EP0854183A1 - Maschinengeschirrspülmittel mit Silberschutz - Google Patents
Maschinengeschirrspülmittel mit Silberschutz Download PDFInfo
- Publication number
- EP0854183A1 EP0854183A1 EP98100112A EP98100112A EP0854183A1 EP 0854183 A1 EP0854183 A1 EP 0854183A1 EP 98100112 A EP98100112 A EP 98100112A EP 98100112 A EP98100112 A EP 98100112A EP 0854183 A1 EP0854183 A1 EP 0854183A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- alkyl
- amino
- triazoles
- acid
- mixtures
- 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.)
- Ceased
Links
- 0 *c1nc(N)n[n]1 Chemical compound *c1nc(N)n[n]1 0.000 description 1
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
- C11D3/0005—Other compounding ingredients characterised by their effect
- C11D3/0073—Anticorrosion 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
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/16—Organic compounds
- C11D3/26—Organic compounds containing nitrogen
- C11D3/28—Heterocyclic compounds containing nitrogen in the ring
Definitions
- the invention relates to the use of 3-amino-5-alkyl-1,2,4-triazoles as Silver protection agents in dishwasher detergents and dishwashing detergents, the 3-amino-5-alkyl-1,2,4-triazoles included as a silver preservative.
- So redox-active inorganic and organic substances are considered Silver preservatives described as additives to the wash liquor, substances that lay as a protective layer on the silver surface and special Bleaching systems that attack the silver surface to a lesser extent.
- WO -A- 95/10588 describes 1,3-N-azoles, preferably imidazole, benzimidazole, Tetrazole, 5-aminotetrazole, 1,2,4-triazole, 3-amino-1,2,4, -triazole and histidine as Silver preservatives described in amounts between 0.05 and 10 wt .-% in low alkaline agents for automatic dishwashing are said to be effective.
- the object of the present invention is to provide a Silver protective agent for automatic dishwashing that is used the usual usage properties for cleaning agents, such as Cleaning performance, adequate foaming power, easy handling and the same leaves unaffected or has improved and and is effective even in small amounts.
- the present invention thus relates to the use of 3-amino-5-alkyl-1,2,4-triazoles as a silver protection agent in dishwasher detergents.
- Another object of the invention is a dishwashing detergent that at least a builder, at least one bleaching compound and at least one Compound selected from the group of 3-amino-5-alkyl-1,2,4-triazoles and contains their mixtures.
- the invention further relates to processes for cleaning Tableware, which are characterized in that one for the protection of silver or silverware dishes 3-amino-5-alkyl-1,2,4-triazoles and / or their Mixtures used.
- Such procedures include, for example, manual or machine Application of 3-amino-5-alkyl-1,2,4-triazoles or their mixtures or such 3-amino-5-alkyl-1,2,4-triazoles or mixtures thereof Preparations in the form of pastes, dusts, melts, oils, films, Solutions, aerosols, lyosols, vapors or foams before, during or after the cleaning process.
- the 3-amino-5-alkyl-1,2,4-triazoles or their salts of the general formula (I) are particularly preferred for achieving the objects according to the invention.
- 3-amino-5-alkyl-1,2,4-triazoles to be used according to the invention can those of the above Registration can be called .: 5, - -Propyl-, -Butyl-, -Pentyl-, -Heptyl-, -Octyl-, -Nonyl-, -Decyl-, -Undecyl-, -Dodecyl-, -Isononyl-, -Versatic-10-acid alkyl-, -Phenyl-, -p-tolyl-, - (4-tert.butylphenyl) -, - (4-methoxyphenyl) -, - (2-, -3-, -4-pyridyl) -, - (2-thienyl) -, - (5-methyl-2-furyl) -, - (5-oxo-2-pyrrolidinyl) -,
- Preferred acids for salt formation are hydrochloric acid, sulfuric acid, Phosphoric acid, carbonic acid, sulphurous acid, organic carboxylic acids such as Acetic, glycolic, citric, succinic acid.
- alkylamino-1,2,4-triazoles or their physiologically acceptable salts in a concentration of 0.001 to 10% by weight, preferably 0.0025 to 2% by weight, particularly preferably 0.01 to 0.04% by weight used.
- Water-soluble and water-insoluble builders especially for binding calcium and magnesium be used.
