EP1572851A1 - Bleach-containing washing or cleaning agents - Google Patents
Bleach-containing washing or cleaning agentsInfo
- Publication number
- EP1572851A1 EP1572851A1 EP03767718A EP03767718A EP1572851A1 EP 1572851 A1 EP1572851 A1 EP 1572851A1 EP 03767718 A EP03767718 A EP 03767718A EP 03767718 A EP03767718 A EP 03767718A EP 1572851 A1 EP1572851 A1 EP 1572851A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- alkali
- weight
- composition according
- acid
- component
- 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
- C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
- C11D17/0008—Detergent materials or soaps characterised by their shape or physical properties aqueous liquid non soap compositions
- C11D17/0013—Liquid compositions with insoluble particles in suspension
-
- 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
- C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
- C11D17/0004—Non aqueous liquid compositions comprising insoluble particles
-
- 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
- C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
- C11D17/0039—Coated compositions or coated components in the compositions, (micro)capsules
-
- 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
- C11D3/3942—Inorganic per-compounds
Definitions
- the present invention relates to particulate detergents or cleaning agents which, as a builder component, have only water-soluble constituents and contain particularly coated alcalipercarbonate particles.
- zeolite Na -A Another known example of such builders that improve primary washing power is zeolite Na -A, which is known to be able to form complexes with calcium ions that are so stable that their reaction with water hardness-forming anions, especially carbonate, is suppressed to form insoluble compounds.
- the builders in particular in textile detergents, are intended to relieve the detachment of the surface from the fiber or generally from the surface to be cleaned. Prevent dirt as well as insoluble compounds forming on the cleaned textile or the surface from the reaction of water hardness-forming cations with water hardness-forming anions.
- co-builders usually polymeric polycarboxylates, are usually used, which, in addition to their contribution to the secondary washing ability, advantageously also include one Show complexing effect against the water hardness-forming cations.
- detergents In addition to the indispensable active ingredients mentioned, such as surfactants and builder materials, detergents generally contain further constituents which can be summarized under the term washing auxiliaries and which include such different active ingredient groups as foam regulators, graying inhibitors, bleaching agents, enzymes and color transfer inhibitors.
- the bleaching agents are particularly important, particularly with regard to the strengthening of the washing or cleaning performance in relation to a large number of different soils.
- auxiliaries include substances that detergent performance in detergents through the oxidative degradation of those on the textile
- Soiling or those that are in the fleet after detachment from the textile support The same applies analogously to cleaning agents for hard surfaces.
- the latter compound which is often abbreviated as sodium percarbonate, is the addition compound of hydrogen peroxide with sodium carbonate (empirical formula 2 Na 2 C0 3 "3 H 2 0 2 ).
- the carbonate salts of the other alkali metals also form H 2 0 2 - Additive compounds due to the storage stability of the alkali percarbonate, which is often perceived as insufficient, in a warm, humid environment and in the presence of other customary detergent and cleaning agent components, in particular silicate components
- the presence of a shell usually causes a change in the dissolution characteristics of the alkali percarbonate. For example, the good water solubility can become non-coated
- Alkali percarbonates when they are present in enzyme-containing detergents or cleaning agents, have a disadvantageous effect, since shortly after the start of the washing or cleaning process, relatively high concentrations of active oxygen are available, which can impair the action of a number of enzymes, including proteases.
- This impairment does not necessarily have to be due to the oxidative degradation ("denaturing") of the enzymatic active ingredient, but can also be due to the fact that some soiling, for example blood, as substrates which are actually to be removed from the enzyme, due to the action of the bleaching agent in a for the enzyme less easily attackable form are converted. Therefore, the aim is to achieve a delayed release of the active oxygen by wrapping the alkali percarbonate.
- the coating of the alkali percarbonate particles described in these documents contains, in addition to magnesium sulfate or a magnesium carboxylate, a salt from the series of alkali carbonates, hydrogen carbonates and sulfates and, as a third component, an alkali silicate, it being possible for the shell components mentioned to be arranged in one or more layers .
