JP2002535445A - Hydrophobizing agents for hard surfaces - Google Patents

Abstract

  (57) [Summary] Cleaned hard surfaces of objects made of metal, glass, porcelain, plastic and coatings of said materials of water-soluble and / or water-dispersible polymers based on lysine, arginine, ornithine, tryptophan or mixtures thereof Use as an additive to wash water used to rinse surfaces.

Description

DETAILED DESCRIPTION OF THE INVENTION

The present invention relates to a water-soluble and / or water-soluble for cleaning post-cleaning hard surfaces of objects made of metal, glass, porcelain, plastic and painted surfaces made of said materials.
Or the use of water-dispersible polymers as additives in washing water. As a result, the surface can be made hydrophobic, and as a result, the formation of a film during post-washing with hard water can be avoided or limited.

In automotive cleaning, hydrophobizing agents have been added to the water of the last cleaning process to hydrophobize the painted surface of the vehicle. This breaks down the scale on the painted surface during drying, and the water drips completely as easily as possible. This avoids the formation of dirt during drying and minimizes the energy consumption of the blower used during drying. Hydrophobizing agents commonly used for this purpose include cationic surfactants and further additives such as carboxylic acid esters, acetal, amino-functional polysiloxanes or copolymers containing tertiary amine functions. . DE
-A-3930028, US-A-5391325, WO-A-92 / 21743, D
See EA-3439440 and DE-A-4323638. The hydrophobizing agents known to date need improvement. Thus, for example, certain products form a film on the windshield of an automobile and cause dirt. Further, known hydrophobizing agents include:
It does not cause permanent hydrophobicization of the surface and is not biodegradable.

The object of the present invention is to provide a biodegradable, fast-adhering and long-lasting action,
Another object of the present invention is to provide a hydrophobizing agent having no property of forming a film on glass.

[0004] The aforementioned problems have been solved for the cleaning of objects made of metal, glass, porcelain, plastic, of water-soluble and / or water-dispersible polymers based on lysine, arginine, ornithine, tryptophan or mixtures thereof. It has been found that this can be achieved by use as an additive to cleaning agents used on hard surfaces as well as on painted surfaces made of the above materials.

The polymer is, for example, a homocondensate of the above-mentioned basic amino acids obtained by condensation of a) lysine, arginine, ornithine, tryptophan or a mixture thereof and b) at least one compound capable of homocondensation, or a polymer thereof. Is a co-condensate of the amino acids

[0006] Suitable polymers are, for example, a) lysine, arginine, ornithine, tryptophan or mixtures thereof and b) monoamines, diamines, triamines, tetraamines, mono-aminocarboxylic acids, lactams, aliphatic amino alcohols, ureas, guanidines. Melamine, carboxylic acids, carboxylic anhydrides, diketene, non-proteinaceous amino acids, alcohols, alkoxylated alcohols, alkoxylated amines, amino sugars, sugar carboxylic acids or mixtures thereof with at least one compound selected from the group consisting of: Can be

From an industrial point of view, a) lysine and b) C ₆ -C ₁₈ -alkylamines, lactams having 5 to 13 carbon atoms in the ring, non-proteinaceous amino acids, carboxylic acids, carboxylic anhydrides and Particular preference is given to condensation products obtained by condensation with at least one compound from the group of diketene.

The compounds of groups (a) and (b) are, for example, 100: 1 to 1: 2 upon condensation.
It is used in a molar ratio of 0, preferably 100: 1 to 1: 5, and usually 10: 1 to 1: 2.

In the condensation, the compounds of group (a) include the basic amino acids lysine, arginine, ornithine and tryptophan, free bases, hydrates and esters with C ₁ -C ₄ -alcohols And salt forms, such as sulfates, hydrochlorides,
Or acetate is used. It is advantageous to use aqueous solutions of lysine hydrate and lysine. Lysine can likewise be used in the form of a cyclic lactam, α-amino-ε-caprolactam. Similarly, lysine mono- or dihydrochloride or lysine ester mono- or dihydrochloride can be used. As long as a salt of a compound of group (a) is used, an inorganic base such as
It is advantageous to use equivalent amounts of sodium hydroxide, potassium hydroxide or magnesium oxide. The alcohol component of the lysine ester mono- and dihydrochlorides is derived, for example, from low-boiling alcohols, such as methanol, ethanol, isopropanol or t-butanol. During the condensation, it is advantageous to use L-lysine dihydrochloride, DL-lysine monohydrochloride and L-lysine monohydrochloride.

Examples of co-condensable compounds of group b) are aliphatic or cycloaliphatic amines, advantageously methylamine, ethylamine, propylamine, butylamine, pentylamine,
Hexylamine, heptylamine, octylamine, nonylamine, decylamine, undecylamine, dodecylamine, tridecylamine, stearylamine, palmitylamine, 2-ethylhexylamine, isononylamine, hexamethylenediamine, dimethylamine, diethylamine, diamine Propylamine, dibutylamine, dihexylamine, ditridecylamine, N-methylbutylamine,
N-ethylbutylamine, cyclopentylamine, cyclohexylamine, N-
Methylcyclohexylamine, N-ethylcyclohexylamine and dicyclohexylamine.