- Water-soluble builders are preferred because they are based on Dishes and hard surfaces tend to be less insoluble To form residues.
- Usual builders preferred within the scope of the invention between 5 and 90% by weight and particularly preferably between 10 and 85% by weight based on the total preparation, they are low molecular weight polycarboxylic acids and their salts, the homopolymers and copolymeric polycarboxylic acids and their salts, the carbonates, phosphates and Sodium and potassium silicates.
- Water-insoluble builders include zeolites, which can also be used, as well as mixtures of the aforementioned builder substances.
- For the cleaning agents according to the invention are preferred trisodium citrate and / or pentasodium tripolyphosphate and silicate builders from the class of alkali disilicates used.
- Oxygen-containing bleaching compounds which are preferred in the Agents according to the invention preferably to 1 to 35 wt .-% and particularly are preferably contained in 5 to 35 wt .-%.
- Oxygen-containing bleaching compounds are the alkali metal perborates and their hydrates and Alkali metal percarbonates, preferred in the context of the invention Sodium perborate, used as mono or tetrahydrate, or sodium percarbonate Find.
- Typical organic bleaching agents are the diacyl peroxides, e.g. Dibenzoyl peroxide.
- Other typical organic bleaches are Peroxyacids, examples being especially the alkylperoxyacids and Arylperoxyacids are called.
- Preferred representatives are (a) the Peroxybenzoic acid and its ring-substituted derivatives, such as alkylperoxybenzoic acids, but also peroxy- ⁇ -naphthoic acid and magnesium monoperphthalate, (b) the aliphatic or substituted aliphatic peroxy acids such as Peroxylauric acid, peroxystearic acid, ⁇ -phthalimidoperoxycaproic acid, o-carboxybenzamidoperoxycaproic acid, N-nonenylamidoperadipic acid and N-nonenylamidopersuccinate, and (c) aliphatic and araliphatic peroxydicarboxylic acids, such as 1,12-diperoxycarboxylic acid, 1,9-diperoxyazelaic acid, Diperocysebacic acid, diperoxybrassylic acid, the diperoxyphthalic acids, 2-decyldiperoxybutane-1,4-diacid, N, N-ter
- Bleach activators can be used in the cleaning agents used according to the invention be present.
- Known bleach activators are compounds that contain one or more N- or O-acyl groups, such as substances from the Class of anhydrides, esters, imides and acylated imidazoles or Oximes. Examples are tetraacetylethylene diamine (TAED), tetraacetyl methylene diamine (TAMD) and tetraacetylhexylenediamine (TAHD), but also pentaacetylglucose (PAG), 1,5-diacetyl-2,2-dioxo-hexahydro-1,3,5-triazine (DADHT) and Isatoic anhydride (ISA).
- TAED tetraacetylethylene diamine
- TAMD tetraacetyl methylene diamine
- TAHD tetraacetylhexylenediamine
- PAG pentaacet
- Enzymes based on the entire preparation are added to the To increase the performance of the cleaning agents or under milder conditions To ensure cleaning performance of the same quality.
- the most common Enzymes used include lipases, amylases, cellulases and proteases.
- Preferred proteases are e.g. B. BLAP®140 from Biozym, Optimase®-M-440 and Opticlean®-M-250 from Solvay Enzymes; Maxacal®CX and Maxapem® or Esperase® from Gist Brocades or Savinase® from Novo. Celluzym® 0.7 T and.
- Lipolase® 30 T from Novo Nordisk. Special use as amylases find Termamyl® 60 T, and Termamyl® 90 T from Novo, Amylase-LT® from Solvay Enzymes or Maxamyl® P5000 from Gist Brocades and Purafect OxAm4000G® from Genencor but also other enzymes can be used will.
- Alkali carriers in amounts of up to 60% by weight, preferably 10-40% by weight.
- Alkali metal hydroxides are considered to be alkali carriers, Alkali metal carbonates, alkali metal bicarbonates, alkali metal sesquicarbonates, Alkali silicates, alkali metasilicates, and mixtures of the the aforementioned substances, in the context of this invention preferably the alkali metal carbonates, in particular sodium carbonate, sodium hydrogen carbonate or Sodium sesquicarbonate can be used.
