EP0859825A1 - Verwendung von polymeren aminodicarbonsäuren in waschmitteln - Google Patents
Verwendung von polymeren aminodicarbonsäuren in waschmittelnInfo
- Publication number
- EP0859825A1 EP0859825A1 EP96934752A EP96934752A EP0859825A1 EP 0859825 A1 EP0859825 A1 EP 0859825A1 EP 96934752 A EP96934752 A EP 96934752A EP 96934752 A EP96934752 A EP 96934752A EP 0859825 A1 EP0859825 A1 EP 0859825A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- bleaching
- acid
- detergents
- acids
- use according
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/39—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 matter of the present invention relates to the use of polymeric aminodicarboxylic acids and of their sodium salts and precursors in bleaching textile detergents, bleaching aids and washing and bleaching liquors for textiles such as are used in the household and in commerce.
- the bleaching detergents that are common today contain as essential components builder substances, surfactants and bleaching agents. While the tenides generally have the task of wetting the textiles to be washed and of removing and dispersing greasy soiling, the main tasks of the builder substances are the negative effects of the water hardness, which can be found on the fabric as incrustations, as deposits on the heating elements of the washing machine and in the impairment of the general washing performance. While soluble silicates, borates and, above all, polymeric phosphates were previously used as builder substances, more recently water-insoluble zeolites and polymeric polycarboxylic acids or their salts have been used primarily as builder substances in detergents.
- Oxygen bleaches are primarily used as bleaching agents in textile detergents, primarily inorganic peroxo compounds, such as sodium perborate or sodium percarbonate, but organic peroxo compounds, for example peroxocarboxylic acids, have also been proposed for this purpose.
- the inorganic peroxo compounds which release hydrogen peroxide in water are often used together with activators which increase the effectiveness of the hydrogen peroxide at low temperatures.
- bleaching detergents and bleaching aids additionally contain stabilizers for the peroxo compounds.
- One of the objects of the present invention was to find improvements in the stabilization of the bleaching agents in the textile washing process.
- polymeric aminodicarboxylic acids, their salts or their hydrolyzable precursors for the polymeric aminodicarboxylic acid are used to stabilize peroxo compounds in bleaching textile detergents, bleaching agents or bleaching or washing liquors for textile treatment.
- This use consists in adding to the bleaching detergents, the bleaching aids or the lye the polymeric aminodicarboxylic acids or their salts or precursors in an amount sufficient for the purpose of stabilizing the peroxo compound for stabilization.
- the advantage of the new use is that the use of the peroxide stabilizers customary hitherto can be largely or completely dispensed with, so that the disadvantages associated with these compounds are avoided.
- the polymer Aminodicarboxylic acids can even achieve a higher stabilization than with known stabilizers.
- polymeric aminodicarboxylic acids used according to the invention are 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, for example, aminocarboxylic acids, hydroxycarboxylic acids, diamines and diols.
- polymeric aminodicarboxylic acids can be substituted on the functional groups, for example by alkyl, hydroxyalkyl or alkoxyalkyl groups.
- polymeric aminodicarboxylic acids which contain at least 50 mol%, in particular at least 80 mol%, of optionally substituted aminodicarboxylic acid units in the molecule are preferably usable according to the invention.
- the soluble salts of these polymers or precursors of these polymers which only hydrolyze with water to give the polymeric aminodicarboxylic acids or their salts, can be used.
- polyasparic acids which, accordingly, by polycondensation of D-, L- or D, L-aspartic acid with the addition of acid or by polycondensation of maleic acid monoammonium salt, if appropriate with the addition of acid and in each case subsequent hydrolysis and optionally neutralization of the in ⁇ formed polysuccinimide.
- the monomer units can be present in the polyaspartic acid or salts thereof in the form of the ⁇ or ⁇ form, the following basic structure resulting with a different tx / ⁇ ratio, if appropriate:
- the molecular weights of the polymeric aminodicarboxylic acids used according to the invention can vary within wide limits. Polymers with molecular weights between approximately 1000 and approximately 30,000 g / mol, in particular those with molecular weights between approximately 2000 g / mol and approximately 20,000 g / mol, in each case based on the acidic forms, are preferably used. The molecular weights can be adjusted by appropriately managing the polycondensation reaction.
