014-07-12
Also published as: DE59404229D1; DE4324396A1; WO1995003389A1; US5935920A; ATE158813T1; DK0710274T3; ES2109012T3; EP0710274B1

Abstract

PCT No. PCT/EP94/02285 Sec. 371 Date Jan. 22, 1996 Sec. 102(e) Date Jan. 22, 1996 PCT Filed Jul. 12, 1994 PCT Pub. No. WO95/03389 PCT Pub. Date Feb. 2, 1995Powdered, paste, or liquid media for cleaning and/or degreasing hard surfaces, especially surfaces of organic polymers (PVC) contain active ingredients of amino acids, carboxylic acids, and nonionic surfactants, possibly supplemented by action-reinforcing auxiliaries and/or demulsifying additives. Processes using these media are also claimed.

Description

"Detergent with high wetting capacity"

The invention relates to powdery, pasty or liquid compositions 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 in each case and nonionic surfactants. The agents can be used as industrial cleaners (as neutral cleaners or as alkaline cleaners) as well as for vehicle and operational cleaning.

DE-A-27 12900 describes a method for cleaning metals by spraying. Here, 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 references to the possible use of amino acids in such cleaners.

GB-A-2231 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 ^ Groupings. Rather, the term aminocarboxylic acid here means carboxylic acids with a tertiary amino function, for example nitrotriesriacetic acid or ethylenediaminetetraacetic acid.

DE-A-3206350 relates to a liquid detergent mixture which has an appropriate viscosity at the time of use. It is specifically intended as a shampoo. Their 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 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, ho ocysteic acid, lysine, ornithine, arynithine, are particularly preferred. Serine, homoserine, tyrosine, threonine, proline, hydroxypro-1in, 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-a inodicarboxylic acid selected from the group consisting of glutamic acid, aspartic acid, aminomalonic acid, a inoadipic acid and 2-amino-2-methylpentanedioic acid or the like Salts. Sodium glutamate is particularly preferred. Optional constituents of the detergent mixture are also nonionic, cationic, amphoteric or zwitterionic surfactants. These detergents can furthermore contain carboxylates, CIQ-CIS alkyl monocarboxylates, i.e. Soaps, especially called.

DE-A-1942236 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 amino acids or their salts containing a further carboxyl and / or amino group. 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-active 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.

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 the amorphous and crystalline, layer-shaped alkali silicates contain and which are characterized in that they additionally contain sulfur-free, 2 to 11 carbon atoms and optionally an additional carboxyl and / or amino group and amino acids and / or their salts. The amino acids ¹ 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. Soaps in particular Ci2-C24-F are preferred ^{e 'ttsäureseifen.} These detergents for textile washing therefore contain the typical detergent constituents called zeolite and / or layered alkali silicates.

German patent application P 43 19798.1 discloses agents for machine 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 characterized ge 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 a readily biodegradable alkali carrier. 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.

This object is achieved by containing powdery, pasty or liquid agents for cleaning and / or degreasing hard surfaces

a) 0.2 to 12% by weight of one or more aliphatic or aromatic monoamino or diamino ono or dicarboxylic acids or monoaminodicarboxylic acid monoamides of the general formula (I)

where a and b independently of one another are integers from 0 to 6,

R * on each C atom independently of one another can denote H, OH, CH3 or C2H5, R2 on each C atom independently of one another can denote H, CH3 which can mean C2H5, R ^{3 stands} for H, CH3 or C2H5, R ⁴ on each C Atom can independently mean H, OH, CH3 or C2H5, R5 on each carbon atom independently and H, CH3 or C2H5 can mean and X is hydrogen, a homo- or heterocyclic radical, preferably phenyl, C (0) 0H or C (0) NH2 and, provided that b> 0, additionally NH ₂ , NH-C (= NH) -NH, NH-C (= 0) -NH ₂ means

or their anions,

b) 1 to 12% by weight of one or more carboxylic acids each having 4 to 24 C atoms, or their anions, c) 4 to 15% by weight of one or more nonionic surfactants,

the rest being 100% by weight of water and / or auxiliaries, preferably selected from builder substances, further surfactants, polymers and complexing agents.

