EP0859825B1 - Verwendung von polymeren aminodicarbonsäuren in waschmitteln - Google Patents
Verwendung von polymeren aminodicarbonsäuren in waschmitteln Download PDFInfo
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- EP0859825B1 EP0859825B1 EP96934752A EP96934752A EP0859825B1 EP 0859825 B1 EP0859825 B1 EP 0859825B1 EP 96934752 A EP96934752 A EP 96934752A EP 96934752 A EP96934752 A EP 96934752A EP 0859825 B1 EP0859825 B1 EP 0859825B1
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- EP
- European Patent Office
- Prior art keywords
- bleaching
- acid
- acids
- weight
- detergents
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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
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/39—Organic or inorganic per-compounds
- C11D3/3902—Organic or inorganic per-compounds combined with specific additives
- C11D3/3937—Stabilising agents
- C11D3/394—Organic compounds
-
- 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
- C11D3/37—Polymers
- C11D3/3703—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- C11D3/3719—Polyamides or polyimides
Definitions
- the subject of the present invention relates to the use polymeric aminodicarboxylic acids and their sodium salts and precursors in bleaching detergents, bleaching aids and detergents Bleaching liquors for textiles, such as those used in the household and in commerce become.
- the bleaching detergents commonly used today contain essential ones Components builder substances, surfactants and bleach. While the surfactants generally have the task of wetting the textiles to be washed and to remove and disperse greasy soiling the main tasks of the builder in it, the negative effects of Water hardness, which can be seen as incrustations on the tissue, as deposits on the heating elements of the washing machine and in the impairment of the general Express washing performance, prevent. While earlier than builder substances soluble silicates, borates and especially polymeric phosphates have recently been used primarily water-insoluble Zeolites and polymeric polycarboxylic acids or their salts as builder substances used in detergents.
- the common one is particularly common Use of zeolites with co-builders, for example polymeric polycarboxylic acids, which improve the effectiveness of the zeolites.
- Younger Time has been suggested as builder substances or co-builder substances polymeric aminodicarboxylic acids and their salts or also precursors of these polymers, which only in water to the polymeric aminodicarboxylic acids hydrolyze, use in textile detergents.
- builder substances polymeric aminodicarboxylic acids and their salts or also precursors of these polymers, which only in water to the polymeric aminodicarboxylic acids hydrolyze, use in textile detergents.
- the main focus of these substances is at the dispersing effect on pigments (primary washing action) and in the prevention of deposits (secondary washing effect).
- Oxygen bleaches are predominantly used as bleaches in laundry detergents used, primarily inorganic peroxo compounds, like sodium perborate or sodium percarbonate, but are for this purpose also organic peroxo compounds, for example peroxocarboxylic acids been proposed.
- the inorganic peroxo compounds in water Release hydrogen peroxide are often used with activators the effectiveness of hydrogen peroxide at low temperatures increase.
- bleaching detergents and bleaching aids additionally stabilizers for the peroxo compounds. It is primarily about Heavy metal complexing agents such as ethylenediaminetetraacetic acid, ethylenediaminetetramethylenephosphonic acid and other polyphosphonic acids or the salts of these acids.
- Heavy metal complexing agents such as ethylenediaminetetraacetic acid, ethylenediaminetetramethylenephosphonic acid and other polyphosphonic acids or the salts of these acids.
- the use of these complexing agents often requires Compromise on other properties of the detergent, so that for these complexing agents for exchange substances that do
- polyamino acids or their derivatives are used as builders or co-builder used in detergent formulations.
- polyaspartic acid and polyglutamic acid are preferred here polyaspartic acid and polyglutamic acid.
- Such polyamino acids show excellent properties as calcium complexing agent.
- amino acids such as L-aspartic acid and L-glutamic acid, as complexing agents usable for transition metals such as iron, cobalt and nickel.
- WO 96/34908 describes a process for the preparation of polymers with recurring Succinyl units, especially polysuccinimide and polyaspartic acid, described.