- European patent application EP 0 623 533 it follows that the dissolution rate of coated sodium percarbonate particles decreases with increasing amount of sodium silicate.
- International patent application WO 97/19890 teaches that sodium percarbonate with a single coating layer of essentially sodium sulfate has sufficient active oxygen stability at least when the sodium percarbonate core material was produced by fluidized bed spray granulation. However, the dense grain structure only led to a slightly lower dissolution rate of the sodium percarbonate.
- European patent application EP 0 922 575 teaches the possibility of extending the dissolution time of sodium percarbonate by the presence of alkali silicate: 0.5% to 30% by weight Alkali silicate with a module greater than 3 and less than 5 either mixed with sodium percarbonate or applied to it in the form of a coating layer.
- the cladding layer consists of 9% by weight sodium silicate.
- special carboxylic acids or hydroxycarboxylic acids can additionally be arranged in one or more enveloping layers.
- Other known stabilizers from the series of magnesium sulfate, sodium sulfate, sodium carbonate and sodium bicarbonate may additionally be present in the coating layer.
- the sodium percarbonate particles coated in this way are used in combination with enzymes in particular for washing textiles or dishwashing, specifically disclosed only containing zeolite or sodium tripolyphosphate.
- detergents which contain sodium percarbonate particles coated with a combination of sodium carbonate, magnesium sulfate and sodium silicate. These dissolve more slowly than the detergent when they are dissolved in water all in all; they are used in zeolite-containing agents.
- the agent can contain all other ingredients commonly used in detergents or cleaning agents, provided that they do not interact in an unreasonable manner with them or with one of them.
- builder block is intended to express that the agents contain no other builder substances than those that are water-soluble and phosphate-free, i.e. all builder substances contained in the agent are summarized in the "block” characterized in this way, at most the Amounts of substances are excluded which, as impurities or stabilizing additives, can be contained in small quantities in the other ingredients of the agents.
- the proportion of Alkali percarbonate particles is 6% by weight to 30% by weight, in particular 10% by weight to 25% by weight.
- the coated alkali percarbonate particles contained in the agents according to the invention have an alkali percarbonate core which can be produced by any manufacturing process and can also contain stabilizers known per se, such as magnesium salts, silicates and phosphates.
- stabilizers known per se, such as magnesium salts, silicates and phosphates.
- the manufacturing processes customary in practice are, in particular, so-called crystallization processes and fluidized bed spray granulation processes.
- Crystallization processes react hydrogen peroxide and alkali carbonate in aqueous phase to alkali percarbonate and the latter is separated from the aqueous mother liquor after crystallization. While in older processes alkali percarbonate was crystallized out in the presence of a higher concentration of an inert salt, such as sodium chloride, processes are now also known in which the crystallization can also take place in the absence of a salting-out agent. Reference is made, for example, to European patent application EP 0 703 190. In fluidized bed spray granulation, an aqueous hydrogen peroxide solution and an aqueous one are used
- Alkali percarbonate particles preferably have at least two coating layers, an innermost layer containing at least one hydrate-forming inorganic salt and an outer layer containing alkali silicate.
- the outer layer containing alkali silicate can either be the outermost outer layer of a sheath comprising at least two layers, or an outer layer which is not the innermost one located directly on the alkali percarbonate, which in turn can be overlaid by one or more layers.
- the innermost cladding layer consists essentially of alkali sulfate, which can also be partially present in hydrated form.
- the term "essentially” is understood to mean that at least in the boundary layer between the alkali percarbonate core and the innermost layer, alkali hydrogen carbonate or a double salt of alkali hydrogen carbonate, such as sesquicarbonate or Wegscheider salt, may also be present.