- the stabilizing effect of the polymeric aminodicarboxylic acids is largely independent of the composition of the detergents or wash liquors in which they are used. In the detergents it is thus possible to use the ingredients which are otherwise customary in these detergents. On the other hand, the choice of certain ingredients can be advantageous if there is a synergistic interaction with certain ingredients of the detergents. This synergistic interaction need not be limited to the effect according to the invention.
- the detergents or bleaches or the bases are preferably about 1% by weight to about 10% by weight of these polymers based on the total weight of the finished composition or on the active ingredients contained in the finished base added.
- the amount of these polymers added is 2% by weight to 7% by weight.
- the bleaching agents to which the stabilizing action of the polymeric aminodicarboxylic acids used according to the invention relates, are bleaching agents which contain active oxygen. Particular importance is attached to the inorganic bleaching agents which contain the active oxygen in such a way that hydrogen peroxide is released when these active ingredients are dissolved in water.
- the most important representatives of this class of substances are the perborates, in particular sodium perborate tetrahydrate and sodium perborate monohydrate, and the peroxohydrate of sodium carbonate known as sodium percarbonate.
- Other such bleaching agents are the peroxohydrates of the various phosphates and the peroxohydrate of urea.
- oxygen bleaching agents are peroxohydrates of organic salts, for example sodium citrate peroxohydrate, and the peroxycarboxylic acids, in particular the solid, largely water-insoluble peroxycarboxylic acids of the diperoxy-alpha, omega-alkanedicarboxylic acids and N-substituted omega-aminoalkane peroxycarboxylic acids.
- the polymers are preferred Aminodicarboxylic acids are used to stabilize sodium perborates or sodium percarbonate.
- the bleach content in bleaching detergents is preferably between about 5 and about 30% by weight, in particular between about 10 and about 25% by weight.
- the content is usually higher, preferably between about 40 and about 90% by weight.
- the bleaching detergents, bleaching aids and bleaching wash liquors in which the polymeric aminodicarboxylic acids are used according to the invention can contain so-called bleach activators.
- the stabilizing effect of the polymers used according to the invention also extends to the peracids formed in this way, without the need to use certain activators.
- Suitable activators have been described in large numbers in the literature and include activators with short-chain acyl radicals such as tetraacetylethylenediamine, tetraacetylglycoluril and pentaacetylglucose as well as activators with long-chain acyl radicals such as isononanoyloxybenzenesulfonate.
- the activator content is generally chosen so that it is sufficient to activate about 10 to about 50% by weight of the hydrogen peroxide released in the wash liquor.
- Bleaching detergents and wash liquors in which the use according to the invention takes place usually contain builder substances, surfactants and, if appropriate, further active substances and auxiliaries as further active substances.
- pure bleaching aids can also contain substances other than the bleaching agent and the stabilizer.
- Other ingredients include, in particular, graying inhibitors, foam regulators, optical brighteners, fabric softening substances, neutral salts, enzymes, fragrances and to mention dyes.
- Further auxiliaries, for example for liquid detergents are hydrotropes and organic solvents.
- Builder substances also referred to as builder substances, mean today in the narrower sense weakly acidic, neutral or alkaline-reacting soluble and / or insoluble compounds which have the property of precipitating or complexing calcium and possibly magnesium ions. As in the case of surfactants, preference is given to the ecologically harmless compounds.
- the fine crystalline synthetic water-containing zeolites in particular the zeolites of types A, X and P, which are able to bind calcium and magnesium ions by ion exchange and the washing action of, are primarily found in detergents Support surfactants.
- Amorphous aluminosilicates and other amorphous or crystalline silicates with exchange capacity are also suitable.
- Further builder constituents which can be used in particular together with the zeolites are (co) polymeric polycarboxylates, such as polyacrylates, polymethacrylates and in particular copolymers of 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 of 50,000 to 100,000.
- Terpolymers which are obtainable from acrylic acid, maleic acid and vinyl acetate with subsequent saponification are also particularly preferred.
- 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 acid is at least 50%.
- vinyl ethers such as vinyl methyl ether
- polyacetal carboxylic acids as described, for example, in US Pat. Nos. 4,144,226 and 4,146,495, and polymeric acids, which are obtained by polymerizing Acrolein and subsequent disproportionation can be obtained using alkalis and are composed of acrylic acid units and vinyl alcohol units or acrol units.
- Usable low molecular weight organic builders are, for example, the polycarbonates preferably used in the form of their sodium salts, such as citric acid and nitrilotriacetic acid (NTA), provided that such use is not objectionable for ecological reasons.