- An optionally substituted 1,4-butanedicarboxylic acid, Butenedicarboxylic acid or a derivative thereof with a triammonium salt combined with a polyvalent acid and with heating polymerized.
- Heavy metals can also be used as stabilizers for bleaches in these polymers how hydrogen peroxide serve in bleaching processes.
- This patent application represents a document within the meaning of Article 54 (3) and (4) EPC.
- One of the objects of the present invention was to improve to find the stabilization of the bleach in the textile washing process.
- polymeric aminodicarboxylic acids, their salts or their hydrolysable to polymeric aminodicarboxylic acid Precursors for the stabilization of peroxo compounds in bleaching Textile detergents, bleaches or bleach or wash liquors for textile treatment be used.
- This use is the bleaching Detergents, bleaching aids or alkalis are the polymeric aminodicarboxylic acids or their salts or precursors in amounts of 1% by weight to 10 % By weight, in each case based on the total weight of the composition or the total weight of the active ingredients contained, on polymeric aminodicarboxylic acid or their salts or precursors.
- polymeric aminodicarboxylic acids used according to the invention are it is formally polycondensation products of aminodicarboxylic acids, such as for example aspartic acid and glutamic acid, either alone or together with other polycondensable monomer units, such as aminocarboxylic acids, Hydroxycarboxylic acids, diamines and diols.
- polymeric aminodicarboxylic acids on the functional groups be substituted, for example by alkyl, hydroxyalkyl or Alkoxyalkyl groups.
- those are preferably usable polymeric aminodicarboxylic acids containing at least 50 mol%, in particular at least 80 mol% of optionally substituted Aminodicarboxylic acid units contained in the molecule.
- polymeric aminodicarboxylic acids which as Aminodicarboxylic acid units, aspartic acid groups, if appropriate also may be substituted.
- the soluble Salts of these polymers or precursors of these polymers the only with water to the polymeric aminodicarboxylic acids or their salts hydrolyze, be used.
- Polyaspartic acids are particularly preferred for the use according to the invention, accordingly by polycondensation of D-, L- or D, L-aspartic acid with the addition of acid or by polycondensation of maleic acid monoammonium salt optionally with the addition of acid and in each case subsequent hydrolysis and optionally neutralization of the intermediate formed polysuccinimides are produced.
- the molecular weights of the polymeric aminodicarboxylic acids used according to the invention can fluctuate within wide limits. Polymers are preferred with molecular weights between about 1000 and about 30,000 g / mol, especially those with molecular weights between about 2000 g / mol and about 20,000 g / mol, each based on the acidic forms used. The Molecular weights can be controlled by appropriate control of the polycondensation reaction to adjust.
- the stabilizing effect of the polymeric aminodicarboxylic acids is largely regardless of the composition of the detergent or wash liquor, in which they are used. So the ingredients in the detergents are used, which is also common in these detergents are. On the other hand, the choice of certain ingredients can be beneficial be when there is a synergistic interaction with certain ingredients the detergent results. This synergistic interaction need not be limited to the effect according to the invention.
- the detergents or bleaches or the bases 1% by weight up to 10 wt .-% of these polymers based on the total weight of the finished agent or on the total contained in the finished lye Active ingredients added.
- the amount added to them is Polymers 2% by weight to 7% by weight.
- bleaching agents on which the stabilizing effect of polymeric aminodicarboxylic acids used according to the invention are bleaches that contain active oxygen.
- active oxygen the active Contain oxygen bound in such a way that when these active ingredients dissolve hydrogen peroxide is released in water.
- Most important representative of this Perborates, in particular sodium perborate tetrahydrate, are substance classes and sodium perborate monohydrate, and what is referred to as sodium percarbonate Peroxohydrate of sodium carbonate.
- Other such bleaches are the peroxohydrates of the various phosphates and the peroxohydrate of Urea.
- oxygen bleaches are Peroxohydrates of organic salts, for example sodium citrate peroxohydrate, and to name the peroxycarboxylic acids, especially those solid, largely water-insoluble peroxycarboxylic acids of the type Diperoxy-alpha, omega-alkanedicarboxylic acids and N-substituted omega-aminoalkane peroxycarboxylic acids.