- the innermost layer of the coated particle preferably makes up 2% by weight .-% to 20% by weight, in particular 3% by weight to 10% by weight and particularly preferably 4% by weight to 8% by weight, based in each case on the coated alkali percarbonate.
- the stated amount of casing is the casing in a hydrate-free form.
- the amount of envelope can increase due to storage in a humid atmosphere due to hydrate formation.
- the coating layer containing the alkali silicate which can be located directly on the alkali percarbonate core, but is preferably arranged as an outer layer, in particular as a second layer on the innermost coating layer described above, preferably makes up 0.2% by weight to 3% by weight. , in particular 0.3% by weight to less than 1% by weight of the coated particle.
- the alkali silicate preferably has a modulus of greater than 2.5, in particular in the range from 3 to 5 and particularly preferably from 3.2 to 4.2.
- component a) has alkali carbonate and alkali hydrogen carbonate preferably in a weight ratio of 10: 1 to 1: 1.
- the component of the bleach activators additionally present in preferred embodiments of the agents according to the invention includes the commonly used Blöder O-acyl compounds, for example multiply acylated alkylenediamines, in particular tetraacetylethylenediamine, acylated glycolurils, in particular tetraacetylglycoluril, N-acylated hydantoins, hydrazides, triazoles, urazoles, dikopylamide, sulfulfazines and cyanurates, also carboxylic anhydrides, especially phthalic anhydride, carboxylic acid esters, especially sodium nonanoyl and isononanoyl phenolsulfonate, and acylated sugar derivatives, especially pentaacetyl glucose, and cationic nitrile derivatives such as trimethylammonium acetonitrile salts.
- Blöder O-acyl compounds for example multiply acylated alkylenediamines, in particular
- the bleach activators may have been coated or granulated with coating substances in a known manner, with tetraacetylethylenediamine granulated with carboxymethyl cellulose having average grain sizes of 0.01 mm to 0.8 mm, as described, for example, by process described in European Patent EP 37 026 can be prepared, granulated 1, 5-diacetyl-2, 4-dioxohexahydro-1, 3, 5-triazine, as can be prepared by the process described in German Patent DD 255 884 , and / or according to the methods described in the international patent applications WO 00/50553, WO 00/50556, WO 02/12425, WO 02/12426 or WO 02/26927 in particle form
- alkyl polyglycosides suitable for incorporation into the agents according to the invention are compounds of the general formula (G) n -OR 12 , in which R 12 is an alkyl or alkenyl radical having 8 to 22 C atoms, G is a glycose unit and n is a number between 1 and 10 mean.
- R 12 is an alkyl or alkenyl radical having 8 to 22 C atoms
- G is a glycose unit
- n is a number between 1 and 10 mean.
- Such compounds and their preparation are described, for example, in European patent applications EP 92 355, EP 301 298, EP 357 969 and EP 362 671 or US Pat. No. 3,547,828.
- Soaps can be considered as further optional surfactant ingredients, whereby saturated fatty acid soaps, such as the salts of lauric acid, myristic acid, palmitic acid or stearic acid, as well as soaps derived from natural fatty acid mixtures, for example coconut, palm kernel or tallow fatty acids, are suitable.
- those soap mixtures are preferred which are composed of 50% by weight to 100% by weight of saturated C 2 -C 8 fatty acid soaps and up to 50% by weight of oleic acid soap.
- Soap is preferably contained in amounts from 0.1% by weight to 10% by weight, in particular from 0.5% by weight to 5% by weight.
- Sodium percarbonate particles PCI, PC2 and PC3 were each mixed in an amount of 13% by weight into an otherwise customary particulate detergent which also had 15% by weight of surfactant and 0.75% by weight of enzyme mixture (protease / amylase / cellulase) and 3.5% by weight of tetraacetyethylene diamine and, as a builder block, 20.5% by weight of sodium carbonate, 5% by weight of sodium hydrogen carbonate, 1% by weight of citric acid, 0.74% by weight of hydroxyethane-1, 1- diphosphonic acid tetrasodium salt and 3 wt .-% sodium polyacrylate contained.