Of the diamines, triamines and tetraamines, advantageously, ethylenediamine, propylenediamine, butylenediamine, neopentyldiamine, hexamethylenediamine, octamethylenediamine, imidazole, 5-amino-1,3
-Trimethylcyclohexylmethylamine, diethylenetriamine, dipropylenetriamine and tripropyltetraamine are preferred. Further suitable amines are 4,4′-methylenebiscyclohexylamine, 4,4′-methylenebis- (2-methyl-cyclohexylamine), 4,7-dioxadecyl-1,1
0-diamine, 4,9-dioxadodecyl-1,12-diamine, 4,7,10
-Trioxatridecyl-1,13-diamine-2- (ethylamino) ethylamine, 3- (methylamino) propylamine, 3- (cyclohexylamino) propylamine, 3- (2-aminoethyl) aminopropylamine, 2- (diethylamino) ethylamine, 3- (dimethylamino) propylamine, dimethyldipropylenetriamine, 4-aminomethyloctane-1,8-diamine, 3- (
Diethylamine) propylamine, N, N-diethyl-1,4-pentanediamine, diethylenetriamine, dipropylenetriamine, bis (hexamethylene)
Triamine, aminoethylpiperazine, aminopropylpiperazine, N, N-bis (aminopropyl) methylamine, N, N-bis (aminopropyl) ethylamine, N, N-bis (aminopropyl) methylamine, N, N-bis (Aminopropyl) ethylamine, N, N-bis (aminopropyl) hexylamine, N, N
N-bis (aminopropyl) octylamine, N, N-dimethyldipropylenetriamine, N, N-bis (3-dimethylaminopropyl) amine, N, N'-1
, 2-ethanediylbis (1,3-propanediamine), N- (hydroxyethyl) piperazine, N- (aminoethyl) piperazine, N- (aminopropyl) piperazine, N- (aminoethyl) morpholine, N- (aminopropyl) ) Morpholine, N- (aminoethyl) imidazole, N- (aminopropyl) imidazole, N- (aminoethyl) hexamethylenediamine, N- (aminopropyl) hexamethylenediamine, N- (aminoethyl) ethylenediamine, N- ( (Aminopropyl) ethylenediamine, N- (aminoethyl) butylenediamine, N- (aminopropyl) butylenediamine, bis (aminoethyl) piperazine, bis (aminopropyl) piperazine, bis (aminoethyl) hexamethylenediamine, bis (aminopropyl) Hexamethylenediamine, bis (aminoethyl) ethylenediamine, bis (aminopropyl) ethylenediamine, bis (aminoethyl) butylenediamine, bis (aminopropyl) butylenediamine, oxypropylamine, such as advantageously hexyloxyamine, octyloxyamine , Decyloxyamine and dodecyloxyamine.

Aliphatic amino alcohols include, for example, 2-aminoethanol, 3-amino-1
-Propanol, 1-amino-2-propanol, 2- (2-aminoethoxy)
Ethanol, 2-[(2-aminoethyl) amino] ethanol, 2-methylaminoethanol, 2- (ethylamino) ethanol, 2-butylaminoethanol,
Diethanolamine, 3-[(hydroxyethyl) amino] -1-propanol,
Diisopropanolamine, bis- (hydroxyethyl) aminoethylamine,
Bis- (hydroxypropyl) aminoethylamine, bis- (hydroxyethyl) aminopropylamine and bis- (hydroxypropyl) aminopropylamine.

Suitable monoaminocarboxylic acids are advantageously glycine, alanine, sarcosine, asparagine, glutamine, 6-aminocaproic acid, 4-aminobutyric acid, 11-
Aminolauric acid, a lactam having 5 to 13 carbon atoms in the ring, such as caprolactam, laurolactam or butyrolactam. Furthermore, glucosamine, melamine, urea, guanidine, polyguanidine, piperidine, morpholine, 2,6-dimethylmorpholine and tryptoamine are applicable. Particular preference is given to: a) lysine and b) hexamethylenediamine, octylamine, monoethanolamine, octamethylenediamine, diaminododecene, decylamine, dodecylamine, caprolactam, laurolactam, aminocaproic acid, aminolauric acid or mixtures thereof. Is a polymer produced by condensation with

Other cocondensable compounds b) are, for example, saturated monocarboxylic acids, unsaturated monocarboxylic acids, polybasic carboxylic acids, carboxylic anhydrides, diketene, monohydroxycarboxylic acids, monobasic polycarboxylic acids. It is a mixture of hydroxycarboxylic acids and the aforementioned compounds. Examples of saturated monobasic carboxylic acids are formic, acetic, propionic, butyric, valeric, caproic, octanoic, nonanoic, lauric, palmitic, stearic, arachidonic, behenic, myristic, 2-ethylhexanoic acid and all naturally occurring fatty acids and mixtures thereof.

