WO1995014075A1 - Activators for inorganic peroxy compounds - Google Patents
Activators for inorganic peroxy compounds Download PDFInfo
- Publication number
- WO1995014075A1 WO1995014075A1 PCT/EP1994/002569 EP9402569W WO9514075A1 WO 1995014075 A1 WO1995014075 A1 WO 1995014075A1 EP 9402569 W EP9402569 W EP 9402569W WO 9514075 A1 WO9514075 A1 WO 9514075A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- formula
- alkyl
- activators
- activator
- phenyl
- Prior art date
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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
- C11D3/3905—Bleach activators or bleach catalysts
- C11D3/3907—Organic compounds
- C11D3/3917—Nitrogen-containing compounds
- C11D3/392—Heterocyclic compounds, e.g. cyclic imides or lactames
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
- A61L2/00—Methods or apparatus for disinfecting or sterilising materials or objects other than foodstuffs or contact lenses; Accessories therefor
- A61L2/16—Methods or apparatus for disinfecting or sterilising materials or objects other than foodstuffs or contact lenses; Accessories therefor using chemical substances
- A61L2/18—Liquid substances or solutions comprising solids or dissolved gases
Definitions
- the invention is directed to the use of N-acylated pyroglutamic acid derivatives as activators for inorganic peroxygen compounds, such as, in particular, hydrogen peroxide and compounds releasing hydrogen peroxide.
- the invention is also directed to bleaching, washing, cleaning and disinfecting agents which contain these activators.
- Inorganic peroxygen compounds are used as oxidizing agents in bleaching, washing, cleaning and disinfecting agents in order to improve the action of such agents.
- hydrogen peroxide and those substances which release hydrogen peroxide in aqueous solution, such as perborates and percarbonates, are used as peroxygen compounds.
- the effect of the inorganic peroxygen compounds depends not only on the pH value, but also on the temperature. While at
- the use of so-called activators is required when using the inorganic peroxygen compounds mentioned at lower temperatures, in particular at 60 ° C or 40 ° C or below.
- the activators are predominantly N-acyl or O-acyl compounds.
- the inorganic peroxygen compounds and the activators form percarboxylic acids, which have a higher oxidation potential than H2O2 and these releasing compounds and therefore also have a good washing, cleaning, bleaching and disinfecting effect in the low temperature range.
- N-acyl compounds Numerous classes of substances have been proposed as activators among the N-acyl compounds, including: N, N, N ', N'-tetraacetylethylene diamine in (TAED), N, N, N', N'-tetraacetylglycoluril (TAGU), N, N'-di (alkoxycarbonyl) hydantoins (US 3,928,223), N-mono- and N, N * -Di (-C * - to C ⁇ alkanoyl-hydantoins (DE-A 14 67 582 and DE-C 19 49 561), N- (C ⁇ ⁇ to C4) alkyloxycarbonylsucciniird.de (US 3,928,223) and N, N'-diacyl-2,5-diketopiperazines (DE-A 20 38 106) -Acyl compounds essentially only enforce TAED Both in the TAED and in several other N-acyl compounds not all
- activators based on N-acyl compounds which essentially approach the property profile of the TAED and / or exceed it in one or the other point. If possible, the activators should be accessible from readily available and biodegradable raw materials.
- R 1 is hydrogen, C 1 -C 4 -alkyl, alkali metal or ammonium
- R 2 is a linear or branched saturated or olefinically unsaturated hydrocarbon radical having 1 to 11 C atoms, the longest chain of which can be interrupted by one or more ether bridges and one or two in addition Substituents from the series carboxy, C ⁇ ⁇ to C ß -alkoxy, -N ((Ci-C ⁇ ) alkyl) 3 + Cl ⁇ ,
- R 1 has the abovementioned meaning and n represents an integer between 2 and 12,
- the preferred compound of the formula (I), which can be in the form of its diastereomers, is cyclo- [pyroglutamyl-pyroglutamyl], which is also known as tetrahydro-dipyrrolo [1,2-a; 1 ', 2'-d] pyrazine-3, 5, 8, 10-tetraon.
- the compound of formula (I) is known - GB 1 068 814 and J. Amer. Chem. Soc. (1952), Vol. 74, 2859-2864 - but was not previously known as an activator.
- the compound (I) which can be obtained in a simple manner from racemic or optically active pyroglutamic acid and acetic anhydride, can be regarded both as N-acylated pyrrolidone and as N-acylated diketopiperazine.