- Dishwashing agents according to the invention can be used to protect the items to be washed or the machine also contain other corrosion inhibitors, whereby also Silver protection agents such as z. B. in DE 43 25 922, DE 41 28 672 or DE 43 38 724 can be used.
- Silver protection agents such as z. B. in DE 43 25 922, DE 41 28 672 or DE 43 38 724 can be used.
- oxygen and nitrogenous organic redox-active compounds such as di- and trihydric phenols, e.g. B. Hydroquinone, pyrocatechol, hydroxyhydroquinone, gallic acid, phloroglucin, Pyrogallol or derivatives of these classes of compounds.
- salt and complex inorganic compounds such as salts of the metals Mn, Ti, Zr, Hf, V, Co and Ce are often used.
- Zinc compounds can also be used Prevention of corrosion on the wash ware.
- surfactants in amounts of up to 15% by weight, in particular 1 to 8% by weight, preferably 2 to 5% by weight, which can preferably belong to the class of nonionic surfactants.
- the alkoxylated alcohols are particularly preferred Alkyl polyglycosides, the fatty acid hydroxylamides and block copolymers Ethylene oxide and propylene oxide.
- alkoxylated alcohols as Reaction products of alkylene oxide, preferably ethylene oxide, with alcohols, preferred in the sense of the present invention, the longer-chain alcohols. In usually arise from n moles of ethylene oxide and one mole of alcohol, depending a complex mixture of addition products from the reaction conditions different degrees of ethoxylation. Another embodiment exists when using mixtures of the alkylene oxides preferred the mixture of Ethylene oxide and propylene oxide. You can also, if desired, by a final etherification with short-chain alkyl groups, such as the Butyl group, to the substance class of "closed" alcohol ethoxylates arrive, which can also be used in the sense of the invention.
- Alkyl polyglycosides are surfactants caused by the reaction of sugars and Alcohols according to the relevant procedures of preparative organic Chemistry can be obtained, depending on the type of manufacture to one Mixture of monoalkylated, oligomeric or polymeric sugar comes.
- Preferred Alkyl polyglycosides can be alkyl polyglucosides, with particular preference the alcohol is a long chain fatty alcohol or a mixture of long chain Is fatty alcohols and the degree of oligomerization of the sugars is between 1 and 10.
- Fatty acid polyhydroxylamides are acylated reaction products of the reductive amination of a sugar (glucose) with ammonia, generally long-chain fatty acids, long-chain fatty acid methyl esters or long-chain fatty acid chlorides are used as acylating agents. Secondary amides are formed when reducing with methylamine or ethylamine instead of with ammonia, such as. B. in S ⁇ FW-Journal, 119, (1993), 794-808. Carbon chain lengths of C 6 to C 12 in the fatty acid residue are preferably 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)
- Detergent Compositions (AREA)
Abstract
Description
Testnote bei Inhibitorzugabe von | |||||
0,0025% | 0,005% | 0,01% | 0,025 | 0,04% | |
3-Amino-5-alkyl-1,2,4-triazol | 3 | 0 | 0 | 0 | 0 |
Testnote bei Inhibitorzugabe von | |||||
0,5% | 1% | 2% | 3% | ||
3-Amino-5-alkyl-1,2,4-triazol | 0 | 0 | 0 | 0 |
Claims (8)
- Verwendung von 3-Amino-5-alkyl-1,2,4-triazolen und/oder ihrer Salze als Silberschutzmittel in Maschinengeschirrspülmitteln.