Examples of unsaturated monobasic carboxylic acids are acrylic acid, methacrylic acid, crotonic acid
Sorbic acid, oleic acid and linoleic acid erucic acid. Polybasic carbo
Examples of acids are oxalic acid, fumaric acid, maleic acid, malonic acid, succinic acid, itacone
Acid, adipic acid, aconitic acid, azelaic acid, pyridinedicarboxylic acid, furan
Dicarboxylic acid, phthalic acid, terephthalic acid, diglycolic acid, glutaric acid, substituted C ₄ Dicarboxylic acid, sulfosuccinic acid, C₁~ C₆-Alkyl succinic acid, C₂-C ₂₆ -Alkenyl succinic acid, 1,2,3-propanetricarboxylic acid, 1,1,3
, 3-propanetetracarboxylic acid, 1,1,2,2-ethanetetracarboxylic acid,
1,2,3,4-butanetetracarboxylic acid, 1,2,2,3-propanetetraca
Rubonic acid, 1,3,3,5-pentanetetracarboxylic acid, 1,2,4-benzene
Tricarboxylic acid and 1,2,4,5-benzenetetracarboxylic acid. anhydrous
Examples of the carboxylic acid include mono- and dianhydrides of butanetetracarboxylic acid.
, Phthalic anhydride, acetyl citric anhydride, maleic anhydride, itaconic anhydride and
And acrolite anhydride.

Particular preference is given to polymers prepared by condensation of a) lysine with b) lauric acid, palmitic acid, stearic acid, succinic acid, adipic acid, ethylhexanoic acid or mixtures thereof.

Suitable as component b) are alkyl diketene having 1 to 30 carbon atoms in the alkyl group and diketene itself. Examples of alkyldiketene are methyldiketene, hexyldiketene, cyclohexyldiketene, octyldiketene, decyldiketene, dodecyldiketene, palmitydiketene, stearyldiketene, oleyldiketene, octadecyldiketene, eicosyldiketene, docosyldiketene and behenyldiketene.

Examples of monohydroxycarboxylic acids are malic acid, tartaric acid, citric acid and isocitric acid. Polyhydroxycarboxylic acids are, for example, tartaric acid, gluconic acid, bis (hydroxymethyl) propionic acid and hydroxylated unsaturated fatty acids, for example dihydroxystearic acid.

Component b) includes other non-proteinaceous amino acids such as anthranilic acid, N-methylamino-substituted acids such as N-methylglycine, dimethylaminoacetic acid, ethanolaminoacetic acid, N-carboxymethylaminocarboxylic acid acid, nitrilotriacetic acid, ethylenediaminetetraacetic acid, ethylene diamino tetraacetic acid, diethylenetriamine pentaacetic acid, hydroxyethylene diamino triacetic acid, diaminosuccinic _acid, C 4 _{-C 26} - aminoalkyl carboxylic acids, for example, 4-amino butyric acid, 6-
Aminocaproic acid and 11-aminoundecanoic acid are relevant. The acids can be used in the condensation in the form of the free acids or in the form of their salts with alkali metal bases or amines.

Component b) includes other alcohols, for example monohydric alcohols having 1 to 22 carbon atoms in the molecule, for example methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, t -Butanol,
Preferred are n-pentanol, hexanol, 2-ethylhexanol, cyclohexanol, octanol, decanol, dodecanol, palmityl alcohol, stearyl alcohol and vinyl alcohol. Other suitable alcohols are, for example, ethylene glycol, propylene glycol, glycerol, 2-8
Polyglycerol, erythritol, pentaerythritol and sorbitol, which have one glycerin unit. The alcohol may be optionally alkoxylated. Examples of such compounds are C ₂ to 1 mole of alcohol.
C ₄ - an alkylene oxide to 200 mol of the addition product. Suitable alkoxides are, for example, ethylene oxide, propylene oxide and isomeric butylene oxide. Advantageously, ethylene oxide or propylene oxide is used or both ethylene oxide and propylene oxide are added to the alcohol in the form of a block, first of all a series of ethylene oxide units,
The propylene oxide units can then be added to the alcohol or propylene oxide and then ethylene oxide can be initially charged to the alcohol.
The random addition of ethylene oxide and propylene oxide and the arrangement of other blocks in the alkoxylation product are conceivable. Particularly preferably, for _{example, C} 1 3 _{/ C 15} - oxo alcohols or ethylene oxide 3-20 mole addition product with respect to higher alcohols 1 mol. The alcohol may optionally contain double bonds, such as, for example, oleyl alcohol. Component b) includes:
For example, alkoxylated amines derived from the abovementioned amines and obtained by reaction with ethylene oxide and / or propylene oxide may be used. Examples include the addition products of 5 to 30 moles of ethylene oxide per mole of stearylamine, oleylamine or palmitylamine. Component c) includes naturally occurring amino sugars, such as chitosan or chitosamine, and compounds obtained from carbohydrates by reductive amination, such as aminosorbitol. The condensation products include carbohydrates such as glucose, sucrose, dextrin, starch and degraded starch, maltose and sugar carboxylic acids such as gluconic acid, glucaric acid, gluconolactone and glucuronic acid, optionally in condensed form. It may be contained.

