[go: up one dir, main page]

EP0268170B1 - Bleaching composition with a constant shelf-life and with improved solution ability - Google Patents

Bleaching composition with a constant shelf-life and with improved solution ability Download PDF

Info

Publication number
EP0268170B1
EP0268170B1 EP87116481A EP87116481A EP0268170B1 EP 0268170 B1 EP0268170 B1 EP 0268170B1 EP 87116481 A EP87116481 A EP 87116481A EP 87116481 A EP87116481 A EP 87116481A EP 0268170 B1 EP0268170 B1 EP 0268170B1
Authority
EP
European Patent Office
Prior art keywords
weight
mixture
constituent
quantities
urea
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.)
Expired - Lifetime
Application number
EP87116481A
Other languages
German (de)
French (fr)
Other versions
EP0268170A2 (en
EP0268170A3 (en
EP0268170B2 (en
Inventor
Heinz-Manfred Wilsberg
Rolf Dr. Puchta
Jochen Dr. Jacobs
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Henkel AG and Co KGaA
Original Assignee
Henkel AG and Co KGaA
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Family has litigation
First worldwide family litigation filed litigation Critical https://patents.darts-ip.com/?family=6314051&utm_source=google_patent&utm_medium=platform_link&utm_campaign=public_patent_search&patent=EP0268170(B1) "Global patent litigation dataset” by Darts-ip is licensed under a Creative Commons Attribution 4.0 International License.
Application filed by Henkel AG and Co KGaA filed Critical Henkel AG and Co KGaA
Priority to AT87116481T priority Critical patent/ATE92519T1/en
Publication of EP0268170A2 publication Critical patent/EP0268170A2/en
Publication of EP0268170A3 publication Critical patent/EP0268170A3/en
Publication of EP0268170B1 publication Critical patent/EP0268170B1/en
Application granted granted Critical
Publication of EP0268170B2 publication Critical patent/EP0268170B2/en
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/39—Organic or inorganic per-compounds
    • C11D3/3902—Organic or inorganic per-compounds combined with specific additives