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. The alkali metal salts, preferably the sodium salts, of these acids are particularly suitable as water-soluble salts. 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.

Unbranched amino acids of the formula (I) or their derivatives are preferably used, that is to say those compounds in which the radicals R to R5 each denote 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. Among 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. 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.

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-a-inobutyric acid, epsilon- Aminocaproic acid, glutamine, glutamic acid, aspartic acid, lysine, ornithine, arginine, serine, ho oserine, tyrosine, threonine, proline, hydroxyproline, aminomalonic acid, aminoadipic acid and 2-amino-2-methylpentanedioic acid. Particularly good results are obtained with glutamic acid.

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 cleaner bath. Such amino acid precursors are, for example, oligopeptides or protein hydrolyzates, lactams such as, for example, epsilon-Caprolacta or anhydrides of polybasic amino acids.

The carboxylic acids of group b) can be represented by the general formula (II)

R ⁶ -C00H (II)

where R6 is an aliphatic, linear or branched hydrocarbon radical with 3 to 23 carbon atoms and 0 to 5 double bonds, preferably with 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. 1-

Further carboxylic acids of the general formula (II) are those in which R ^{6 is} an R ⁷ -CÖH4-C (0) -CH = -CH- group, in which R ^{7 is} a linear or branched alkyl radical having 8 means up to 14 carbon atoms.

The nonionic surfactants of group c) are selected from the group of ethoxylated and / or ethoxylated and propoxylated fatty alcohols of the general formula (III)

R8-0- (E0) _x - (P0) _y -H (III)

in which

Rδ is 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 is a number in the range from 2 to 10 and y is a number in the range from 0 to 8 and E0 stand for a -CH2-CH2-O- group and PO for a -CH (CH3) -CH2-0- group.

The nonionic surfactants are to be selected so that they comply with the statutory provisions (detergent law) with regard to their biodegradability. In order to limit the tendency of the detergents to foam, it is recommended that the cloud points of the nonionic surfactants lie 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 that can be used are end-capped ethoxylation products of fatty alcohols of the general formula R'-0- (E0) _n -R ", in which R ^{1 is} an alkyl or alkenyl radical with 6-18 C atoms, R" is an alkyl radical with 4 -8 carbon 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 cleaner solution) are described in more detail, for example, in the published documents DE-A-3727378 and DE-A-3935374. $

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.

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 further auxiliaries customary for cleaners, such as builder substances, further surfactants, polymers and / or complexing agents.

When formulated as a powder, the auxiliaries mentioned are added in powder form to the active compound combination of groups a), b) and c) in such proportions that the total mixture contains the active compounds from groups a), b) and c) in the stated 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.

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. According to Rö pp 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.

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 appropriate, after temperature adjustment and / or dilution - as an oily phase float on the aqueous 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 the cleaning solutions are diluted. 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.

Such ammonium compounds of the formula (IV) are suitable as cationic surfactants:

_R a

R ^D - N ⁺ - R ^d X- (IV)

suitable which contain one, two or three unsubstituted or linear or branched carbon chains substituted by hydroxyl groups. Ammonium compounds of the general formula R ^a RbR ^C RdN ⁺ χ- are preferably used, in which at least one, preferably two, of the radicals R are unsubstituted or optionally substituted by a hydroxyl group. HO

are radicals with 1-2 carbon atoms and at least one of the remaining radicals R is 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.

In particular, ammonium salts are used as cationic surfactants in which R ^a and R ^{D are} methyl, R ^{c is} methyl, 2-hydroxyethyl, benzyl, 2-hydroxydodecyl or 2-hydroxyhexadecyl and R ^{d is} 2-hydroxydodecyl, 2-hydroxyhexadecyl, lauryl, hexadecyl or stearyl .

Compounds of the general formula R ^a R ^D 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} a 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 CsH5N ⁺ -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.