- the polymers are preferred Aminodicarboxylic acids to stabilize sodium perborates or sodium percarbonate used.
- the bleach content in bleaching detergents is preferred between about 5 and about 30% by weight, in particular between about 10 and about 25% by weight.
- pure bleaching agents which are also used as additives in washing liquors the content is usually higher, preferably between about 40 and about 90% by weight.
- the hydrogen peroxide when dissolved in water can release the bleaching detergents, bleaching aids and bleaching wash liquors in which the polymeric aminodicarboxylic acids are used according to the invention, contain so-called bleach activators.
- bleach activators are mainly N-acyl and O-acyl compounds, which in are able to be stronger in the bleach with hydrogen peroxide to react bleaching peroxycarboxylic acids.
- the stabilizing effect the polymers used according to the invention also extend to these peracids so formed, without depending on the use of certain Activators would arrive.
- Suitable activators are in large numbers in the literature and include short chain activators Acyl residues such as tetraacetylethylenediamine, tetraacetylglycoluril and Pentaacetylglucose as well as activators with long chain acyl residues such as Isononanoyloxybenzenesulfonate.
- the activator content is generally like this chosen so that it is sufficient, about 10 to about 50 wt .-% of the released To activate hydrogen peroxide in the wash liquor.
- bleaching detergents and wash liquors in which the use according to the invention takes place as further active ingredients builder substances, Surfactants and, where appropriate, other active ingredients and auxiliaries.
- pure bleaching aids can also contain other substances Bleach and stabilizer included.
- further ingredients are in particular graying inhibitors, foam regulators, optical Brighteners, fabric softening substances, neutral salts, enzymes, fragrances and to mention dyes.
- Other tools, for example for liquid ones Detergents are hydrotropes and organic solvents.
- the fine crystalline is primarily found in detergents synthetic water-containing zeolites, especially the zeolites of types A, X and P, which are capable of calcium and magnesium ions bind by ion exchange and the washing effect of the surfactants support.
- Amorphous aluminosilicates and others are also suitable amorphous or crystalline silicates with exchange capacity.
- polymeric polycarboxylates such as polyacrylates, polymethacrylates and especially copolymers from acrylic acid and maleic acid, preferably those with 50% to 10% maleic acid.
- the molecular weight of the homopolymers is generally between 1,000 and 100,000, that of the copolymers between 2,000 and 200,000, preferably 50,000 to 120,000, based on free acid.
- a particularly preferred acrylic acid-maleic acid copolymer has a molecular weight from 50,000 to 100,000.
- Terpolymers made from acrylic acid, maleic acid and vinyl acetate followed by Saponification are available.
- Suitable, albeit less preferred Compounds of this class are copolymers of acrylic acid or methacrylic acid with vinyl ethers, such as vinyl methyl ether, in which the proportion of the acid is at least 50%.
- Polyacetal carboxylic acids such as for example, they are described in U.S. Patents 4,144,226 and 4,146,495 are, as well as polymeric acids, which by polymerization of Obtain acrolein and subsequent disproportionation using alkalis and from acrylic acid units and vinyl alcohol units or acrol units are built up.
- useful low molecular weight organic builders are the polycarboxylic acids preferably used in the form of their sodium salts, such as citric acid and nitrilotriacetic acid (NTA), if such Use for ecological reasons is not objectionable.
- NTA nitrilotriacetic acid
- phosphates also become used as builder substances, in particular pentasodium triphosphate, optionally also pyrophosphates and ortophosphates, the first Line act as a precipitant for water hardness.
- Suitable inorganic, non-complexing builder salts are the bicarbonates, carbonates, borates or silicates of the alkalis, which are also referred to as "washing alkalis".
- alkali silicates the sodium silicates with a ratio of Na 2 O: SiO 2 such as 1: 1 to 1: 3.5 and the crystalline sodium disilicates with a layer structure are particularly worth mentioning.
- Combinations of sodium carbonate and sodium silicate are often used as builder materials, particularly in detergents which contain little or no phosphate or zeolite, in which case both substances can also be granulated together if necessary.