The above-mentioned components can be used in the form of the free base (for example amines) or the corresponding salts in the condensation, for example ammonium salts with inorganic or organic acids. In the case of carboxylic acids, the cocondensable compounds (b) can be used in the condensation in the form of the free carboxylic acids or of their alkali metal, alkaline earth metal or ammonium salts.

The condensation can be carried out in an organic solvent or an aqueous medium without diluent. Advantageously, the reaction is carried out in an aqueous medium at a temperature of from 120 to 300 ° C., for example from 10 to 98% by weight of the group (a
) And (b). In a particularly preferred embodiment of the process for preparing such compounds, 20 to 70% by weight of components (a) and (b)
At a temperature of 140 to 250 ° C. in water at atmospheric pressure. However, the condensation is carried out in an organic solvent, for example dimethylformamide, dimethylsulfoxide, dimethylacetamide, glycol, polyethylene glycol, propylene, glycol, polypropylene glycol, monohydric alcohols, addition products of ethylene oxide and / or monohydric alcohols, amines or carboxylic acids And in propylene oxide. Reactants (a) and (
If an aqueous solution of b) is used as starting material, water can optionally be distilled off before or during the condensation. The condensation can be carried out at atmospheric pressure with removal of the water. Advantageously, the water formed during the condensation is removed from the reaction mixture. The condensation can be performed at elevated pressure, atmospheric pressure or reduced pressure. The condensation time is, for example, between 1 minute and 50 hours, preferably between 30 minutes and 16 hours. The condensation product is
It has, for example, a molar mass _{Mw of} from 300 to 1,000,000, preferably from 500 to 100,000.

The condensation can optionally also be carried out in the presence of an inorganic acid as catalyst. The concentration of the inorganic acid is, for example, from 0.001 to 5% by weight, preferably from 0.01 to 1% by weight.
Examples of inorganic acids suitable as catalysts are hypophosphorous acid, hypodiphosphorous
acid), phosphonic acid, hydrochloric acid, sulfuric acid or a mixture of said acids. Alkali metal-, ammonium- and alkaline earth metal salts of the acids can be used as catalysts.

The water-soluble and / or water-dispersible condensate consisting of the above compounds (a) and (b) can be used as an additive to the washing water used for the cleaned hard surface. The water-soluble and water-insoluble condensates can be used in each case alone and in the form of a mixture in any proportion of such condensates as additives to the wash water. This achieves, among other things, the hydrophobization of painted surfaces made of metal and plastic, in particular of automobiles. Formulations used as an additive to the wash water and containing at least one condensate of the type described above can be obtained from Putz- und Reinigungsm
Meets the quality standards for car care and cleaning agents, ittel e. V., Frankfurt, SOEFW, Vol. 104, 1/1978, p. 26, and does not cause undesired filming and fouling on glass plates . Therefore, the above-mentioned condensates, particularly lysine condensates, are also suitable as a rinsing agent for dishwashers. The biodegradability of the lysine condensate
Modified Strum test and OECD according to OECD Guideline 301B
Measured in a modified SCAS test according to Guideline 302A. OEC
According to D201, the condensates to be used according to the invention have in many cases significantly reduced algal toxicity compared to most cationic surfactants. Hydrophobizing agents to be used according to the invention for hard surfaces break down water films on metal or painted surfaces,
And the water drips as easily as possible. As a result, the formation of lime stains is avoided during drying.

The hydrophobizing agents to be used according to the invention are preferably used in a mixture with virtually any other component. Such a mixture has, for example, the following composition (all percentages are given in% by weight): at least one cationic hydrophobic component comprising the condensate to be used according to the invention. 50%, hydrophobic silicone-free oil 0-15% (preferably 10-15%, particularly preferably 2%
-5%), silicone oil 0-10% (preferably 0.5% -7.5%, particularly preferably 1% -7%)
%), Emulsified wax 0 to 15% (when emulsified wax is added, 0.5% to 10%,
Particular preference is given to using 2% to 8%), wetting and emulsifying agents 0 to 20% (preferably 2% to 12%, particularly preferably 2.5%)
-10%), acidifying agent 0.1-10% (preferably 0.3-5%, particularly preferably 0.5-3%)
0.1 to 25% of the solubilizer (preferably 1 to 20%, particularly preferably 2.5 to 15%)
Other modifying additives, such as perfumes, dyes, foam formers and brighteners 0-5%, and the balance to 100% with water.

As the cationic hydrophobic component, the condensates according to the invention are used alone or in combination with known cationic hydrophobic surfactants. Suitable cationic hydrophobic surfactants are widely described in the literature. Particularly _preferred, C 8 _{-C 25} - alkyl ammonium salts, quaternary _C 8 _{-C 25} - alkyl _{imidazolines,} C 8 _{-C 22} - alkyl ester quat _{(quat), C 8 ~C 25} - alkyl - substituted amine And 2
An oligoamine having four amine groups.

Suitable silicone-free oils include, for example, saturated and unsaturated C₁₂~ C₂₅ -Hydrocarbons, C₆~ C₂₀-Alkylbenzene, C₁₂~ C₂₅-Alcohol,
C₁₂~ C₂₅-Alcohol and C₂~ C₈Esters with carboxylic acids, C₁~ C ₈ -Alcohol and C₈~ C₂₅-Esters with fatty acids are relevant. Of these oils
Examples are paraffin oil, citrus terpene, pine oil, higher alcohols and fatty acids.
Methyl esters and acetates of higher alcohols.