- NTA nitrilotriacetic acid
- phosphates are also used as builder substances, in particular pentasodium triphosphate, optionally also pyrophosphates and ortophosphates, which act primarily as precipitants 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".
- the alkali silicates the sodium silicates with a ratio of Na 2 O: Si O 2 such as 1: 1 to 1: 3.5 and the crystalline sodium disilicates with a layer structure are particularly worth mentioning.
- detergents which contain little or no phosphate or zeolite combinations of sodium carbonate and sodium silicate are often used as builder materials, in which case both substances can then also be granulated together if necessary.
- the polymeric aminodicarboxylic acids active according to the invention also have a builder or cobuilder effect in addition to their peroxide-stabilizing action, some of the builder substances which are otherwise necessary in the detergents can also be omitted.
- the content of builder substances in bleaching laundry detergents is usually between about 10 and about 50% by weight, in particular between about 15 and about 40% by weight, but in special cases can also be above or below these values and, if appropriate, for example in the case of liquid detergents or bleaching aids, are completely absent. All surfactants customary in washing or cleaning agents are also suitable as surfactants, ie anionic, nonionic, zwitterionic and cationic surfactants.
- anionic and nonionic surfactants and mixtures of surfactants from these two classes are preferably used.
- the type of surfactant and the surfactant content primarily depend on the area in which the agents are used. While bleaching aids often do without any surfactant, the surfactant content in laundry detergents is higher and generally includes nonionic and anionic surfactants. With regard to the total detergent, the proportion of surfactants is usually between about 4% by weight and about 30% by weight, in particular between about 6% by weight and about 25% by weight, but values also above and are possible below these limits.
- Suitable anionic surfactants are, for example, those of the sulfonate and sulfate type.
- alkanesulfonates which are obtainable from C12-Ci8-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 ⁇ c-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 Cjo-C2 ⁇ -oxoalko - get, and those secondary alcohols of this chain length. Also the sulfuric acid monoesters of those ethoxylated with 1 to 6 moles of ethylene oxide Long-chain primary and secondary alcohols (ether sulfates) are suitable. Sulfated fatty acid monoglycerides are also suitable.
- Soaps from natural or synthetic preferably saturated fatty acids can be used.
- natural fatty acids e.g. Soap mixtures derived from coconut, palm kernel or tallow fatty acids.
- Preferred are those which are composed of 50 to 100% saturated Ci2-Cj8 fatty acid soaps and 0 to 50% oleic acid soap.
- the anionic surfactants can be in the form of their sodium, potassium and ammonium salts and also as soluble salts of organic bases, such as mono-, di- or triethanolamine.
- the sodium salts are preferably used.
- the nonionic surfactants are, above all, the adducts of 1 to 40, preferably 2 to 20, moles of ethylene oxide with 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 useful.
- the corresponding alkoxylation products which also contain propylene oxide in addition to ethylene oxide can also be used.
- non-or not completely water-soluble polyglycol ethers with 2 to 7 ethylene glycol ether residues in the molecule are also of interest, in particular if they are used together with water-soluble, nonionic or anionic surfactants.
- R is a primary straight-chain or in the 2-position methyl-branched aliphatic radical having 8 to 22, preferably 12 to 18 carbon atoms
- G is a symbol which represents a glycose unit with 5 or 6 carbon atoms
- the degree of oligomerization x is between 1 and 10 lies.
- 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.
- nonionic surfactants are long-chain amine oxides and polyhydroxy fatty acid amides, as can be obtained by reductive amination of monosaccharides with ammonia or lower alkylamines and subsequent acylation with fatty acid esters.
- Suitable graying inhibitors for bleaching detergents are preferably carboxymethyl cellulose, methyl cellulose, methyl hydroxyethyl cellulose and mixtures of these compounds.
- polymers of vinylpyrrolidone and hydrophilic polyamides and polyesters can also be used.
- foam regulators in bleaching detergents soaps are preferably with a high proportion of C24 CI8 _ ⁇ F et tklaren used organopolysiloxanes, paraffins and long-chain amide compounds, it is vor ⁇ geous to use mixtures of various regulators.
- optical brighteners are mostly derivatives of diaminostilbenedisulfonic acid or its alkali metal salts, and also substituted 4,4'-distyryl-diphenyls.
- Enzymes from the classes of proteases, lipases, amylases, cutinases and cellulases and mixtures thereof can be considered.