- agents were also produced which were otherwise of the same composition, but which only used sodium sulfate as the starting material in Example 1
- the washing results (Y values) given in Table 2 were obtained for the agents with soluble builder block.
- the comparative agents with water-insoluble builder performed less well.
- the superior washing power of the agents containing alkali silicate-coated sodium percarbonate can be seen in the removal of soiling which can be removed with the aid of enzymes.
Landscapes
- 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)
Abstract
Description
Claims
Applications Claiming Priority (5)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE10261161 | 2002-12-20 | ||
DE10261161 | 2002-12-20 | ||
DE10320196 | 2003-05-07 | ||
DE10320196A DE10320196A1 (en) | 2002-12-20 | 2003-05-07 | Detergents or cleaning agents containing bleach |
PCT/EP2003/013539 WO2004058931A1 (en) | 2002-12-20 | 2003-12-02 | Bleach-containing washing or cleaning agents |
Publications (2)
Publication Number | Publication Date |
---|---|
EP1572851A1 true EP1572851A1 (en) | 2005-09-14 |
EP1572851B1 EP1572851B1 (en) | 2007-03-21 |
Family
ID=32683486
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP03767718A Revoked EP1572851B1 (en) | 2002-12-20 | 2003-12-02 | Bleach-containing washing or cleaning agents |
Country Status (7)
Country | Link |
---|---|
US (1) | US7456143B2 (en) |
EP (1) | EP1572851B1 (en) |
AT (1) | ATE357497T1 (en) |
AU (1) | AU2003292165A1 (en) |
DE (1) | DE50306874D1 (en) |
ES (1) | ES2283831T3 (en) |
WO (1) | WO2004058931A1 (en) |
Families Citing this family (13)
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DE10320197A1 (en) * | 2002-12-20 | 2004-07-08 | Degussa Ag | Enveloped controlled-release peroxygen compounds, process for their preparation and their use |
ATE299471T1 (en) * | 2003-05-07 | 2005-07-15 | Degussa | COATED SODIUM PERCARBONATE GRANULES WITH IMPROVED STORAGE STABILITY |
EP1628912A2 (en) * | 2003-05-23 | 2006-03-01 | Degussa AG | Use of pulverulent mixtures containing hydrogen peroxide and hydrophobed silicon dioxide for the controlled release of hydrogen peroxide or oxygen |
DE102004054495A1 (en) | 2004-11-11 | 2006-05-24 | Degussa Ag | Sodium percarbonate particles with a thiosulfate containing shell layer |
US8241624B2 (en) | 2008-04-18 | 2012-08-14 | Ecolab Usa Inc. | Method of disinfecting packages with composition containing peracid and catalase |
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IT1270000B (en) | 1994-09-22 | 1997-04-16 | Solvay Interox | PROCESS FOR THE MANUFACTURE OF PERSAL PARTICLES |
CZ285638B6 (en) * | 1994-10-07 | 1999-10-13 | Eka Chemicals Ab | Particles containing peroxo-compound and agent containing thereof |
DE4439069A1 (en) | 1994-11-02 | 1996-05-09 | Degussa | Percarbonate containing detergent, bleach and detergent composition |
DE19501120A1 (en) | 1995-01-17 | 1996-07-18 | Henkel Kgaa | Enzyme-containing bleaching detergent |
US5858957A (en) * | 1995-01-26 | 1999-01-12 | The Procter & Gamble Company | Process for the manufacture of granular detergent compositions comprising nonionic surfactant |
DE19534274A1 (en) * | 1995-09-15 | 1997-03-20 | Degussa | Process for reducing the dissolution time in the production and / or coating of sodium percarbonate |