Emulsifying waxes can include aqueous emulsions of natural and synthetic waxes. Emulsion _C 2 -C of an unsaturated carboxylic acid ₄ - polyalkylene copolymers,
In particular, ethylene / acrylic acid wax is particularly preferred.

As the wetting agent and emulsifier, alcohol and 1 to 5 mol of ethylene oxide and / or 1 to 10 mol of propylene oxide and / or butylene oxide 1
. Alkoxylated obtained by reaction of 5 mole C _{10 -C} 25 _- fatty alcohol and oxo alcohols are preferred. Similarly, propylene oxide and / or
Alternatively, block polymers of butylene oxide and ethylene oxide having a content of ethylene oxide units of less than 30% by weight are also suitable.

Suitable acidifying agents are C ₁ -C ₃ -carboxylic acids, especially acetic acid.

Suitable solubilizers are, for example, water-soluble glycols, polyglycols, monoalkyl glycols, monoalkyl polyglycols, dialkyl diglycols and dialkyl polyglycols, wherein said polyglycol is from 2 to 10 Ethylene oxide-, propylene oxide- and / or butylene oxide units may be present in a random or block distribution, and the alkyl group may have 1 to 6 carbon atoms. Preference is given to using mono-C ₁ -C ₄ -alkyl glycols, particularly preferably monobutyl glycol.

The hydrophobizing agents are used, for example, in aqueous diluents, for example for hydrophobizing paint-, glass-, porcelain- or metal surfaces or textile or leather materials. In this case, the formulated hydrophobizing agent is mixed with water in a ratio of 1: 100 to 1: 3000, preferably 1:50.
Dilute at a mass ratio of 0 to 1: 2000. Optionally, a volatile alcohol that can be mixed with water can be added. In the case of hydrophobizing textile and leather materials, the formulated hydrophobizing agent is diluted with water in a weight ratio of from 1: 5 to 1: 500, preferably from 1:10 to 1: 100. Because the polymers according to the invention have a hydrophobizing action and improved sliding properties, these polymers can also be used advantageously as chain greases and lubricants.

The average molecular weight Mw of the condensation product was measured by gel permeation chromatography (GPC) using a mixture of acetonitrile and water at a volume ratio of 20 to 80 as a mobile phase. Waters Ultrahydrogel 500, 250, 250 and 12 as stationary phases
A column packed with 0 was used. At the time of GPC, a UV detector was used, and the wavelength of the light used was 230 nm. Pullulan-Standard with a narrow molar mass distribution was used for calibration. The numerical values are described in mass%.

EXAMPLES The following hydrophobic components were tested for their effectiveness as hydrophobizing agents and preservatives.

Rinsing agent 1: Polylysine having a molecular weight of 4000 Rinsing agent 2: Condensation product of L-lysine and aminated caproic acid in a molar ratio of 1: 1 L-lysine monohydrate (656.8 g, 4.0 mol), Aminocaproic acid (524.7 g, 4.0 mol) and sodium hypophosphite (0.1 g) were added to 2.
Charge into a 5 l pressure vessel and evacuate with nitrogen three times. Thereafter, the apparatus is hermetically sealed and heated at 200 ° C. for 6 hours, while maintaining the internal pressure at 7.65 bar.
After depressurizing the apparatus to atmospheric pressure, the temperature is maintained at 180 ° C. for 30 minutes to distill off residual solvents and volatile products. The resulting red, low-viscosity melt solidifies on cooling to room temperature. By adding water and subsequently neutralizing with concentrated sulfuric acid to pH 7.5, a raw material solution having a concentration of about 54% is produced. The molecular weight _Mw of the resulting polymer is 3550.

Rinsing agent 3: Condensation product of L-lysine and hexamethylenediamine at a molar ratio of 5: 1 L-lysine (1078.7 g, 7.38 mol), hexamethylenediamine (1
71.5 g, 1.48 mol) and propylene glycol (1 liter) in a 5 liter glass vessel equipped with a reflux condenser and a distillation column under a constant nitrogen flow under a constant nitrogen flow of 170.
Heat at 4 ° C. for 4 hours, during which time water is distilled off. After this, the remaining solvent and volatile products are separated in a round bottom flask. The resulting dark brown, highly viscous melt is dissolved in water and adjusted to pH 7.5 using methacrylic acid.

Rinsing agent 4: Condensation product of L-lysine and adipic acid at a molar ratio of 5: 1 L-lysine monohydrate (410.5 g, 2.5 mol), adipic acid (73
. 1 g, 0.5 mol), sodium hypophosphite (0.1 g) and water (176 g)
) Is heated in a 2 liter glass vessel equipped with a reflux condenser and a distillation column under a constant nitrogen flow at 152 ° C. for 5 hours, during which water is distilled off. Thereafter, a water-jet vacuum is applied for 1 hour to separate the remaining solvent and volatile products. The resulting red, low-viscosity melt is cooled to 100 ° C. After cooling to room temperature, the clear red solution formed after the addition of 400 g of water is adjusted to pH 7.5 with 72 g of concentrated sulfuric acid. The molecular weight M _w of the resulting polymer is 2160.