In principle, all nitrogen-containing polymers which can be cationically modified or converted into the corresponding ammonium salts either by protonation or alkylation, usually methylation, of the 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.

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-dialkylaminoalkylacrylates, dialkylamine or vinylpyridine, and methylated quaternary polymers such as polydiallyldimethyl ammonium 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 ^. Protonated polyethyleneimine (25% AS), methylated polyethyleneimine (25% AS) or protonated N, N-dimethylaminoethyl acrylate-acrylamide copolymer (100% AS) are preferably used (AS = active substance).

By adding suitable complexing agents, the performance of the agents according to the invention can be further improved when mixed 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) A inophosphonic acids, h) phosphonopolycarboxylic acids, and water-soluble ones Salts, preferably 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 .-%.

A large number of suitable complexing agents are known. They can belong to different chemical groups. The following are preferably used individually or in a mixture:

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, n-3-n-propanoic acid, β-hydroxyethyl) glycine, N- (1,2-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 hydroxyl or amino groups and 1-aminoethane-1 , l-diphosphonic acid, its higher homologues with up to 8 carbon atoms and hydroxy or amino group Pen-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-l, 2,4-tricarboxylic acid.

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 builder substances usually 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, ) 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 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 active ingredient-rich pastes 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 in the case of pasty compositions and 5 to 15% by weight in the case of the use of liquid compositions. uses aqueous solutions.

In technical cleaners, it is known to combine the nonionic surfactants with anionic surfactants. Accordingly, within the framework of the The present invention also processes in which the aqueous cleaning solution in addition to the agents according to the invention additionally 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 -CH2-CH2-O- groups in the molecule, s) alkylarylsulfonates with an alkylbenzene radical with a linear or branched alkyl group with 7 to Contains 9 carbon atoms in 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 industrial 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.

Ausföhrunαsbeispiele

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.

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 to 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 "-".

The formulations from each group identified as the fastest wetting formulations after these tests, 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% was set. The results are shown in Table 4.

Examples 1-3: powder products and liquid concentrates

Cleaning / degreasing agents according to the invention were produced with the following composition (in% by weight): Example 1 (powder product):

Trisodium nitrilotriacetate 13.8

Sodium metasilicate 15.0

Sodium carbonate 41.2

3,5,5-trimethylhexanoic acid 10.0

L-glutamic acid 10.0

Octanol x 3.5 E0 x 2 PO 10.0

Example 2 (aqueous concentrate):

Triethanolamine 18.2

Sodium carbonate 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

Cιo / i2-alcohol mixture x 6 E0 x 8 PO 7.0

Water 52.5

Example 3 (aqueous concentrate):

Trinatriu nitritrotriacetate 6.5

Coco alkyl dimethyl ammonium betaine 1.4

2,2-dimethyloctanoic acid 1.5

L-glutamic acid 0.5

Octanol x 3.5 E0 x 2 PO 2.9

Octanol x 4.7 E0 5.5

Water 81.7 Tab. 1: Cleaning solutions I composition in% by weight

Ex. 4 * Ex. 5 Ex. 6 Ex. 7 Comp. 1 cf. 2

Trinatium- 0.97 0.97 0.97 0.7 0.97 0.97 nitrilotriacetate

Natriu - 1.05 1.05 0.7 1.4 1.4 1.4 metasilicate

Sodium carbonate 2.88 2.88 2.18 3.15 3.23 3.23

Trisodium - - 1.05 - - - orthophosphate

3,5,5-trimethyl-0.7-0.7 0.49-0.7 hexanoic acid

Octanoic acid - 0.7 - - - -

A inopentandi- 0.7 - - 0.35 0.7 - acid

(L-glutamic acid) gam a-aminobutyric acid - 0.7 - - - -

Glycine 0.7

Octanol x 3.5 EO x 2 PO 0.7 0.7 0.7 0.91 0.7 0.7

Water 93 93 93 93 93 93

Degreasing time (%) 100 100 110 130 200 180 ^r ) 7% by weight solution of the cleaning powder according to Example 1.