- Ausführungsform nach Anspruch 1 dadurch gekennzeichnet, daß 3-Amino-5-alkyl-1,2,4-triazolen der Formel (I) in der R für einen linearen oder verzweigten, gesättigten oder ungesättigten, gegebenenfalls durch Hydroxy- oder Alkoxylgruppen substituierten Alkylrest mit 1 bis 15 C-Atomen oder eine gegebenenfalls durch Hydroxy-, primäre, sekundäre, tertiäre Aminogruppen, Alkoxy- Alkylthio- oder Thiolgruppen substituierte Aryl-, Furyl-, Tetrahydrofuryl, Thienyl-, Pyridyl-, Pyrrolidinyl-, 5-Oxo-2-pyrrolidinyl-, Pyrryl-, Imidazolyl-, Pyrimidylgruppe steht
bzw. deren Gemische und/oder deren Salze, bevorzugt mit Salzsäure, Schwefelsäure, Phosphorsäure, Kohlensäure, schweflige Säure, organische Carbonsäuren wie Essig-, Glykol-, Citronen-, Bernsteinsäure bzw. deren Gemische verwendet werden - Ausführungsform nach Anspruch 1 und 2 dadurch gekennzeichnet, daß die 3-Amino-5-alkyl-1,2,4-triazole ausgewählt sind aus der Gruppe der 5,- -Propyl-, -Butyl-, -Pentyl-, -Heptyl-, -Octyl-, -Nonyl-, -Decyl-, -Undecyl-, -Dodecyl-, -Isononyl-, -Versatic-10-säurealkyl-, -Phenyl-, -p-Tolyl-, -(4-tert. Butylphenyl)-, -(4-Methoxyphenyl)-, -(2-, -3-, -4-Pyridyl)-, -(2-Thienyl)-, -(5-Methyl-2-furyl)-, -(5-Oxo-2-pyrrolidinyl)-, -3-amino-1,2,4-triazole
- Ausführungsform nach den Ansprüchen 1 bis 3 dadurch gekennzeichnet, daß die 3-Amino-5-alkyl-1,2,4-triazole ausgewählt sind aus der Gruppe der 5-Pentyl-, 5-Heptyl-, 5-Nonyl-, 5-Undecyl-, 5-Isononyl-, 5-Versatic-10-säurealkyl-3-amino-1,2,4-triazole sowie Mischungen dieser Substanzen.
- Ausführungsform nach den Ansprüchen 1 bis 4 dadurch gekennzeichnet, daß die 3-Amino-5-alkyl-1,2,4-triazole bzw. deren Gemische oder deren Salze bzw. deren Gemische in Mengen zwischen 0,001 und 10 Gew.-% , vorzugsweise 0,0025 bis 2 Gew.-% bezogen auf die gesamte Reinigungsmittelzusammensetzung verwendet werden.
- Ausführungsform nach den Ansprüchen 1 bis 5 dadurch gekennzeichnet, daß die 3-Amino-5-alkyl-1,2,4-triazole bzw. deren Gemische und/oder deren Salze bzw. deren Gemische zwischen 0,01 und 0,04 Gew.-% jeweils bezogen auf die gesamte Reinigungsmittelzusammensetzung verwendet werden.
- Geschirrspülmittel dadurch gekennzeichnet, daß mindestens eine Buildersubstanz, mindestens eine Bleichverbindung und mindestens eine Verbindung ausgewählt aus der Gruppe der 3-Amino-5-alkyl-1,2,4-triazole und ihrer Salze als Silberschutzmittel enthalten sind.
- Geschirrspülmittel nach Anspruch 7 dadurch gekennzeichnet, daß 10 bis 90 Gew.-% einer Buildersubstanz, 1 bis 35 Gew.-% einer Bleichverbindung und mindestens 0,01 bis 10 Gew% einer Verbindung, ausgewählt aus der Gruppe der 3-Amino-5-alkyl-1,2,4-triazole und ihrer Salze als Silberschutzmittel enthalten sind.