- the builder content is included bleaching laundry detergents usually between about 10 and about 50 % By weight, in particular between about 15 and about 40% by weight, can, however, in Special cases are also above or below these values and, if necessary, for liquid detergents or bleaching aids, for example absence.
- surfactants customary in washing or cleaning agents also come as surfactants.
- Surfactants i.e. anionic, nonionic, zwitterionic and cationic surfactants.
- anionic and nonionic surfactants and mixtures of surfactants from these two classes are used.
- the type of surfactant and the surfactant content depend primarily depends on the area in which the funds are used.
- Whole bleaching aids in many cases without surfactant the surfactant content in laundry detergents is higher and generally includes nonionic and anionic surfactants.
- the proportion of surfactants is usually based on the total detergent between about 4% by weight and about 30% by weight, in particular between about 6% by weight and about 25% by weight, but also values above and below of these limits are possible.
- Suitable anionic surfactants are, for example, those of the sulfonate and sulfate type.
- the surfactants of the sulfonate type are alkylbenzenesulfonates (C 9 -C 15 -alkyl) and olefin sulfonates, ie mixtures of alkene and hydroxyalkanesulfonates and disulfonates, such as are obtained, for example, from C 12 -C 18 monoolefins with a terminal or internal double bond by sulfonating with gaseous Sulfur trioxide and subsequent alkaline or acidic hydrolysis of the sulfonation products is considered.
- alkanesulfonates which are obtainable from C 12 -C 18 alkanes by sulfochlorination or sulfoxidation and subsequent hydrolysis or neutralization or by bisulfite addition to olefins, and the esters of ⁇ -sulfofatty acids (ester sulfonates), for example the ⁇ -sulfonated methyl esters of hydrogenated coconut, palm kernel or tallow fatty acids, as well as the sulfosuccinic acid esters and the sulfonated glycerol esters of saturated fatty acids.
- Suitable surfactants of the sulfate type are the sulfuric acid monoesters from primary alcohols of natural and synthetic origin, ie from fatty alcohols, for example coconut oil alcohols, tallow fatty alcohols, oleyl alcohol, lauryl, myristyl, palmityl or stearyl alcohol, or the C 10 -C 20 oxo alcohols, and those secondary Alcohols of this chain length.
- the sulfuric acid monoesters of the long-chain primary and secondary alcohols (ether sulfates) ethoxylated with 1 to 6 moles of ethylene oxide are also suitable.
- Sulfated fatty acid monoglycerides are also suitable.
- Soaps made from natural or synthetic, preferably saturated, fatty acids can also be used.
- Soap mixtures derived from natural fatty acids for example coconut, palm kernel or tallow fatty acids, are particularly suitable.
- Preferred are those which are composed of 50 to 100% of saturated C 12 -C 18 fatty acid soaps and 0 to 50% of oleic acid soap.
- the anionic surfactants can be in the form of their sodium, potassium and ammonium salts as well as soluble salts of organic bases, such as mono-, di- or Triethanolamine are present.
- the sodium salts are preferably used.
- the addition products from 1 to are especially suitable as nonionic surfactants 40, preferably 2 to 20 moles of ethylene oxide to 1 mole of a long chain aliphatic compound having essentially 10 to 20 carbon atoms from the group of alcohols, carboxylic acids, fatty amines, carboxamides or alkanesulfonamides for the detergents according to the invention.
- the addition products of 8 to 20 moles of ethylene oxide are particularly important to primary alcohols, e.g. to coconut or tallow fatty alcohols Oleyl alcohol, on oxo alcohols, or on secondary alcohols with 8 to 18, preferably 12 to 18 carbon atoms.
- the corresponding ones can also be used Alkoxylation products that also contain propylene oxide in addition to ethylene oxide contain.
- water-soluble nonionic surfactants In addition to the water-soluble nonionic surfactants, not completely water-soluble polyglycol ethers with 2 to 7 ethylene glycol ether residues of interest in the molecule, especially when they are together used with water-soluble, non-ionic or anionic surfactants become.