Rinsing agent 5: Condensation product of L-lysine and lauric acid in a molar ratio of 5: 1 L-lysine monohydrate (410.5 g, 2.5 mol), lauric acid (10
0.16 g, 0.5 mol), sodium hypophosphite (0.1 g) and water (17
6 g) is heated in a 2 liter glass vessel equipped with a reflux condenser and a distillation column under a constant nitrogen flow at 160 ° C. for 5 hours, during which water is distilled off. Thereafter, a water-jet vacuum is applied for 4 hours to separate the remaining solvent and volatile products. The resulting red, low-viscosity melt is cooled to 100 ° C. After cooling to room temperature, the clear red solution formed by adding 400 g of water is adjusted to pH 7.5 using 72 g of concentrated sulfuric acid. The molecular weight M _w of the resulting polymer is 3150.

Comparative rinsing agent 1: ditallow fatty dimethyl ammonium chloride Comparative rinsing agent 2: ditallow aliphatic isopropyl ester dimethyl ammonium meso sulphate The action of hydrophobizing agents and preservatives was determined by Putz-und Reinigugsmittel eV Fra
nkfurt (SOEFW Vol. 104, 1/1978, page 26) tested in a simplified screening according to the quality standards for car care and cleaners. Test methods for rinsing agents 1 to 5 and comparative rinsing agents For this, a solution consisting of 10% of active substance and 5% of butyl glycol was adjusted to pH 5 with dilute acetic acid and brought to 100% with water. For use, this concentration was diluted 1: 500 or 1: 1000 with tap water having a hardness of 20 ° (dH). The test is carried out on a 40 x 60 cm size open air, which has been completely cleaned with a commercial cleaner based on ionic and nonionic surfactants, on a black painted metal plate, washed with 100 ml of isopropanol And air dried.

To determine the water resistance or hydrophobizing capacity of the solution, a metal plate placed on a gentle slope was moistened with tap water and sprayed with about 100 ml of the solution to be tested (20 cm from the metal plate). Distance nozzle). The evaluation was visually performed using an evaluation scale of 1 to 5. Evaluation 1 shows that the scaling of the scale is spontaneous, that the wetting is completely destroyed and that relatively large water droplets are not formed; evaluation 3 shows that the water film is slowly decomposed, Indicated water droplets remain and no wet parts remain on the metal plate; rating 5 indicates incomplete decomposition and visible wet parts.

The metal plate was subsequently dried with air and washed with a total of about 10 liters of tap water for 2 minutes. Visual remeasurement of a vertically placed metal plate is a measure of the quality of the shelf life.

The hydrophobizing and preservative results obtained with rinsing agents 1 to 5 and the comparative rinsing agents of the prior art and water according to the test method described above are listed in the table below.

[0043]

[Table 1]

[Procedural Amendment] Submission of translation of Article 34 Amendment

[Submission date] January 27, 2001 (2001.1.27)

[Procedure amendment 1]

[Document name to be amended] Statement

[Correction target item name] Claim 1

[Correction method] Change

[Contents of correction]

[Procedure amendment 2]

[Document name to be amended] Statement

[Correction target item name] Claim 2

[Correction method] Change

[Contents of correction]

[Procedure amendment 3]

[Document name to be amended] Statement

[Correction target item name] 0004

[Correction method] Change

[Contents of correction]

[0004] The above-mentioned problem is related to the cleaning of hardened surfaces of metal, glass, porcelain, plastic objects and of water-soluble polymers based on lysine, arginine, ornithine, tryptophan or mixtures thereof and of said materials. It has been found that this can be achieved by using it as an additive to cleaning agents used on painted surfaces.

[Procedure amendment 4]

[Document name to be amended] Statement

[Correction target item name] 0011

[Correction method] Change

[Contents of correction]