- the optically active starting compound L-pyroglutamic acid is easily accessible from L-glutamic acid obtained by fermentation.
- N-acylated pyroglutamic acid derivative of the formula (I) proved to be a very effective activator: on average over six test stains on cotton (stained with tea, coffee, red wine, curry, tomato ketchup and clay), the bleaching effectiveness of this activator comes close to that of the TAED and clearly exceeds this for soiling like tomato.
- N-acylated racemic or optically active pyroglutamic acid derivatives of the general formulas (II) and (III) which can be used as activators can be obtained in a manner known per se by acylation of DL-, L- or D-pyroglutamic acid with an acyl halide or carboxylic anhydride.
- Activators according to formula (II) have proven to be surprisingly effective, although only one mole of peracid can be formed per mole: when used at the same weight, the bleaching effect of these activators when washing at 60 ° C. is comparable to that of TAED.
- the radical R 1 is H, methyl, ethyl, propyl or butyl or in the form of the cation Li, Na, K or NH4. Substances with R 1 equal to H or alkali metal, in particular Na, are preferred. In principle, R * - * - can also stand for an equivalent of an alkaline earth metal, but such substances are not preferred because of the undesirable content of
- Alkaline earth ions in the washing and bleaching liquors should not be increased.
- substances with the preferred meaning for R 1 are obtained directly.
- the solubility of compounds of the formula (II) can be increased by converting R * * * - H to R 1 to Na, which is particularly expedient if R 2 is a longer hydrocarbon radical, benzyl or phenyl.
- R 2 is particularly advantageously a linear alkyl group having 1 to 11 carbon atoms, such as methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, decyl, undecyl.
- Olefinic hydrocarbon residues such as vinyl, allyl, propen-2-yl are possible, but are less preferred.
- the number and size of the substituents on the hydrocarbon residue is generally kept low to limit the molecular weight of the resulting percarboxylic acid.
- the aromatic radical R 2 is substituted phenyl with preferably one or two carboxy or sulfo groups is preferred.
- N is particularly advantageously 2, 3, 4 and 10.
- the dicarboxylic acids required for the preparation of these compounds namely succinic acid, glutaric acid, adipic acid and dodecanedioic acid, their dichlorides with 2 mol
- R * - * - is also preferably hydrogen or sodium in the case of the substances of the formula (III).
- the use according to the invention relates to the activation of inorganic peroxygen compounds, in particular H2O2, and those compounds which release hydrogen peroxide in the aqueous phase.
- inorganic peroxygen compounds in particular H2O2
- perborates especially sodium perborate monohydrate, sodium perborate tetrahydrate, super-oxidized sodium perborate, and sodium percarbonate (2 Na2CO3-3 H2O2).
- Perphosphates, persilicates and persulfates can also be used.
- Several inorganic per-compounds can also be present during activation.
- inorganic peroxygen compounds and activators are used in a ratio of 1 mol of active oxygen to 0.05 to 1 mol, preferably 1 to 0.1 to 0.5 mol, of activator.
- the activators to be used according to the invention can be used for activation in pure form or with auxiliaries, such as granulation aids, stabilizers, pH-regulating substances; Suitable forms of addition are powders, pastes, tablets, granules or coated granules.
- the activators and inorganic peroxygen compounds can also be used in the aqueous-organic phase in addition to the purely aqueous phase come.
- the usual washing, bleaching and cleaning liquors have a purely aqueous environment.
- An aqueous-organic environment can be useful in disinfection applications and in technical oxidation processes.
- the pH of the reaction medium can be between about 4 and 13, but is preferably carried out in the alkaline range, usually at pH 8 to 11, since in this range both the in situ formation of the organic peracid proceeds well and the stability of the Perconnections is satisfactory.
- Another object of the invention is directed to bleaching, washing, cleaning and disinfecting agents which contain an inorganic peroxygen compound and an activator from the series of the N-acylated compounds which can be used according to the invention and described above
- the agent can contain one or more inorganic peroxygen compounds and one or more activators, including at least one activator according to the invention and, if required, commercially available or other known activators.
- Activators and inorganic peroxygen compounds to be used according to the invention can be combined with all the usual constituents of detergents and bleaches in order to obtain detergents and bleaches which are used for textile treatment in low and high temperatures
- the main constituents of such detergents and bleaches are, in addition to the per-compounds and activators mentioned, builders and surfactants.