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE19701031A DE19701031C2 (de) | 1997-01-15 | 1997-01-15 | Verwendung von 3-Amino-5-alkyl-1,2,4-Triozolen als Silberschutzmittel |
DE19701031 | 1997-01-15 |
Publications (1)
Publication Number | Publication Date |
---|---|
EP0854183A1 true EP0854183A1 (de) | 1998-07-22 |
Family
ID=7817355
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP98100112A Ceased EP0854183A1 (de) | 1997-01-15 | 1998-01-07 | Maschinengeschirrspülmittel mit Silberschutz |
Country Status (3)
Country | Link |
---|---|
US (1) | US6147043A (de) |
EP (1) | EP0854183A1 (de) |
DE (1) | DE19701031C2 (de) |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
GB2429459A (en) * | 2005-08-23 | 2007-02-28 | Reckitt Benckiser Inc | Dishwashing detergent composition |
CN104258907A (zh) * | 2014-09-18 | 2015-01-07 | 中国工程物理研究院化工材料研究所 | 一种银-氨基四唑金属有机框架材料及其制备方法和应用 |
Families Citing this family (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE19758262A1 (de) * | 1997-12-31 | 1999-07-08 | Henkel Kgaa | Alkylaminotriazolhaltige, granulare Komponente für den Einsatz in Maschinengeschirrspülmitteln (MGSM) und Verfahren zu dessen Herstellung |
DE10049657C2 (de) * | 2000-10-07 | 2003-02-27 | Henkel Kgaa | Maschinelles Geschirreinigungsverfahren und maschinelle Geschirrspülmittel mit verbessertem Korrosionsschutz |
US9422398B2 (en) | 2014-05-30 | 2016-08-23 | Industrial Technology Research Institute | Copolymer, and method for preparing a monomer used to form the copolymer |
Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
GB736100A (en) * | 1953-11-20 | 1955-08-31 | Unilever Ltd | Improvements in detergent compositions |
DE2934461A1 (de) * | 1979-08-25 | 1981-03-26 | Henkel KGaA, 40589 Düsseldorf | Korrosionsinhibitoren fuer buntmetalle |
US4734257A (en) * | 1985-05-31 | 1988-03-29 | Henkel Kommanditgesellschaft Auf Aktien | Method of inhibiting corrosion of nonferrous metals in aqueous systems using 3-amino-5-(ω-hydroxyalkyl)-1,2,4-triazoles |
WO1995010588A1 (en) * | 1993-10-14 | 1995-04-20 | Unilever N.V. | Detergent compositions containing silver anti-tarnishing agents |
Family Cites Families (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3606990A (en) * | 1970-02-12 | 1971-09-21 | Colgate Palmolive Co | Process for washing laundry and detergent composition for working of this process |
DE3341152A1 (de) * | 1983-11-14 | 1985-05-23 | Henkel KGaA, 4000 Düsseldorf | Korrosionsinhibitoren fuer aluminium |
DE4128672A1 (de) * | 1991-08-29 | 1993-03-04 | Henkel Kgaa | Verwendung von stark alkalischen mitteln zur verhinderung des anlaufens von silberbestecken in geschirrspuelmaschinen |
DE4338724A1 (de) * | 1993-11-12 | 1995-05-18 | Henkel Kgaa | Silberkorrosionsschutzmittel II |
DE4325922A1 (de) * | 1993-08-02 | 1995-02-09 | Henkel Kgaa | Silberkorrosionsschutzmittel I |
US5480576A (en) * | 1993-10-14 | 1996-01-02 | Lever Brothers Company, Division Of Conopco, Inc. | 1,3-N azole containing detergent compositions |
-
1997
- 1997-01-15 DE DE19701031A patent/DE19701031C2/de not_active Expired - Fee Related
-
1998
- 1998-01-07 EP EP98100112A patent/EP0854183A1/de not_active Ceased
- 1998-01-15 US US09/007,474 patent/US6147043A/en not_active Expired - Fee Related
Patent Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
GB736100A (en) * | 1953-11-20 | 1955-08-31 | Unilever Ltd | Improvements in detergent compositions |
DE2934461A1 (de) * | 1979-08-25 | 1981-03-26 | Henkel KGaA, 40589 Düsseldorf | Korrosionsinhibitoren fuer buntmetalle |
US4734257A (en) * | 1985-05-31 | 1988-03-29 | Henkel Kommanditgesellschaft Auf Aktien | Method of inhibiting corrosion of nonferrous metals in aqueous systems using 3-amino-5-(ω-hydroxyalkyl)-1,2,4-triazoles |
WO1995010588A1 (en) * | 1993-10-14 | 1995-04-20 | Unilever N.V. | Detergent compositions containing silver anti-tarnishing agents |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
GB2429459A (en) * | 2005-08-23 | 2007-02-28 | Reckitt Benckiser Inc | Dishwashing detergent composition |
CN104258907A (zh) * | 2014-09-18 | 2015-01-07 | 中国工程物理研究院化工材料研究所 | 一种银-氨基四唑金属有机框架材料及其制备方法和应用 |
Also Published As
Publication number | Publication date |
---|---|
DE19701031A1 (de) | 1998-07-16 |
US6147043A (en) | 2000-11-14 |
DE19701031C2 (de) | 1998-12-10 |
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