Of the diamines, triamines and tetraamines, advantageously, ethylenediamine, propylenediamine, butylenediamine, neopentyldiamine, hexamethylenediamine, octamethylenediamine, imidazole, 5-amino-1,3
-Trimethylcyclohexylmethylamine, diethylenetriamine, dipropylenetriamine and tripropyltetraamine are preferred. Further suitable amines are 4,4′-methylenebiscyclohexylamine, 4,4′-methylenebis- (2-methyl-cyclohexylamine), 4,7-dioxadecyl-1,1
0-diamine, 4,9-dioxadodecyl-1,12-diamine, 4,7,10
-Trioxatridecyl-1,13-diamine-2- (ethylamino) ethylamine, 3- (methylamino) propylamine, 3- (cyclohexylamino) propylamine, 3- (2-aminoethyl) aminopropylamine, 2- (diethylamino) ethylamine, 3- (dimethylamino) propylamine, dimethyldipropylenetriamine, 4-aminomethyloctane-1,8-diamine, 3- (
Diethylamine) propylamine, N, N-diethyl-1,4-pentanediamine, bis (hexamethylene) triamine, aminoethylpiperazine, aminopropylpiperazine, N, N-bis (aminopropyl) methylamine, N, N-bis (Aminopropyl) ethylamine, N, N-bis (aminopropyl) methylamine, N, N-bis (aminopropyl) ethylamine, N, N-bis (aminopropyl) hexylamine, N, N-bis (aminopropyl) Octylamine, N,
N-dimethyldipropylenetriamine, N, N-bis (3-dimethylaminopropyl) amine, N, N′-bis- (3-aminopropyl) -1,2-ethanediamine, N- (hydroxyethyl) piperazine, N- (aminoethyl) piperazine, N- (aminopropyl) piperazine, N- (aminoethyl) morpholine, N-
(Aminopropyl) morpholine, N- (aminoethyl) imidazole, N- (aminopropyl) imidazole, N- (aminoethyl) hexamethylenediamine,
N- (aminopropyl) hexamethylenediamine, N- (aminoethyl) ethylenediamine, N- (aminopropyl) ethylenediamine, N- (aminoethyl)
Butylenediamine, N- (aminopropyl) butylenediamine, bis (aminoethyl) piperazine, bis (aminopropyl) piperazine, bis (aminoethyl)
Hexamethylenediamine, bis (aminopropyl) hexamethylenediamine, bis (aminoethyl) ethylenediamine, bis (aminopropyl) ethylenediamine, bis (aminoethyl) butylenediamine, bis (aminopropyl) butylenediamine, oxypropylamine, for example, advantageously Are hexyloxypropylamine, octyloxypropylamine, decyloxypropylamine and dodecyloxypropylamine.

[Procedure amendment 5]

[Document name to be amended] Statement

[Correction target item name] 0015

[Correction method] Change

[Contents of correction]

[0015] Examples of unsaturated monobasic carboxylic acids are acrylic acid, methacrylic acid, crotonic acid, sorbic acid, oleic acid, linoleic acid and erucic acid. Examples of polybasic carboxylic acids are oxalic acid, fumaric acid, maleic acid, malonic acid, succinic acid, itaconic acid, adipic acid, aconitic acid, azelaic acid, pyridinedicarboxylic acid, furandicarboxylic acid, phthalic acid, terephthalic acid , diglycolic acid, glutaric acid, substituted _{C 4} - dicarboxylic acid, sulfosuccinic _acid, C 1 -C ₆ - alkyl succinic acids, _{C 2} -
C ₂₆ - alkenyl succinic acid, 1,2,3 propane tricarboxylic acid, 1,1,
3,3-propanetetracarboxylic acid, 1,1,2,2-ethanetetracarboxylic acid, 1,2,3,4-butanetetracarboxylic acid, 1,2,2,3-propanetetracarboxylic acid, 1, 3,3,5-pentanetetracarboxylic acid, 1,2,4-benzenetricarboxylic acid and 1,2,4,5-benzenetetracarboxylic acid. The carboxylic anhydrides include, for example, mono- and dianhydrides of butanetetracarboxylic acid, phthalic anhydride, acetylcitric anhydride, maleic anhydride, itaconic anhydride and aconitic anhydride.

[Procedure amendment 6]

[Document name to be amended] Statement

[Correction target item name] 0017

[Correction method] Change

[Contents of correction]

Suitable as component b) are alkyl diketene having 1 to 30 carbon atoms in the alkyl group and diketene itself. Examples of alkyldiketene are methyldiketene, hexyldiketene, cyclohexyldiketene, octyldiketene, decyldiketene, dodecyldiketene, palmitydiketene, stearyldiketene, oleyldiketene, eicosyldiketene, docosyldiketene and behenyldiketene.

[Procedure amendment 7]

[Document name to be amended] Statement

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[Correction method] Change

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Examples of monohydroxycarboxylic acids are malic acid, citric acid and isocitric acid. Polyhydroxycarboxylic acids are, for example, tartaric acid, gluconic acid, bis (hydroxymethyl) propionic acid and hydroxylated unsaturated fatty acids, for example dihydroxystearic acid.

[Procedure amendment 8]

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[Correction target item name] 0019

[Correction method] Change

[Contents of correction]

Component b) includes other non-proteinaceous amino acids such as anthranilic acid, N-methylamino-substituted acids such as N-methylglycine, dimethylaminoacetic acid, ethanolaminoacetic acid, N-carboxymethylaminocarboxylic acid acid, nitrilotriacetic acid, ethylenediaminetetraacetic acid, ethylene diamino tetraacetic acid, diethylenetriamine peta acid, hydroxyethylene diamino triacetic acid, diaminosuccinic acid, C 4 _-C 26 _- aminoalkyl carboxylic acids, for example, corresponding the 11-aminoundecanoic acid. The acids can be used in the condensation in the form of the free acids or in the form of their salts with alkali metal bases or amines.

