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
  • C11D3/16—Organic compounds
  • C11D3/26—Organic compounds containing nitrogen
  • C11D3/33—Amino carboxylic acids
• • 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
  • C11D3/3947—Liquid compositions
• • 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
  • C11D7/00—Compositions of detergents based essentially on non-surface-active compounds
  • C11D7/22—Organic compounds
  • C11D7/32—Organic compounds containing nitrogen
  • C11D7/3245—Aminoacids
• • 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
  • C11D7/00—Compositions of detergents based essentially on non-surface-active compounds
  • C11D7/22—Organic compounds
  • C11D7/32—Organic compounds containing nitrogen
  • C11D7/3281—Heterocyclic compounds

Definitions

• the invention relates to machine dishwashing detergents Alkalinity, methylglycinediacetic acid (MGDA) or a salt of which contain and which preferably have a reduced content of Have bleach.
• MGDA methylglycinediacetic acid
• US-A 3 673 098 discloses caustic compositions without Bleaching agents based on KOH and nitrilotriacetic acid (NTA) based.
• Fr-A 1 590 416 also discloses caustic compositions without bleach based on alkali hydroxides, Pyrophosphates and NTA based.
• EP-A-530 635 discloses acidic to mildly alkaline Compositions (pH 5-9) that do not contain complexing agents contain and on builders, enzymes and optionally Oxygen bleaching is based.
• DE-A-3 833 047 discloses acidic compositions (pH 2-6) with hydrolases and builders or complexing agents.
• the Examples disclose high NTA or EDTA share (up to 30%). While these compositions can e.g. Eliminate tea residues well, there is milk residue their effect, measured on a scale from 0 to 10, however always under 5.
• biodegradable complexing agents such as ⁇ -alanine diacetic acid ( ⁇ -ADA) and iso-serine diacetic acid (ISDA), in detergents is in the DE-A-3 829 847 and DE-A-4 036 995. If those Publications Application examples for dishwasher detergents contained, it is machine dishwashing detergent, which in about 0.5% aqueous solution has a pH of more than 10.5.
• DE-A-4 319 935 describes the use of MGDA in Dishwasher detergents disclosed without an example specify.
• MGDA methylglycinediacetic acid
• MGDA is supposed to be a better one, especially for blood-soiled laundry Have effect, as phosphonates and with tea soiled Laundry have about the same effect as phosphonates.
• the same publication discloses that MGDA in a dishwashing detergent, similar to NTA, a very good one Deposit inhibition on glass, metal and porcelain shows, whereby a dishwashing detergent is disclosed which in solution provides pH of more than 10.5. It will too suggested MGDA in very strongly alkaline conditions to use for dairy cleaning.
• a dishwashing detergent excellent cleaning performance for dishes have both milk and milk Tea residue is contaminated.
• This task is accomplished by a Dishwasher detergent dissolved, the methylglycinediacetic acid or their salts as complexing agents and is characterized in that it is approximately 0.5% aqueous solution does not exceed a pH of 10.4.
• Milk residues consist of a mixture of denatured proteins (casein), fats, sugars and mineral deposits and consist of around 70% calcium phosphate (Ca 3 (PO 4 ) 2 ).
• Complexing agents therefore have a significant influence on the removal of milk residues because they dissolve calcium phosphates by complexing the calcium ions.
• Tea residues are also based on Ca deposits, that arise when brewing tea with hard water.
• tea residues are usually different Requirements for a dishwasher detergent as Milk residues, which can be seen from the fact that the detergent disclosed in DE-A 3 833 047 in the acidic range (pH 2-6) Tea residues removed satisfactorily, at Milk residues cannot convince.
• the ability (based on the weight of the complexing agent) to complex calcium ions at a certain pH value depends on the stability constant of the calcium complex (pK c ), the acidic character of the complexing agent (pK 3 ) and its molecular weight.
• the theoretical is at pH 10.4 Degree of complexation for calcium phosphates when using NTA at 360 mg / g and when using MGDA at 340 mg / g, and at pH 8 the theoretical values are 510 mg / g for NTA and 490 mg / g for MGDA.
• MGDA was only used in dishwashing detergents used in about 0.5% aqueous solution have a pH of more than 10.4.
• Dishwashing detergents that contain MGDA and one of them 0.5% aqueous solution with a pH of up to 10.4 deliver better both tea residues and milk residues can remove and overall a better washing result have as dishwashing detergent, which instead of MGDA another Contain complexing agents such as the common NTA.