- builders are in particular sodium aluminum silicates (zeolites), condensed phosphates, alkali silicates, alkali carbonates, complexing aminocarboxylic acids, polyphosphonic acids, polyvalent hydroxycarboxylic acids and polycarboxylic acids and salts of the acids mentioned.
- non-ionic surfactants such as fatty alcohol and alkylphenol polyethylene glycol ethers and long-chain alkyl glycosides
- anionic surfactants such as alkyl benzene sulfonates and sulfates of fatty alcohols and polyethylene glycol monoethers
- Other substances in the detergents and bleaches are electrolytes, pH regulators, stabilizers, foam regulators, graying inhibitors, optical brighteners, enzymes, softeners.
- the substances and amounts to be used in such agents are known to the person skilled in the art - an overview, together with literature, is provided by HG Hauthal in "Chemistry in Our Time” 26 (1992) No. 6, 293-303).
- the detergents and bleaches according to the invention are usually composed as follows:
- Surfactants 5 to 60% by weight, preferably 20 to 40% by weight
- Builders from the group sodium aluminum silicates, condensed phosphates, alkali silicates,
- Alkali carbonates, and mixtures thereof 0 to 20% by weight, preferably 1 to 8% by weight
- Polyphosphonic acids, polycarboxylic acids or their salts and their mixtures 2 to 35% by weight, preferably 10 to 25% by weight, of inorganic peroxygen compounds from the group sodium perborates and
- Pure bleaching agents as they can be used as additives for bleach-free detergents, are generally composed as follows:
- inorganic peroxygen compounds in particular Na perborate onohydrate or tetrahydrate or / and
- N-acylated pyroglutamic acid derivatives to be used as activators
- peroxide stabilizers such as
- Cleaning agents according to the invention generally contain surfactants, builders, peroxygen compounds and activators to be used according to the invention; Abrasives also contain abrasive components.
- Disinfectants according to the invention are generally based on a combination of inorganic per-compounds and activators to be used according to the invention and auxiliaries from the series of stabilizers, surfactants, pH-regulating substances and, if desired, organic solvents and others microbiocidal substances as the peracids resulting from the activators and per-compounds.
- the aqueous phase was washed with acetic ester, adjusted to pH 2, extracted with ethyl acetate, dried (MgSC> 4) and the solvent was removed on a rotary evaporator. 26.3 g were obtained as a colorless solid.
- the * - * - H NMR spectroscopic data are consistent with the structure.
- N-Nonanoyl-2-pyrrolidone-5-carboxylic acid sodium salt The product prepared according to Example 3 was dissolved in 100 ml of ethanol, and the solution was mixed with an amount of ethanolic NaOH (1 molar) equivalent to the carboxylic acid; then the solvent was removed.
- Example 6 From the course of the peracid formation and its degradation it can be seen that the activator according to Example 1 is readily soluble under the test conditions and after a short time about 62% of the theoretically possible amount of peracid is available.
- the activators of Examples 2 to 4 show a higher stability of the formed Peracid. Peracid formation is accelerated by using an activator in the salt form over that in the acid form.
- Example 6
- the test is carried out in a launderometer (type Atlas) using a bleach and activator-free commercial detergent from the US market (TIDE-Ultra®).
- the bleaching action of the activator according to Example 4 was tested on six test soils on cotton (bandy black clay; WFK-BW: tea, curry, red wine, coffee, tomato ketchup) in comparison with TAED in the launderometer (Atlas).