- Alkyl glycosides of the general formula RO- (G) x can also be used as nonionic surfactants, in which R is a primary straight-chain or aliphatic radical which is methyl-branched in the 2-position and has 8 to 22, preferably 12 to 18, carbon atoms, and G is a symbol , which stands for a glycose unit with 5 or 6 carbon atoms, and the degree of oligomerization x is between 1 and 10.
- the so-called alkyl glucosides in which G represents a glucose unit are particularly preferred, in particular those in which x has values between 1 and 3.
- Long-chain amine oxides and are also suitable as nonionic surfactants Polyhydroxy fatty acid amides, such as those obtained by reductive amination of monosaccharides with ammonia or lower alkylamines and subsequent acylation are available with fatty acid esters.
- Graying inhibitors are preferably suitable for bleaching detergents Carboxymethyl cellulose, methyl cellulose, methyl hydroxyethyl cellulose and mixtures of these compounds.
- Carboxymethyl cellulose, methyl cellulose, methyl hydroxyethyl cellulose and mixtures of these compounds are usable also polymers of vinyl pyrrolidone and hydrophilic polyamides and polyester.
- Soap with a high content of C 18 -C 24 fatty acids, organopolysiloxanes, paraffins and long-chain amidic compounds are preferably used as foam regulators in bleaching detergents, it being advantageous to use mixtures of different regulators.
- optical brighteners are mostly derivatives of diaminostilbenedisulfonic acid or their alkali metal salts, and substituted 4,4'-distyryl diphenyls.
- Enzymes come from the classes of proteases, lipases, amylases, Cutinases and cellulases and mixtures thereof.
- the enzymes can adsorbed on carriers or embedded in coating substances in order to protect them against premature decomposition. Even the invention Polymers used aminodicarboxylic acids seem to inactivate the Counteract enzymes.
- the polymers used according to the invention are usually already the ready-made bleaching detergents or Bleach added.
- the wash liquors then arise through dissolution the bleaching detergent in the necessary concentration in water or by adding bleaching aids to solutions of bleach-free Detergents in water.
- the washing and bleaching lye by separate dosing of individual Manufacture or refresh components.
- the addition of the polymers used according to the invention separately, either in solid form or in the form of stock solutions.
- the effect of the polymers used according to the invention in the alkali is not to special conditions, such as special temperatures or pH values bound.
- the 4 detergents A to D differ as follows: laundry detergent component A B C. D Maleic acid-acrylic acid copolymer (Sokalan CP5) x x Diethylene triamine pentamethylene phosphonate x Polyaspartic acid (MW 17000) according to J. Org. Chem. 26 , 1084 (1961) x Polyaspartic acid (MW 2500) according to EP 256 366 x
- washing tests themselves were carried out in a Miele washing machine type W 701 in the normal washing program without prewash under the following conditions: Washing temperature 60 ° C Amount of water in the wash cycle 20 liters Water hardness 16 ° d Detergent dosage 105 g / wash loading with white filling laundry 3 kg
- the cleaning ability was on artificially produced soiling tested in the form of appropriate test fabrics with a size about 10 x 10 cm in addition to the white fill fabric in the washing machine were introduced. After the wash was finished, the Test fabric dried, ironed and using a reflectance photometer measured. The results are given in percent light reflectance on barium sulfate as white standard (100%). Show higher values purer tissue. In each case, three parallel experiments were carried out and averaged their results. Tables 3 and 4 show the Average values of the measured remissions for different test tissues. In addition it is stated which smallest difference is still significant the individual test tissues can be viewed (LSD).
- the bleach-stabilizing effect was also investigated by determining the active oxygen content in the wash liquor in the course of the washing process.
- Table 5 shows the mean values of the iodometric titration results after 4, 10 and 30 minutes of washing time in percent, based on the calculated starting content of active oxygen of 100% from the dosage. These values also clearly show the bleach-stabilizing effect of the polymeric aminodicarboxylic acids.