• the sufficient Amount of complexing agent MGDA has the amount of Oxygen bleach can be reduced without changing thereby the flushing performance and in particular the ability Remove milk residues and tea residues, worsened. This surprising finding even opens up the possibility of using a sufficiently large amount of complexing agents completely on the use of To avoid oxygen bleach.
• the dishwashing detergent according to the invention can be liquid or be powdery and also in the form of a single layer or multi-layer tablet. Appropriate Dosage forms and methods of obtaining them are the Known specialist.
• the dishwasher detergents according to the invention preferably contain one or more enzymes such as Amylase, protease, lipase or cellulase. Through the combined application of amylase and protease were the best cleaning results.
• the ones here are particularly suitable for the pH ranges described use effectively; for example, the temperature stable amylase Termamyl (Novo) at pH 7-8 das Optimal of your spectrum of activity.
• the enzymes come in Granulate form or in solution with commercially available Concentrations or activities are used, the Enzyme content is 0.5-6, preferably 1-4% by weight can.
• Suitable builders are homo- and copolymers Polycarboxylic acids and their partially or completely neutralized salts, monomeric polycarboxylic acids and Hydroxycarboxylic acids and their salts, carbonates, bicarbonates, Borates, phosphates, silicates, aluminosilicates and mixtures such substances.
• Preferred salts of the above compounds are the ammonium and / or alkali salts, i.e. the lithium, Sodium, potassium and rubidium salts and particularly preferred the sodium salt used.
• Suitable polycarboxylic acids are.acyclic, alicyclic, heterocyclic and aromatic carboxylic acids, these contain at least two carboxy groups, each through preferably no more than two carbon atoms from each other are separated.
• Polycarboxylates containing two carboxy groups include for example water-soluble salts of succinic acid, Malonic acid, (ethylenedioxy) diacetic acid, maleic acid, Diglycolic acid, tartaric acid, tartronic acid and fumaric acid.
• Polycarboxylates containing three carboxy groups include for example, water-soluble citrates.
• Corresponding is suitable as a hydroxycarboxylic acid, for example Citric acid.
• one of aspartic acid can also be used HOOC-CH (NH 2 ) -CH 2 -COOH derived polymer with monomer units of the formula to be named.
• the homopolymer of is also suitable as the polycarboxylic acid Acrylic acid.
• borate builders can also such builders are used, the borates among the Detergent storage conditions or rinsing conditions release.
• Suitable phosphates are polyphosphates such as tripolyphosphate, Pyrophosphate, orthophosphate and the polymeric metaphosphate.
• polyphosphates such as tripolyphosphate, Pyrophosphate, orthophosphate and the polymeric metaphosphate.
• Suitable silicates are sodium silicates such as sodium disilicate, Sodium metasilicate and crystalline layered silicates. Sodium aluminosilicates are also suitable (Zeolite).
• a builder system from the salt of one is particularly preferred Hydroxycarboxylic acid or from the mixture of one Hydroxycarboxylic acid and the salt of a hydroxycarboxylic acid.
• Both the hydroxycarboxylic acid and the salt of Hydroxycarboxylic acid can be completely or partially Tripolyphosphate can be replaced, although this is not preferred becomes.
• the builder system preferably consists of a Hydroxypolycarboxylic acid with 2-4 carboxyl groups (or acidic inorganic salts), which are used to adjust the pH value with their Salt can be mixed.
• Citric acid is preferred or a mixture of sodium citrate with citric acid used.
• the required pH value is suitable depending on the others Components of the mixture e.g. Mix with one predominant proportion of citric acid.
• the water content of liquid dishwashing detergent can be 40-80 % By weight.
• the liquid dishwashing detergents also contain 0.2-5.0% by weight, preferably 0.5-2% by weight, of a thickener.
• a thickener preferably 0.5-2% by weight
• Carboxyvinyl polymers such as those marketed by BF Goodrich under the production name "Carbopol”, proved to be very useful.
• Inorganic compounds which have thickening properties in this product composition can also be used. Examples of this are natural or synthetic thickeners based on differently structured silicate structures. Their use is described in various patents, for example in US-A-4 933 101 or EP-A2-0 407 187.
• nonionic surfactants are suitable as surfactants. These include, for example, water-soluble ethoxylated C 6-16 fatty alcohols and C 6-16 mixed ethoxylated / propoxylated fatty alcohols and mixtures thereof, and also polyglucosides.
• Another class of non-ionic surfactants includes polyhydroxy fatty acid amides.
• the dishwasher detergent according to the invention can further contain one or more foam control agents. All those used in this area are suitable for this Foam control agents such as silicones and Paraffin oil.