ES2525677T3 (en) | 1995-10-17 | 2014-12-29 | Ab Enzymes Oy | Cellulases, genes that encode them and their uses |
DE19544293C2 (en) | 1995-11-28 | 1998-01-29 | Degussa | Encased sodium percarbonate particles and their use |
IT1290477B1 (en) * | 1997-03-26 | 1998-12-04 | Solvay Interox | PROCESS TO PRODUCE A PERSAL |
GB2313603A (en) | 1996-05-31 | 1997-12-03 | Procter & Gamble | Detergent compositions |
DE29721184U1 (en) | 1997-11-29 | 1998-01-15 | Roland Man Druckmasch | Sheet guiding device in a printing press |
EP0962424A1 (en) * | 1998-06-05 | 1999-12-08 | SOLVAY (Société Anonyme) | Coated sodium percarbonate particles, process for their preparation, their use in detergent compositions and detergent compositions containing them |
DE19830946A1 (en) * | 1998-07-10 | 2000-01-13 | Degussa | Process for the preparation of coated peroxygen compounds |
EP0992575A1 (en) * | 1998-10-09 | 2000-04-12 | Akzo Nobel N.V. | Bleaching agent |
DE19908069A1 (en) | 1999-02-25 | 2000-08-31 | Henkel Kgaa | Compounded acetonitrile derivatives as bleach activators in detergents |
DE19908051A1 (en) * | 1999-02-25 | 2000-08-31 | Henkel Kgaa | Process for the preparation of compounded acetonitrile derivatives |
GB9913547D0 (en) * | 1999-06-10 | 1999-08-11 | Unilever Plc | Particulate detergent composition containing zeolite |
DE10007608A1 (en) * | 2000-02-18 | 2001-08-30 | Henkel Kgaa | Particulate laundry and other detergents contain genetically modified protease of subtilisin type and coated particulate alkali percarbonate |
GB0007650D0 (en) * | 2000-03-29 | 2000-05-17 | Unilever Plc | Laundry treatment for fabrics |
KR100366556B1 (en) * | 2000-04-26 | 2003-01-09 | 동양화학공업주식회사 | Granular coated sodium percarbonate and process for preparing them |
DE10038832A1 (en) | 2000-08-04 | 2002-03-28 | Henkel Kgaa | Coated bleach activators |
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DE10049237A1 (en) | 2000-09-28 | 2002-04-11 | Basf Ag | Coated, granular N-alkylammonium acetonitrile salts and their use as a bleach activator |
US20030166484A1 (en) * | 2000-09-28 | 2003-09-04 | Kingma Arend Jouke | Coated, granular n-alkylammonium acetonitrile salts and use thereof as bleach activators |
-
2003
- 2003-12-02 AT AT03767718T patent/ATE357497T1/en not_active IP Right Cessation
- 2003-12-02 DE DE50306874T patent/DE50306874D1/en not_active Expired - Lifetime
- 2003-12-02 WO PCT/EP2003/013539 patent/WO2004058931A1/en active IP Right Grant
- 2003-12-02 AU AU2003292165A patent/AU2003292165A1/en not_active Abandoned
- 2003-12-02 ES ES03767718T patent/ES2283831T3/en not_active Expired - Lifetime
- 2003-12-02 EP EP03767718A patent/EP1572851B1/en not_active Revoked
-
2005
- 2005-06-20 US US11/159,382 patent/US7456143B2/en not_active Expired - Fee Related
Non-Patent Citations (1)
Title |
---|
See references of WO2004058931A1 * |
Also Published As
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WO2004058931A1 (en) | 2004-07-15 |
DE50306874D1 (en) | 2007-05-03 |
EP1572851B1 (en) | 2007-03-21 |
ATE357497T1 (en) | 2007-04-15 |
US7456143B2 (en) | 2008-11-25 |
ES2283831T3 (en) | 2007-11-01 |
US20050239681A1 (en) | 2005-10-27 |
AU2003292165A1 (en) | 2004-07-22 |
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