Tab. 2: Cleaner solutions II compositions in% by weight

Ex. 8 * Ex. 9 Ex. 10 Ex. 11 Comp. 3 cf. 4

Water 93.35 93.35 93.35 93.35 93.35 94.57

Triethanolamine 2.55 2.55 2.55 2.55 2.55 2.55

Sodium carbonate 0.28 0.28 0.28 0.28 0.28 0.56

2-ethylhexanoic acid 1.19 1.19 1.19 1.19 1.19 -

Aminopentanedioic acid 0.18 - - - - 0.18 (L-glutamic acid)

L-aspartic acid - 0.18 - ^' - -

L-Asparagine - - 0.18 - -. -

L-arginine - - - 0.18 - -

Octylphosphonic acid 0.14 0.14 0.14 0.14 0.14 0.14

Nitrilitri (methylene 0.42 0.42 0.42 0.42 0.42 0.42 phosphonic acid)

Sodium hydroxide 0.91 0.91 0.91 0.91 0.91 0.42

Cιo / 12 ~ Alcoholic x 0.98 0.98 0.98 0.98 1.16 1.16 6 EO x 8 PO

Degreasing time (%) 100 110 120 120 220 -

^r ) 14% by weight solution of the concentrate according to Example 2.

S

Tab. 3: Cleaner solutions III compositions in wt

Ex. 12 * Comp. 5 cf. 6

Water 97.44 97.44 97.44

Trisodium 0.91 0.91 0.91 nitrilotriacetate

Coco alkyl dimethyl 0.20 0.20 0.20 ammonium betaine

2,2-dimethyloctanoic acid 0.21-0.21

Aminopentadioic acid 0.07 0.07 _

(L-glutamic acid)

Octanol 0.41 0.41 0.41 x 3.5 E0 x 2 PO

Octanol x 4.7 E0 0.76 0.97 0.83

Degreasing time 100 170 150

(%)

^r ) 14% by weight solution of the concentrate according to Example 3. IQ

Tab. 4 Application variations of the solutions according to Tab. 1-3

Test substance Application temperature Degreasing type (° C) Time (%)

Ex. 4 syringes 60 100

Ex. 4 diving 50 120

Ex. 4 diving 20 150

Ex. 8 syringes 60 120

Ex. 8 syringes 40 130

Ex. 8 diving 60 150

Ex. 12 diving 60 110

Cf. 2 syringes 60 190

Cf. 3 syringes 60 220

Cf. 6 syringes 60 170

Claims

• 90 patent claims

1. Containing powdery, pasty or liquid agents for cleaning and / or degreasing hard surfaces

a) 0.2 to 12% by weight of one or more aliphatic or aromatic monoamino or diaminomono or dicarboxylic acids or monoamino dicarboxylic acid monoamides of the general formula (I)

where a and b independently of one another are integers from 0 to 6,

R 1 on each C atom can independently mean H, OH, CH3 or C2H5,

R2 on each C atom can independently denote H, CH3 or C2H5,

R3 represents H, CH3 or C2H5,

R4 on each C atom can independently mean H, OH, CH3 or C2H5,

R5 on each C atom independently of one another and can mean H, CH3 or C2H5 and

X is hydrogen, a homo- or heterocyclic radical, preferably phenyl, C (0) OH or C (0) NH2 and, provided that b> 0, additionally NH ₂ , NH-C (= NH) -NH ₂ , NH-C (= 0) -NH ₂ means

or their anions,

b) 1 to 12% by weight of one or more carboxylic acids each having 4 to 24 C atoms, or their anions, c) 4 to 15% by weight of one or more nonionic surfactants, the rest being 100% by weight of water and / or auxiliaries, preferably selected from builder substances, further surfactants, polymers and complexing agents.

2. Composition according to claim 1, characterized in that in the general formula (I) the amino acids or amino acid derivatives of group a) Rl, R ² , R3, R4 and R5 each represent hydrogen.