- the enzymes can be adsorbed on carriers or embedded in Hü11 substances to protect them against premature decomposition.
- the polymers aminodicarboxylic acids used according to the invention also seem to counteract the inactivation of the enzymes. Since the stabilizing effect of the polymeric aminodicarboxylic acids used according to the invention develops both in solid and in liquid, bleaching detergents or bleaches and also in the alkalis intended for use on the textile, the polymers are usually already the pre-assembled bleaching detergents or bleach added.
- wash liquors are then formed by dissolving the bleaching detergent in the required concentration in water or by adding bleaching aids to solutions of bleach-free detergents in water.
- bleaching aids to solutions of bleach-free detergents in water.
- the polymers used according to the invention can also be added 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 bound to special conditions, such as special temperatures or pH values.
- polymeric aminodicarboxylic acids were used alone or together with aminophosphonic acids as heavy metal complexing agents.
- the cleaning ability was determined on the basis of the light emission of the washed fabrics and the peroxide-stabilizing effect was determined on the basis of the analytically determined peroxide contents of the wash liquor.
- the detergents used had the following composition (in percent by weight): Sodium dodecy1benzo1su1fonate 9%
- Graying inhibitor defoamer, optical brightener, salts from raw materials and water remainder to 100
- the 4 detergents A to D differ as follows:
- Washing temperature 60 ° C
- Water hardness 16 ° d
- Detergent dosage 105 g / wash cycle
- Load with a 3 kg white wash
- the cleaning ability was tested on artificially produced standard soils which were introduced into the washing machine in the form of corresponding test fabrics with a size of approximately 10 ⁇ 10 cm in addition to the white filler fabric.
- the test fabrics were dried, ironed and measured using a reflectance photometer. The results are output in percent light remission, based on barium sulfate as the white standard (100%). Show higher values purer tissue. In each case, three parallel tests were carried out and the results averaged. Tables 3 and 4 show the mean values of the measured remissions for various test tissues. In addition, it is indicated which smallest difference can still be considered significant for the individual test tissues (LSD).
- test fabrics were used: a) dust / wool fat on cotton b) dust / skin fat on finished cotton c) dust / skin fat on polyester-cotton blend d) milk / cocoa on cotton e) mascara on polyester-cotton blend f) red wine on cotton g) wild berries on polyester-cotton blend h) currant on polyester-cotton blend i) tea on refined cotton k) coffee on refined cotton
- 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 titratation results after 4, 10 and 30 minutes of washing time in percent, based on the starting content of active acid, calculated from the dosage. 100%. These values also clearly show the bleach-stabilizing effect of the polymeric aminodicarboxylic acids.
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- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Wood Science & Technology (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Detergent Compositions (AREA)
- Polyamides (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Description
Claims
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 true EP0859825A1 (de) | 1998-08-26 |
EP0859825B1 EP0859825B1 (de) | 1999-12-29 |
Family
ID=7775976
Family Applications (1)
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) |
Families Citing this family (66)
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EP4331564A1 (de) | 2022-08-29 | 2024-03-06 | Analyticon Discovery GmbH | Antioxidative zusammensetzung |
WO2024051922A1 (en) | 2022-09-06 | 2024-03-14 | Symrise Ag | A fragrance mixture (iii) |
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Family Cites Families (8)
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 |
DE19516399A1 (de) * | 1995-05-04 | 1996-11-07 | Bayer Ag | Verfahren zur Herstellung von Polymeren mit wiederkehrenden Succinyleinheiten |
-
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 WO PCT/EP1996/004543 patent/WO1997016518A1/de not_active Application Discontinuation
- 1996-10-18 EP EP96934752A patent/EP0859825B1/de not_active Revoked
- 1996-10-18 DE DE59604067T patent/DE59604067D1/de not_active Revoked
- 1996-10-18 ES ES96934752T patent/ES2142096T3/es not_active Expired - Lifetime
Non-Patent Citations (1)
Title |
---|
See references of WO9716518A1 * |
Also Published As
Publication number | Publication date |
---|---|
DE19540086A1 (de) | 1997-04-30 |
ES2142096T3 (es) | 2000-04-01 |
DE59604067D1 (de) | 2000-02-03 |
EP0859825B1 (de) | 1999-12-29 |
WO1997016518A1 (de) | 1997-05-09 |
ATE188245T1 (de) | 2000-01-15 |
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