• the foam control agents are in the invention Machine dishwashing detergent preferably with less than 5% by weight of the total weight of the detergent.
• the machine dishwashing detergents according to the invention can be used as Bleaching agents prefer chlorine-free, active oxygen releasing bleaches such as inorganic perhydrates or contain organic peracids and their salts.
• inorganic perhydrates are perborates, Percarbonates and persulfates such as peroxymonopersulfate.
• the inorganic perhydrates are usually alkali metal salts, such as lithium, sodium, potassium or rubidium salts, especially the sodium salts.
• the inorganic perhydrates can in the detergent as crystalline solids without protection. For certain perhydrates however, it is advantageous to use them as granular To use compositions with a coating are provided, the better the granular products Gives storage stability.
• the preferred perborate is sodium perborate, which can be present as a monohydrate with the formula NaBO 2 H 2 O 2 or as a tetrahydrate with the formula NaBO 2 H 2 O 2 .3H 2 O.
• the preferred percarbonate is sodium percarbonate with the formula 2Na 2 CO 3 3H 2 O 2 .
• the percarbonate is preferably used in a coated form to increase its stability.
• Organic peracids all conventionally include bleaching agents used organic peracids, including for example perbenzoic acid and peroxycarboxylic acids such as Mono- or diperoxyphthalic acid, 2-octydiperoxysuccinic acid, Diperoxydodecanedicarboxylic acid, Diperoxyazelaic acid and Imidoperoxycarboxylic acid and optionally its salts.
• perbenzoic acid and peroxycarboxylic acids such as Mono- or diperoxyphthalic acid, 2-octydiperoxysuccinic acid, Diperoxydodecanedicarboxylic acid, Diperoxyazelaic acid and Imidoperoxycarboxylic acid and optionally its salts.
• the dishwasher detergent according to the invention can continue to contain one or more bleach activators. These are preferred in detergents for dishwashing operations at temperatures below 60 ° C used to achieve a sufficient bleaching effect.
• N- and O-acyl compounds are particularly suitable such as acylated amines, acylated glycolurils or acylated sugar compounds.
• TAED N, N ', N'-tetraacetylethylenediamine
• PAG pentaacetylglucose
• TAGU tetraacetylglycoluril
• Dishwasher detergent is an oxygen bleach an amount of less than 1% by weight, based on the active Oxygen on. The amount of bleach activator used will be adjusted accordingly.
• the machine dishwashing detergent s a large percentage of MGDA, like 25% or more, preferably 30% or more, in each case based on the free acid, and an oxygen bleach is not used.
• the dishwasher detergent according to the invention can also contain a silver / copper anti-corrosion agent.
• This term includes funds that start up Non-ferrous metals, especially silver and copper, prevent or mitigate.
• Preferred silver / copper anti-corrosion agents are benzotriazole or bis-benzotriazoles as well as their substituted derivatives.
• Suitable agents are organic and / or inorganic redox-active substances and paraffin oil.
• Benzotriazole derivatives are those compounds in which the available substitution sites of the aromatic ring are partially or completely substituted.
• Linear or branched chain C 1-20 alkyl groups as well as hydroxy, thio, phenyl or halogen such as fluorine, chlorine, bromine and iodine are suitable as substituents.
• Preferred substituted benzotriazole is tolyltriazole.
• Suitable bis-benzotriazoles are those in which the benzotriazole groups are each connected in the 6-position by a group X, in which X is a bond, a straight-chain alkylene group which is optionally substituted by one or more C 1-4 alkyl groups and preferably has 1-6 carbon atoms , a cycloalkyl radical having at least 5 carbon atoms, a carbonyl group, a sulfuryl group, an oxygen or a sulfur atom.
• the aromatic rings of the bis-benzotriazoles can be substituted as defined above for the benzotriazole.
• Suitable organic redox-active substances are, for example, ascorbic acid, indole, methionine, an N-mono- (C 1 -C 4 alkyl) glycine, an N, N-di (C 1 -C 4 alkyl) glycine, 2- phenylglycine or a coupler and / or developer compound chosen from the group of diaminopyridines, aminohydroxypyridines, dihydroxypyridines, heterocyclic hydrazones, aminohydroxypyrimidines, dihydroxypyrimidines, tetraaminopyrimidines, triaminohydroxypyrimidines, Diaminodihydroxypyrimidine, Dihydroxynaphtaline, naphthols, pyrazolones, hydroxyquinolines, aminoquinolines, primary aromatic amines, which in ortho, meta or para position have a further free or with C 1 -C 4 alkyl or C 2 -C 4 hydroxyalkyl groups substituted hydroxy or amino
• Suitable inorganic redox-active substances are for example, metal salts and / or metal complexes selected from the group of manganese, titanium, zirconium, hafnium, Vanadium, cobalt and cerium salts and / or complexes, wherein the metals in one of the oxidation states II, III, IV, V or VI are available.