- laundry detergent CU addition Active oxygen levels during the washing process 4 min 10 min 30 min A 5 ppm 84.6 60.5 40.4 B 5 ppm 94.9 86.3 82.2 C. 5 ppm 89.6 80.2 70.4 D 5 ppm 98.8 92.2 89.7
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Description
Beispiel | Inhaltsstoffe | Gehalt in Gramm pro Liter |
1 | NaBO3 x 4H2O | 1,00 |
2 | NaBO3 x 4H2O Maleinsäure - Acrylsäure - Copolymer - Na-Salz | 1,00 0,2225 |
3 | NaBO3 x 4H2O Maleinsäure - Acrylsäure - Copolymer - Na-Salz Diethylentriaminpentamethylenphosphonat | 1,00 0,2225 0,025 |
4 | NaBO3 x 4H2O Polyasparaginsäure (Mol-Gew. 2500) hergestellt gemäß EP 256 366 | 1,00 0,2225 |
5 | NaBO3 x 4H2O Polyasparaginsäure (Mol-Gew. 17000) hergestellt gemäß J. Org. Chem. 26, 1084 (1961) | 1,00 0,2225 |
Aktivsauerstoffgehalte (relativ in %) | |||||
Temperatur | 1 | 2 | 3 | 4 | 5 |
20 °C | 100 | 100 | 100 | 100 | 100 |
30 °C | 99,4 | 99,8 | 100 | 100 | 98,8 |
40 °C | 98,7 | 98,8 | 99,4 | 98,2 | 98,8 |
50 °C | 89,4 | 94,5 | 98,7 | 98,2 | 98,2 |
60 °C | 19,9 | 61,3 | 98,7 | 97,5 | 92,6 |
10 Min. bei 60 °C | 2,5 | 23,9 | 98,1 | 97,5 | 86,5 |
20 Min. bei 60 °C | 1,8 | 8,0 | 96,9 | 97,5 | 83,4 |
30 Min. bei 60 °C | - | 4,3 | 94,4 | 97,5 | 77,3 |
Natriumdodecylbenzolsulfonat | 9 % |
Natrium-Talgfettalkoholsulfat | 4 % |
Kokosalkohol + 5 EO | 4 % |
Talgfettalkohol mit 5 EO | 2 % |
Kokosfettsäurenatriumseife | 1 % |
Zeolith A (wasserfrei gerechnet) | 24 % |
Na2CO3 | 12 % |
Natriumsilikat (Na2O : SiO2 = 3,3) | 3 % |
Natriumperboratmonohydrat | 16 % |
Tetraacetylethylendiamin | 5 % |
Protease polymeres Polycarboxylat oder polymere | 1 % |
Aminodicarbonsäure (Natriumsalze) Diethylentriaminpentamethylenphosphonsäure- | 5,5 % |
Natriumsalz Vergrauungsinhibitor, Entschäumer, optischer Aufheller, Salze aus Rohstoffen | 0 oder 0,4 % |
und Wasser | Rest zu 100 % |
Waschmittel | ||||
Bestandteil | A | B | C | D |
Maleinsäure-Acrylsäure-Copolymerisat (Sokalan CP5) | x | x | ||
Diethylentriaminpentamethylenphosphonat | x | |||
Polyasparaginsäure (MG 17000) gemäß J. Org. Chem. 26, 1084 (1961) | x | |||
Polyasparaginsäure (MG 2500) gemäß EP 256 366 | x |
Waschtemperatur | 60 °C |
Wassermenge im Waschgang | 20 Liter |
Wasserhärte | 16 °d |
Waschmitteldosierung | 105 g/Waschgang |
Beladung | mit weißer Füllwäsche 3 kg |
Waschmittel | Cu-Zusatz | Remissionswerte bei den Testanschmutzungen a - e | ||||
a | b | c | d | e | ||
A | 0 | 68,9 | 74,8 | 63,6 | 76,7 | 62,7 |
A | 5 ppm | 68,2 | 74,1 | 63,3 | 67,8 | 63,8 |
B | 5 ppm | 69,3 | 74,6 | 62,5 | 74,7 | 64,8 |
C | 5 ppm | 68,7 | 72,5 | 63,1 | 70,5 | 62,9 |