- Washing time 15 minutes (laboratory washing machine)
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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Health & Medical Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- General Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Wood Science & Technology (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Inorganic Chemistry (AREA)
- Epidemiology (AREA)
- Animal Behavior & Ethology (AREA)
- General Health & Medical Sciences (AREA)
- Public Health (AREA)
- Veterinary Medicine (AREA)
- Detergent Compositions (AREA)
Abstract
Description
Claims
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
EP94926143A EP0729503A1 (en) | 1993-11-15 | 1994-08-03 | Activators for inorganic peroxy compounds |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DEP4338922.8 | 1993-11-15 | ||
DE19934338922 DE4338922A1 (en) | 1993-11-15 | 1993-11-15 | Activators for inorganic peroxygen compounds |
Publications (1)
Publication Number | Publication Date |
---|---|
WO1995014075A1 true WO1995014075A1 (en) | 1995-05-26 |
Family
ID=6502600
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/EP1994/002569 WO1995014075A1 (en) | 1993-11-15 | 1994-08-03 | Activators for inorganic peroxy compounds |
Country Status (3)
Country | Link |
---|---|
EP (1) | EP0729503A1 (en) |
DE (1) | DE4338922A1 (en) |
WO (1) | WO1995014075A1 (en) |
Cited By (39)
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---|---|---|---|---|
WO1997041202A1 (en) * | 1996-04-26 | 1997-11-06 | Henkel Kommanditgesellschaft Auf Aktien | Acyl lactames as bleach activators for detergents and cleaners |
EP0730631B1 (en) * | 1993-11-25 | 1999-07-07 | WARWICK INTERNATIONAL GROUP LIMITED (Company No. 2982784) | Bleaching compositions |
US6221820B1 (en) | 1997-12-31 | 2001-04-24 | Henkel Kommanditgesellschaft Auf Aktien | Granular component containing alkylaminotriazole for use in machine dishwashing detergents |
US6221824B1 (en) | 1999-02-25 | 2001-04-24 | Henkel Kommanditgesellschaft Auf Aktien | Process for the production of compounded acetonitrile derivatives |
US6225276B1 (en) | 1997-02-07 | 2001-05-01 | Henkel Kommanditgesellschaft Auf Aktien | pH-controlled release of detergent components |
US6225274B1 (en) | 1996-11-29 | 2001-05-01 | Henkel Kommandigesellschaft Auf Aktien | Acetonitrile derivatives as bleaching activators in detergents |
US6329335B1 (en) | 1997-03-07 | 2001-12-11 | Henkel Kommanditgesellschaft Auf Aktien | Detergent tablets |
US6380147B1 (en) | 1998-06-03 | 2002-04-30 | Henkel Kommanditgesellschaft Auf Aktien | Detergents containing amylase and protease |
US6410500B1 (en) | 1997-12-30 | 2002-06-25 | Henkel Kommanditgesellschaft Auf Aktien | Moulded body dishwasher detergents with soil release polymers |
US6417152B1 (en) | 1997-07-30 | 2002-07-09 | Henkel Kommanditgesellshaft Auf Aktien | Detergent containing glucanase |
US6462006B1 (en) * | 1998-04-30 | 2002-10-08 | Henkel Kommanditgesellschaft Auf Aktien | Solid machine dishwashing detergent with phosphate and crystalline lamellar silicates |
US6541233B1 (en) | 1997-07-30 | 2003-04-01 | Henkel Kommanditgesellschaft Auf Aktien | β-glucanase from a bacillus |
US6686327B1 (en) | 1999-10-09 | 2004-02-03 | Cognis Deutschland Gmbh & Co. Kg | Shaped bodies with improved solubility in water |
US6703357B1 (en) | 1997-07-30 | 2004-03-09 | Henkel Kommanditgesellschaft Auf Aktien | Cleaning agent for hard surfaces, containing glucanase |
US6936581B2 (en) | 2000-04-19 | 2005-08-30 | Cognis Deutschland Gmbh & Co. Kg | Processes for preparing anhydrous detergent granules |
US6992056B1 (en) | 1997-12-30 | 2006-01-31 | Henkel Kgaa | Process for preparing detergent tablets having two or more regions |
US7087570B2 (en) | 1999-12-24 | 2006-08-08 | Cognis Deutschland Gmbh & Co. Kg | Detergent tablets |
US7091168B2 (en) | 2000-06-29 | 2006-08-15 | Cognis Deutschland Gmbh & Co. Kg | Liquid detergents |