• Organic and inorganic redox-active substances which as Silver / copper anti-corrosion agents are suitable also mentioned in WO 94/26860 and WO 94/26859, on the Content hereby referred.
• Suitable paraffin oil are predominantly branched aliphatic hydrocarbons with a number of carbon atoms in the range from 20 to 50.
• the paraffin oil is preferably selected from predominantly branched chain C 25-45 species with a ratio of cyclic to noncyclic hydrocarbons of 1:10 to 2: 1 , preferably from 1: 5 to 1: 1.
• a silver / copper anticorrosive in the machine dishwashing detergent according to the invention is present, it is preferably 0.01 to 5% by weight, particularly preferably with 0.1 to 2 wt .-% of the total weight.
• the proportion of MGDA on the dishwasher detergent is high enough, such as 25% or more, preferably 30% or more, each based on is the free acid, so that there is no bleaching agent can also be used on a silver / copper anti-corrosion agent to be dispensed with.
• the machine dishwashing detergents according to the invention are not caustic and therefore do not require a specially secured one Packaging. A good washing result can be achieved with one relatively low use of 15-20 g powder or 20-50 ml of liquid detergent can be achieved. All ingredients are according to current knowledge, neither toxic nor otherwise harmful to health.
• the cleaning agents described here therefore also represent an environmentally and consumer-friendly Alternative to conventional cleaners with Complexing agents in the strongly basic area work.
• the methylglycinediacetic acid used according to the invention has the following structural formula:
• Methylglycinediacetic acid is particularly preferred as free acid or used as sodium or potassium salt and is preferably in an amount of 3% to 90%, based on the free acid, contained in the detergent.
• the amount of MGDA is preferably at least 5%, based on the free acid.
• an approximately 0.5% aqueous solution of the detergent has a pH of no more than 10.4.
• the pH is preferably about 0.5% aqueous solution of the detergent according to the invention more than 6 to 10.4, particularly preferably from 7 to 10.0.
• MGDA is not commercially available in its pure form and therefore a 77% solution in water was used. A larger amount of the commercially available product had to be used, as shown in the table. Two values are given in the table for MGDA. The first value indicates the amount in g of the commercial product, and the second value corresponds to the corresponding amount of pure substance (100%). S ⁇ FW Journal 122, 1996, 392-397 Ex. 1 Ex. 2 Quantities in g. (%) Ex.
• the following example shows that when replacing part of the builder of a dishwasher detergent with methylglycinediacetic acid at low pH values excellent washing performance can be achieved and especially contrary to theoretical expectations Ability to remove milk residues and tea residues higher than other common complexing agents such as NTA.
• the example illustrates the invention.
• Liquid dishwashing detergents with a Composition as shown in Table 1 is made (both according to the invention using MGDA and using the NTA used in the prior art), and their washing performance was measured using dishes that both Contained milk and tea residues, determined. In this Test was essentially the DIN standard No. 44990, part 2 followed. It became a Bosch SMS 5062 dishwasher used. The water had a hardness of 19 ° dH (3.39 mmol Calcium carbonate), the temperature of the water was 65 ° C and 20 ml of detergent were used in each case. The results The flushing performance was assessed on a scale of 1-5 (5 for 100% clean dishes are rated) and are also listed in Table 1.
• the non-ionic surfactant is a common, low-foaming ethoxylated and propoxylated fatty alcohol. Common proteases and amylases are used.

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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)

Applications Claiming Priority (3)

Related Parent Applications (1)

Publications (3)

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• 1997
  • 1997-06-20 DE DE59704543T patent/DE59704543D1/de not_active Expired - Fee Related
  • 1997-06-20 DE DE59712930T patent/DE59712930D1/de not_active Expired - Lifetime
  • 1997-06-20 ES ES97928266T patent/ES2160355T3/es not_active Expired - Lifetime
  • 1997-06-20 AT AT01105118T patent/ATE389709T1/de not_active IP Right Cessation
  • 1997-06-20 EP EP97928266A patent/EP0906407B1/fr not_active Revoked
  • 1997-06-20 AT AT97928266T patent/ATE205250T1/de not_active IP Right Cessation
  • 1997-06-20 EP EP01105118A patent/EP1113070B1/fr not_active Revoked
  • 1997-06-20 CA CA002258218A patent/CA2258218A1/fr not_active Abandoned
  • 1997-06-20 ES ES01105118T patent/ES2300287T3/es not_active Expired - Lifetime
  • 1997-06-20 WO PCT/EP1997/003256 patent/WO1997049792A1/fr not_active Ceased

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