D | 5 ppm | 69,7 | 72,9 | 64,7 | 73,9 | 65,0 |
LSD | 0,8 | 1,1 | 1,5 | 2,3 | 1,0 |
Waschmittel | Cu-Zusatz | Remissionswerte bei den Testanschmutzungen f - k | ||||
f | g | h | i | k | ||
A | 0 | 72,1 | 72,5 | 71,3 | 59,9 | 84,1 |
A | 5 ppm | 59,7 | 60,7 | 60,2 | 37,4 | 80,5 |
B | 5 ppm | 72,7 | 70,6 | 70,5 | 54,3 | 84,2 |
C | 5 ppm | 69,0 | 68,6 | 68,9 | 50,8 | 83,0 |
D | 5 ppm | 70,4 | 70,7 | 71,1 | 56,8 | 83,9 |
LSD | 1,4 | 1,2 | 1,0 | 2,0 | 0,4 |
Waschmittel | CU-Zusatz | Aktivsauerstoffgehalte während des Waschvorgangs | ||
4 min | 10 min | 30 min | ||
A | 5 ppm | 84,6 | 60,5 | 40,4 |
B | 5 ppm | 94,9 | 86,3 | 82,2 |
C | 5 ppm | 89,6 | 80,2 | 70,4 |
D | 5 ppm | 98,8 | 92,2 | 89,7 |
Claims (7)
- Verwendung von polymeren Aminodicarbonsäuren oder deren Salzen oder zu polymeren Aminodicarbonsäuren hydrolysierbaren Vorläufern in bleichenden Waschmitteln, Bleichmitteln oder Bleich- oder Waschlaugen für die Textilbehandlung zur Stabilisierung enthaltener Peroxobleichmittel, dadurch gekennzeichnet, daß dem bleichenden Textilwaschmittel, dem Bleichmittel bzw. der Lauge 1 Gew.-% bis 10 Gew.-%, jeweils bezogen auf das Gesamtgewicht des Mittels bzw. des Gesamtgewichts der enthaltenen Wirkstoffe, an polymerer Aminodicarbonsäure oder deren Salzen oder Vorläufern zugesetzt wird.
- Verwendung nach Anspruch 1, dadurch gekennzeichnet, daß es sich bei der polymeren Aminodicarbonsäure oder deren Salz oder Vorläufer um ein Polymeres handelt, das zu einem wesentlichen Teil aus Asparaginsäure- oder Glutaminsäureeinheiten oder deren Vorläufereinheiten besteht.
- Verwendung nach einem der Ansprüche 1 oder 2, dadurch gekennzeichnet, daß das verwendete Polymer zu mehr als 50 Mol %, vorzugsweise zu mehr als 80 Mol % aus Einheiten der Asparaginsäure besteht.
- Verwendung nach Anspruch 3, dadurch gekennzeichnet, daß das verwendete Polymer durch Polykondensation von Asparaginsäure und anschließende Hydrolyse des gebildeten Polysuccinimids sowie gegebenenfalls Neutralisation hergestellt worden ist.
- Verwendung nach Anspruch 3, dadurch gekennzeichnet, daß das verwendete Polymer durch Polykondensation von Maleinsäuremonoammoniumsalz und anschließende Hydrolyse des gebildeten Polysuccinimids sowie gegebenenfalls Neutralisation hergestellt worden ist.
- Verwendung nach einem der Ansprüche 1 bis 5, dadurch gekennzeichnet, daß dem bleichenden Textilwaschmittel, dem Bleichmittel bzw. der Lauge 2 Gew.-% bis 7 Gew.-%, jeweils bezogen auf das Gesamtgewicht des Mittels bzw. des Gesamtgewichts der enthaltenen Wirkstoffe, an polymerer Aminodicarbonsäure oder deren Salzen oder Vorläufern zugesetzt wird.