US7199096B1 (en) | 1999-11-09 | 2007-04-03 | Cognis Deutschland Gmbh & Co. Kg | Detergent tablets |
WO2007054203A2 (en) | 2005-11-08 | 2007-05-18 | Henkel Ag & Co. Kgaa | Enzyme/substrate system for generating hydrogen peroxide containing sorbitol oxidase consisting of streptomyces c0elic0l0r and sorbitol |
US7300782B2 (en) | 2001-12-21 | 2007-11-27 | B.R.A.I.N. Biotechnology Research And Information Network Ag | Glycosyl hydrolases |
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DE102007003885A1 (en) | 2007-01-19 | 2008-07-24 | Lanxess Deutschland Gmbh | Use of a builder system comprising alkali metal tripolyphosphate and iminodisuccinic acid to produce automatic dishwasher formulations |
DE102007016391A1 (en) | 2007-04-03 | 2008-10-09 | Henkel Ag & Co. Kgaa | Detergent or cleaning agent for preventing transfer of textile color of colored textiles from uncolored or different colored textiles in laundry, particularly in tenside containing aqueous solution, has color transfer inhibitor |
EP1980237A1 (en) * | 2006-01-06 | 2008-10-15 | Ajinomoto Co., Inc. | Gelling agent |
US7510859B2 (en) | 2002-12-20 | 2009-03-31 | Henkel Kommanditgesellschaft Auf Aktien | Subtilisin variants with improved perhydrolase activity |
DE102007049830A1 (en) | 2007-10-16 | 2009-04-23 | Henkel Ag & Co. Kgaa | New protein variants by circular permutation |
DE102007051092A1 (en) | 2007-10-24 | 2009-04-30 | Henkel Ag & Co. Kgaa | Subtilisin from Becillus pumilus and detergents and cleaners containing this new subtilisin |
DE102008000029A1 (en) | 2008-01-10 | 2009-07-16 | Lanxess Deutschland Gmbh | Use of phosphate reduced building system comprising alkali tripolyphosphate and imino disuccinic acid, for manufacturing formulations e.g. for the automatic or mechanical dish cleaning and crockery cleaning machines on ships |
US7601678B2 (en) | 2001-02-07 | 2009-10-13 | Henkel Ag & Co. Kgaa | Washing and cleaning agents comprising fine microparticles with cleaning agent components |
US7691618B2 (en) | 2004-04-23 | 2010-04-06 | Henkel Ag & Co. Kgaa | Alkaline proteases and detergents and cleaners comprising these alkaline proteases |
US7803604B2 (en) | 2000-07-28 | 2010-09-28 | Henkel Ag & Co. Kgaa | Amylolytic enzyme extracted from Bacillus sp. A 7-7 (DSM 12368) and washing and cleaning agents containing this novel amylolytic enzyme |
US7811076B2 (en) | 2003-12-23 | 2010-10-12 | Henkel Ag & Co. Kgaa | Alkaline protease and washing and cleaning products containing said novel alkaline protease |
US7888104B2 (en) | 2000-11-28 | 2011-02-15 | Henkel Ag & Co. Kgaa | Cyclodextrin glucanotransferase (CGTase), obtained from<I>Bacillus agaradherens<λ>(DSM 9948) and detergents and cleaning agents containing said novel cyclodextrin glucanotransferase |
US8263541B2 (en) | 2005-08-19 | 2012-09-11 | Henkel Ag & Co. Kgaa | Triazine derivative dye transfer inhibitors, washing products containing the same and uses therefor |
US8262804B2 (en) | 2007-10-12 | 2012-09-11 | Basf Se | Dishwasher detergent formulations comprising a mixture of hydrophobically modified polycarboxylates and hydrophilically modified polycarboxylates |
DE102015002877A1 (en) | 2015-03-09 | 2016-09-15 | Henkel Ag & Co. Kgaa | Granular detergent or cleaner with improved dissolution rate |
DE102004047777B4 (en) | 2004-10-01 | 2018-05-09 | Basf Se | Alpha-amylase variants with increased solvent stability, process for their preparation and their use |
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US5703104A (en) * | 1995-07-07 | 1997-12-30 | Durham Pharmaceuticals Llc | Cyclic amides and derivatives thereof |
US6175374B1 (en) * | 1995-10-13 | 2001-01-16 | Agfa-Gevaert | Method for stable electro (stato) graphic reproduction of a continuous tone image |
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Citations (3)
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EP0135444A1 (en) * | 1983-09-12 | 1985-03-27 | Laboratoires Serobiologiques S.A. | Pyroglumatic derivatives, process for their preparation , intermediates and bactericidal and/or fungicidal cosmetic or pharmaceutical compositions |