[Procedure amendment 9]

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[Correction target item name] 0020

[Correction method] Change

[Contents of correction]

Component b) includes other alcohols, for example monohydric alcohols having 1 to 22 carbon atoms in the molecule, for example methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, t -Butanol,
Preferred are n-pentanol, hexanol, 2-ethylhexanol, cyclohexanol, octanol, decanol, dodecanol, palmityl alcohol and stearyl alcohol. Other suitable alcohols are, for example, ethylene glycol, propylene glycol, glycerol, polyglycerol having 2 to 8 glycerin units, erythritol, pentaerythritol and sorbitol. The alcohol may be optionally alkoxylated.
Examples of such compounds are the addition products of 1 to 200 mol of C ₂ -C ₄ -alkylene oxide per mol of alcohol. Suitable alkoxides are, for example, ethylene oxide, propylene oxide and isomeric butylene oxide.
Advantageously, ethylene oxide or propylene oxide is used, or both ethylene oxide and propylene oxide are added to the alcohol in the form of blocks, first of all a series of ethylene oxide units and subsequently of propylene oxide units to the alcohol. Alternatively, it is possible to initially charge propylene oxide and then ethylene oxide to the alcohol. The random addition of ethylene oxide and propylene oxide and the arrangement of other blocks in the alkoxylation product are conceivable. Particular preference is given, for example, to addition products of 3 to 20 mol of ethylene oxide per mol of C ₁₃ / C ₁₅ -oxo alcohol or higher alcohol. The alcohol may optionally contain double bonds, such as, for example, oleyl alcohol. As component b), use may be made, for example, of alkoxylated amines derived from the abovementioned amines and obtained by reaction with ethylene oxide and / or propylene oxide. Examples include the addition products of 5 to 30 moles of ethylene oxide per mole of stearylamine, oleylamine or palmitylamine. Component c) includes naturally occurring aminopolysaccharides, such as chitosan or chitosamine, and compounds obtained from carbohydrates by reductive amination, such as aminosorbitol. The condensation products include carbohydrates such as glucose, sucrose, dextrin, starch and degraded starch, maltose and sugar carboxylic acids such as gluconic acid, glucanic acid, gluconolactone and glucuronic acid, optionally in condensed form. It may be contained.

──────────────────────────────────────────────────続 き Continued on the front page (72) Inventor Hans-Peter Seelmann-Eggebert Germany Limburger Hof Weinbeitstrasse 2 (72) Inventor Dieter Steckicht Germany Germany Ludwigshafen Fen Königstrasse 4 F-term (reference) ) 4H003 BA12 DA05 DA11 DC02 EB38 FA21 4J001 DA01 DA03 DB03 DC03 EA02 EA04 EA06 EA08 EA33 EA34 EA35 EA36 EA37 EC02 EC04 EC05 EC06 EC08 EC14 EC77 EC79 ED05 ED06 ED57 ED59 ED64 EE24 EE25 EE24 EA25 EE25

Claims (8)

[Claims] 1. A metal of a water-soluble and / or water-dispersible polymer based on lysine, arginine, ornithine, tryptophan or mixtures thereof,
Use as an additive in cleaning water used for post-cleaning of cleaned hard surfaces of objects made of glass, porcelain, plastic as well as painted surfaces made of said materials. 2. Use according to claim 1, wherein the polymer is obtained by condensation of (a) lysine, arginine, ornithine, tryptophan or a mixture thereof with (b) at least one cocondensable compound. 3. The polymer comprises: (a) lysine, arginine, ornithine, tryptophan or a mixture thereof; and (b) monoamine, diamine, triamine, tetraamine, mono-aminocarboxylic acid, lactam, aliphatic amino alcohol, urea, guanidine. Melamine, carboxylic acids, carboxylic anhydrides, diketene, non-proteinaceous amino acids, alcohols, alkoxylated alcohols, alkoxylated amines, amino sugars, sugar carboxylic acids or mixtures thereof with at least one compound from the group 3. Use according to claim 1 or 2, obtained. 4. The polymer comprises (a) lysine and (b) a C ₆ -C ₁₈ -alkylamine, a lactam having 5 to 13 carbon atoms in the ring, a non-proteinaceous amino acid, a carboxylic acid, a carboxylic anhydride. Use according to any one of claims 1 to 3, obtained by condensation with at least one compound consisting of diketene. 5. The polymer of group (a) in a molar ratio of 100: 1 to 1:20:
5. Use according to any one of claims 2 to 4, obtained by condensation of the compound of (b). 6. The polymer of group (a) :( m) in a molar ratio of 100: 1 to 1: 5.
5. Use according to any one of claims 2 to 4, obtained by condensation of the compound of b). 7. The polymer of group (a) :( b) in a molar ratio of 10: 1 to 1: 2.
5. Use according to any one of claims 2 to 4, which is obtained by condensation of a compound of the above). 8. The polymer as claimed in claim 1, wherein (a) lysine and (b) hexamethylenediamine, octylamine, monoethanolamine, octamethylenediamine, diaminododecane, decylamine, dodecylamine, caprolactam, laurolactam, aminocaproic acid, aminolauric acid 8. A method according to claim 1, which is obtained by condensation with lauric acid, palmitic acid, stearic acid, succinic acid, adipic acid, ethylhexanoic acid or a mixture thereof.
Use as described in section.