- Verwendung nach einem der Ansprüche 1 bis 6, dadurch gekennzeichnet, daß es sich bei der stabilisierten Perverbindung um Natriumperborattetrahydrat, Natriumperboratmonohydrat, Natriumpercarbonat, Wasserstoffperoxid oder Gemische dieser Perverbindungen handelt.
Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE19540086 | 1995-10-27 | ||
DE19540086A DE19540086A1 (de) | 1995-10-27 | 1995-10-27 | Verwendung von polymeren Aminodicarbonsäuren in Waschmitteln |
PCT/EP1996/004543 WO1997016518A1 (de) | 1995-10-27 | 1996-10-18 | Verwendung von polymeren aminodicarbonsäuren in waschmitteln |
Publications (2)
Publication Number | Publication Date |
---|---|
EP0859825A1 EP0859825A1 (de) | 1998-08-26 |
EP0859825B1 true EP0859825B1 (de) | 1999-12-29 |
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Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP96934752A Revoked EP0859825B1 (de) | 1995-10-27 | 1996-10-18 | Verwendung von polymeren aminodicarbonsäuren in waschmitteln |
Country Status (5)
Country | Link |
---|---|
EP (1) | EP0859825B1 (de) |
AT (1) | ATE188245T1 (de) |
DE (2) | DE19540086A1 (de) |
ES (1) | ES2142096T3 (de) |
WO (1) | WO1997016518A1 (de) |
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Citations (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO1996034908A1 (de) * | 1995-05-04 | 1996-11-07 | Bayer Aktiengesellschaft | Verfahren zur herstellung von polymeren mit wiederkehrenden succinyleinheiten |
Family Cites Families (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
IT1240684B (it) * | 1990-04-26 | 1993-12-17 | Tecnopart Srl | Poliamminoacidi quali builders per formulazioni detergenti |
EP0561452A1 (de) * | 1992-03-20 | 1993-09-22 | Unilever N.V. | Zusammensetzung für Geschirrspülmaschinen, die Polyaminosäuren als Gerüststoffe enthalten |
DE4232170C2 (de) * | 1992-09-25 | 1999-09-16 | Henkel Kgaa | Schwachalkalische Geschirreinigungsmittel |
DE4305368A1 (de) * | 1993-02-22 | 1994-08-25 | Bayer Ag | Verfahren zur Herstellung von Polyasparaginsäure und ihrer Salze |
IT1263963B (it) * | 1993-02-24 | 1996-09-05 | Enichem Spa | Composizioni per il lavaggio di materiali tessili |
CA2132112A1 (en) * | 1993-09-21 | 1995-03-22 | David Elliott Adler | Acid catalyzed process for preparing amino acid polymers |
DE4342316A1 (de) * | 1993-12-11 | 1995-06-14 | Basf Ag | Verwendung von Polyasparaginsäure in Wasch- und Reinigungsmitteln |
-
1995
- 1995-10-27 DE DE19540086A patent/DE19540086A1/de not_active Withdrawn
-
1996
- 1996-10-18 AT AT96934752T patent/ATE188245T1/de not_active IP Right Cessation
- 1996-10-18 DE DE59604067T patent/DE59604067D1/de not_active Revoked
- 1996-10-18 WO PCT/EP1996/004543 patent/WO1997016518A1/de not_active Application Discontinuation
- 1996-10-18 ES ES96934752T patent/ES2142096T3/es not_active Expired - Lifetime
- 1996-10-18 EP EP96934752A patent/EP0859825B1/de not_active Revoked
Patent Citations (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO1996034908A1 (de) * | 1995-05-04 | 1996-11-07 | Bayer Aktiengesellschaft | Verfahren zur herstellung von polymeren mit wiederkehrenden succinyleinheiten |
Also Published As
Publication number | Publication date |
---|---|
EP0859825A1 (de) | 1998-08-26 |
DE19540086A1 (de) | 1997-04-30 |
ES2142096T3 (es) | 2000-04-01 |
ATE188245T1 (de) | 2000-01-15 |
WO1997016518A1 (de) | 1997-05-09 |
DE59604067D1 (de) | 2000-02-03 |
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