EP0399584A2 (en) * | 1989-05-10 | 1990-11-28 | Unilever N.V. | Bleach activation and bleaching compositions |
EP0427224A1 (en) * | 1989-11-08 | 1991-05-15 | Kao Corporation | Novel polycationic compound and bleach composition containing the same |
-
1993
- 1993-11-15 DE DE19934338922 patent/DE4338922A1/en not_active Withdrawn
-
1994
- 1994-08-03 EP EP94926143A patent/EP0729503A1/en not_active Withdrawn
- 1994-08-03 WO PCT/EP1994/002569 patent/WO1995014075A1/en not_active Application Discontinuation
Patent Citations (3)
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EP0135444A1 (en) * | 1983-09-12 | 1985-03-27 | Laboratoires Serobiologiques S.A. | Pyroglumatic derivatives, process for their preparation , intermediates and bactericidal and/or fungicidal cosmetic or pharmaceutical compositions |
EP0399584A2 (en) * | 1989-05-10 | 1990-11-28 | Unilever N.V. | Bleach activation and bleaching compositions |
EP0427224A1 (en) * | 1989-11-08 | 1991-05-15 | Kao Corporation | Novel polycationic compound and bleach composition containing the same |
Non-Patent Citations (2)
Title |
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J. A. KING ET. AL.: "The Reaction of Glutamic Acid with Acetic Anhydride and Pyridine", JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, vol. 74, no. 10, 24 May 1952 (1952-05-24), WASHINGTON, DC US, pages 2859 - 2864 * |
See also references of EP0729503A1 * |
Cited By (42)
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---|---|---|---|---|
EP0730631B1 (en) * | 1993-11-25 | 1999-07-07 | WARWICK INTERNATIONAL GROUP LIMITED (Company No. 2982784) | Bleaching compositions |
WO1997041202A1 (en) * | 1996-04-26 | 1997-11-06 | Henkel Kommanditgesellschaft Auf Aktien | Acyl lactames as bleach activators for detergents and cleaners |
US6225274B1 (en) | 1996-11-29 | 2001-05-01 | Henkel Kommandigesellschaft Auf Aktien | Acetonitrile derivatives as bleaching activators in detergents |
US6407052B2 (en) | 1997-02-07 | 2002-06-18 | Henkel Kommanditgesellschaft Auf Aktien | pH-controlled release of detergent components |
US6225276B1 (en) | 1997-02-07 | 2001-05-01 | Henkel Kommanditgesellschaft Auf Aktien | pH-controlled release of detergent components |
US6329335B1 (en) | 1997-03-07 | 2001-12-11 | Henkel Kommanditgesellschaft Auf Aktien | Detergent tablets |
US6417152B1 (en) | 1997-07-30 | 2002-07-09 | Henkel Kommanditgesellshaft Auf Aktien | Detergent containing glucanase |
US6541233B1 (en) | 1997-07-30 | 2003-04-01 | Henkel Kommanditgesellschaft Auf Aktien | β-glucanase from a bacillus |
US6703357B1 (en) | 1997-07-30 | 2004-03-09 | Henkel Kommanditgesellschaft Auf Aktien | Cleaning agent for hard surfaces, containing glucanase |
US6992056B1 (en) | 1997-12-30 | 2006-01-31 | Henkel Kgaa | Process for preparing detergent tablets having two or more regions |
US6410500B1 (en) | 1997-12-30 | 2002-06-25 | Henkel Kommanditgesellschaft Auf Aktien | Moulded body dishwasher detergents with soil release polymers |
US6221820B1 (en) | 1997-12-31 | 2001-04-24 | Henkel Kommanditgesellschaft Auf Aktien | Granular component containing alkylaminotriazole for use in machine dishwashing detergents |
US6462006B1 (en) * | 1998-04-30 | 2002-10-08 | Henkel Kommanditgesellschaft Auf Aktien | Solid machine dishwashing detergent with phosphate and crystalline lamellar silicates |
US6380147B1 (en) | 1998-06-03 | 2002-04-30 | Henkel Kommanditgesellschaft Auf Aktien | Detergents containing amylase and protease |
US6221824B1 (en) | 1999-02-25 | 2001-04-24 | Henkel Kommanditgesellschaft Auf Aktien | Process for the production of compounded acetonitrile derivatives |
US6686327B1 (en) | 1999-10-09 | 2004-02-03 | Cognis Deutschland Gmbh & Co. Kg | Shaped bodies with improved solubility in water |
US7199096B1 (en) | 1999-11-09 | 2007-04-03 | Cognis Deutschland Gmbh & Co. Kg | Detergent tablets |