3. Composition according to one or both of claims 1 and 2, characterized gekenn¬ characterized in that in the general formula (I) a = 0.

4. Composition according to claim 3, characterized in that in the general formula (I) R3 is hydrogen.

5. Composition according to one or more of claims 1 to 4, characterized gekenn¬ characterized in that the amino acids or amino acid derivatives of the general formula (I) are chiral with respect to the carbon atom carrying the amino group and are preferably in the L-form.

6. Composition according to one or more of claims 1 to 5, characterized gekenn¬ characterized in that the carboxylic acids of group b) of the general formula (II)

R ⁶ -C00H (II)

correspond, where R *> is an aliphatic, linear or branched hydrocarbon radical having 3 to 23 carbon atoms and 0 to 5 double bonds, preferably having 5 to 9 carbon atoms and 0 or a double bond.

7. Composition according to one or more of claims 1 to 5, characterized gekenn¬ characterized in that the carboxylic acids of group b) of the general formula (II)

R6-C00H (II) -2Z

correspond, where R ^{6 is} an R ⁷ -C6H4-C (0) -CH = CH group, in which R7 is a linear or branched alkyl radical having 8 to 14 carbon atoms.

8. Composition according to one or more of claims 1 to 7, characterized gekenn¬ characterized in that the nonionic surfactants of group c) are selected from the group of ethoxylated and / or ethoxylated and propoxylated fatty alcohols of the general formula (III)

Rß-0- (E0) _x - (P0) _y -H (III)

in which

RÖ is 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 is a number in the range from 2 to 10 and y is a number in the range from 0 to 8 and E0 stand for a -CH2-CH2-O- group and PO for a -CH (CH3) -CH2-0- group.

9. Composition according to one or more of claims 1 to 8, characterized in that it

the amino acids or amino acid derivatives from group a) or their anions in amounts between 0.4 and 4% by weight

and or

contain the nonionic surfactants from group c) in amounts between 5 and 10% by weight. -2.3

10. Composition according to one or more of claims 1 to 9, characterized gekenn¬ characterized in that they contain cationic surfactants, betaines and / or cationically modified polymers in amounts between 0.01 and 3 wt .-%.

11. Composition according to one or more of claims 1 to 10, characterized ge indicates that it contains 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 water-soluble salts, preferably 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% by weight. % contain.

12. Composition according to one or more of claims 1 to 11, characterized in that it comprises 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) in the form of their water-soluble salts, preferably ammonium or alkali metal salts, in particular in the form of Li, Na or K salts.

13. Composition according to one or more of claims 1 to 12, characterized in that it additionally 0.05-14.5 wt .-% mixed ether of the general formula R'-0- (E0) _n -R " contain 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 is a number from 2-6.

14. Composition according to one or more of claims 1 to 13, characterized in that the amino acid of group a) is glutamic acid.

15. A method for cleaning and / or degreasing hard surfaces, characterized in that the surfaces with 2 to 50 wt .-% aqueous solutions of the composition according to one or more of claims 1 to 14 by dipping or spraying at temperatures between 10 and 70 ° C in contact.

16. The method according to claim 15, characterized in that 2 to 10 wt .-% aqueous solutions in powdery compositions, 2 to 15 wt .-% aqueous solutions in the use of pasty agents and 5 when using liquid agents up to 15% by weight aqueous solutions.

17. The method according to one or both of claims 15 and 16, characterized ge indicates that the aqueous cleaning solution additionally 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 having 10 to 18 carbon atoms and 1 to 6 -CH2-CH2-O- groups in the molecule, s) alkylarylsulfonates with an alkyl benzene radical with a linear or branched alkyl group contains with 7 to 9 carbon atoms in 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.

18. The method according to one or more of claims 15 to 17, characterized in that the surfaces are surfaces made of organic polymers, preferably lacquered surfaces and / or surfaces made of polycarbonates, polyurethanes, polyolefins, halogenated polyolefins, in particular Polyvinyl chloride.