US7087570B2 (en) | 1999-12-24 | 2006-08-08 | Cognis Deutschland Gmbh & Co. Kg | Detergent tablets |
US6936581B2 (en) | 2000-04-19 | 2005-08-30 | Cognis Deutschland Gmbh & Co. Kg | Processes for preparing anhydrous detergent granules |
US7091168B2 (en) | 2000-06-29 | 2006-08-15 | Cognis Deutschland Gmbh & Co. Kg | Liquid detergents |
US7803604B2 (en) | 2000-07-28 | 2010-09-28 | Henkel Ag & Co. Kgaa | Amylolytic enzyme extracted from Bacillus sp. A 7-7 (DSM 12368) and washing and cleaning agents containing this novel amylolytic enzyme |
US7888104B2 (en) | 2000-11-28 | 2011-02-15 | Henkel Ag & Co. Kgaa | Cyclodextrin glucanotransferase (CGTase), obtained from<I>Bacillus agaradherens<λ>(DSM 9948) and detergents and cleaning agents containing said novel cyclodextrin glucanotransferase |
US7601678B2 (en) | 2001-02-07 | 2009-10-13 | Henkel Ag & Co. Kgaa | Washing and cleaning agents comprising fine microparticles with cleaning agent components |
US7300782B2 (en) | 2001-12-21 | 2007-11-27 | B.R.A.I.N. Biotechnology Research And Information Network Ag | Glycosyl hydrolases |
US7510859B2 (en) | 2002-12-20 | 2009-03-31 | Henkel Kommanditgesellschaft Auf Aktien | Subtilisin variants with improved perhydrolase activity |
US7811076B2 (en) | 2003-12-23 | 2010-10-12 | Henkel Ag & Co. Kgaa | Alkaline protease and washing and cleaning products containing said novel alkaline protease |
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US8263541B2 (en) | 2005-08-19 | 2012-09-11 | Henkel Ag & Co. Kgaa | Triazine derivative dye transfer inhibitors, washing products containing the same and uses therefor |
WO2007054203A2 (en) | 2005-11-08 | 2007-05-18 | Henkel Ag & Co. Kgaa | Enzyme/substrate system for generating hydrogen peroxide containing sorbitol oxidase consisting of streptomyces c0elic0l0r and sorbitol |
EP1980237A4 (en) * | 2006-01-06 | 2012-01-18 | Ajinomoto Kk | Gelling agent |
EP1980237A1 (en) * | 2006-01-06 | 2008-10-15 | Ajinomoto Co., Inc. | Gelling agent |
DE102007003143A1 (en) | 2007-01-16 | 2008-07-17 | Henkel Kgaa | New alkaline protease from Bacillus gibsonii and detergents and cleaners containing this novel alkaline protease |
DE102007003885A1 (en) | 2007-01-19 | 2008-07-24 | Lanxess Deutschland Gmbh | Use of a builder system comprising alkali metal tripolyphosphate and iminodisuccinic acid to produce automatic dishwasher formulations |
DE102007016391A1 (en) | 2007-04-03 | 2008-10-09 | Henkel Ag & Co. Kgaa | Detergent or cleaning agent for preventing transfer of textile color of colored textiles from uncolored or different colored textiles in laundry, particularly in tenside containing aqueous solution, has color transfer inhibitor |
US8262804B2 (en) | 2007-10-12 | 2012-09-11 | Basf Se | Dishwasher detergent formulations comprising a mixture of hydrophobically modified polycarboxylates and hydrophilically modified polycarboxylates |
DE102007049830A1 (en) | 2007-10-16 | 2009-04-23 | Henkel Ag & Co. Kgaa | New protein variants by circular permutation |
DE102007051092A1 (en) | 2007-10-24 | 2009-04-30 | Henkel Ag & Co. Kgaa | Subtilisin from Becillus pumilus and detergents and cleaners containing this new subtilisin |
DE102008000029A1 (en) | 2008-01-10 | 2009-07-16 | Lanxess Deutschland Gmbh | Use of phosphate reduced building system comprising alkali tripolyphosphate and imino disuccinic acid, for manufacturing formulations e.g. for the automatic or mechanical dish cleaning and crockery cleaning machines on ships |
DE102015002877A1 (en) | 2015-03-09 | 2016-09-15 | Henkel Ag & Co. Kgaa | Granular detergent or cleaner with improved dissolution rate |
DE102015002877B4 (en) | 2015-03-09 | 2024-09-12 | Henkel Ag & Co. Kgaa | Washing or cleaning active extrudates, their production and use in granular washing or cleaning agents |
Also Published As
Publication number | Publication date |
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EP0729503A1 (en) | 1996-09-04 |
DE4338922A1 (en) | 1995-05-18 |
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