Definitions

  • the invention relates to a bleaching agent mixture which, if required, can be added to a detergent by the consumer or additionally added to a wash liquor in order to increase the bleaching effect during the washing treatment, in particular in the temperature range between 30 ° C and 60 ° C.
  • Bleaching agents consist of a combination of a perhydrate, in particular sodium perborate, with a bleach activator, a bleach activator being understood to mean those hydrolyzable compounds which form peracids with the perhydrate in aqueous solution. Since mixtures of the two components already react with one another in the presence of small amounts of atmospheric moisture and thus suffer loss of activity, it is necessary to separate the powder particles of the individual components as spatially as possible, which is achieved by mixing with larger proportions of powdered blending or diluting agents and / or envelopes one of the two components can be done. If the components are added to a detergent, this can already act as a separating and blending agent. However, there is then no longer any possibility for the consumer to dose the bleaching component individually according to the respective requirements or, for example when washing highly sensitive textiles, to dispense entirely with a bleaching component.
  • Wrapping one of the bleaching components is a relatively complex process.
  • individual enveloping agents can delay or complicate the dissolution and release of the bleaching component in cold or moderately warm water.
  • conventional release agents and blending agents for example sodium sulfate, sodium carbonate or disodium hydrogenphosphate, have considerable disadvantages, regardless of whether they are in anhydrous, partially hydrated or fully hydrated form.
  • the salt mixtures containing water of crystallization tend to clump when temperatures of 30 ° C to 35 ° C are reached or exceeded during storage or transport. Mixtures free of water of crystallization are stable in storage, but tend to cake and form lumps in the induction boxes of conventional household washing machines, with the result that these portions remain in the induction chambers.
  • Sequestrant with the proviso that the average grain size of the components (a) to (c) is 0.1 to 0.6 mm and the proportion of particles with a grain size of more than 1.6 mm is less than 1% by weight.
  • the sodium perborate is preferably present as a monohydrate and is preferably present in amounts of 10 to 30% by weight and in particular 15 to 25% by weight. Its average grain size is generally 0.2 to 0.6 mm, the proportion of dusty to fine-grained perborate with a particle size of less than 0.1 mm should be less than 5% by weight, preferably less than 1% by weight . Furthermore, the content of the perborate used in particles with a grain size of more than 0.8 mm should not be more than 10% by weight and with more than 1.6 mm should not be more than 1% by weight. Suitable grain fractions consist of 85 to 100% particles 0.1 to 0.8 mm in size.
  • the tetraacetylethylenediamine (TAED) is present in amounts of 5 to 30% by weight, preferably 10 to 25% by weight and in particular 15 to 23% by weight. If the perborate is used as tetrahydrate, the weight ratio of TAED to perborate is advantageously 1: 1 to 1: 5. The weight ratio of TAED to perborate monohydrate is advantageously 5: 3 to 1: 2, preferably 1.5: 1 to 1: 1.5.
  • the average particle size of the TAED should preferably not be more than 0.5 mm, in particular not more than 0.4 mm.
  • the TAED used preferably contains less than 10% by weight of particles with a particle size greater than 0.6 mm and less than 1% by weight of particles with a particle size greater than 0.8 mm.
  • the TAED can also be in granulated form, provided that these granules consist of a correspondingly fine-grained TAED and a water-soluble granulating agent, as is the case, for. B. is described in EP-C 0 037 026.
  • the granulating agent consists of cellulose ethers in proportions of less than 10%, based on TAED granules.
  • Possible components (c) are water-soluble, phosphate-free salts which do not bind or give off crystal water in the range from + 1 ° C. to + 45 ° C. or do not melt in this range. These include sodium chloride, sodium nitrate, sodium acetate trihydrate, borax and their mixtures. Another suitable cutting agent is urea. Furthermore, the substances mentioned can be blended with anhydrous sodium sulfate up to a content of at most 40% by weight, preferably up to at most 30% by weight (based on the mixture of the separating and blending agents). Higher levels of anhydrous sodium sulfate lead to a product that is very difficult to wash in and should therefore be avoided. Likewise, salts containing water of crystallization, which undergo a phase change in the specified temperature range, such as crystallized sodium sulfate and crystallized soda, lead to deteriorated powder properties and are therefore to be avoided as additives.
  • salts containing water of crystallization which undergo a phase change in the specified temperature range, such
  • Particularly suitable release agents have been found to be those which have a solubility of more than 30 g / 100 g of water in the temperature range from 5 ° C. to 20 ° C. These include in particular urea and sodium acetate trihydrate as well as sodium chloride.
  • the average grain size of component (c) is advantageously between 0.1 mm and 0.6 mm, the proportion of particles with a grain size of over 1.6 mm being less than 1% by weight.
  • the proportion of particles with a grain size of less than 0.01 mm is advantageously less than 2% by weight, preferably less than 1% by weight.
  • the agents are prepared by simply mixing the constituents, it being advantageous that TAED and perborate monohydrate are not mixed directly with one another without the presence of the separating and blending agent.
  • the procedure is to mix the 3 components simultaneously in one operation or to either mix one of components (a) and (b) with component (c) and then add the missing component. Mixing can be carried out continuously or in batches with the aid of conventional mechanical mixing devices.
  • anionic and nonionic surfactants of the sulfonate, sulfate and polyglycol ether adduct type are suitable as optional component (d), for example alkylbenzenesulfonates with linear Cio- 13- alkyl residues, alpha-sulfo fatty acids and acid esters with 12 to 18 C atoms in the fatty acid residue, alkane sulfonates with 12 to 18 carbon atoms and ethoxylates of linear or methyl-branched alcohols with 12 to 18 carbon atoms and 2 to 20 ethylene glycol ether groups.
  • Particularly suitable sequestering agents are amino group-containing phosphonic acids in the form of the water-soluble salts, such as aminotri- (methylenephosphonic acid), ethylenediaminetetra- (methylenephosphonic acid), diethylenetriaminepenta- (methylenephosphonic acid) and their higher homologues. They are usually in the form of sodium salts.
  • Other suitable sequestering agents are homo- and copolymers of acrylic, methacrylic and maleic acid, for example an acrylic acid-maleic acid copolymer in a ratio of 5: 1 to 1: 1, which are also generally in the form of the Na salts.
  • the proportion of surfactants can be, for example, 0 to 12% by weight and the proportion of sequestering agents can be 1 to 3% by weight.
  • the average grain size of the optional components suitably corresponds to the average grain size of components (a) to (c).
  • These additives can increase the cleaning ability and in the case of the sequestering agents to a certain extent also the shelf life of the agents. They have no appreciable influence on the induction behavior.
  • the mixtures according to the invention are notable for good storage stability and, in particular, for a very good and residue-free detergent capacity in conventional household washing machines.
  • the washed-in bleach activator distributes and dissolves quickly and evenly in the wash liquor and thus guarantees a good bleaching result.
  • the dry mixtures were free-flowing and did not suffer any loss of activity within 6 weeks when packaged at storage temperatures between 20 ° C and 35 ° C.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Inorganic Chemistry (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

A granular, storable bleach mixture suitable for addition to a detergent composition or to a wash liquor comprising a mixture of (a) from 5 to 35% by weight sodium perborate, preferably as monohydrate, (b) from 5 to 30% by weight tetra-acetyl ethylene-diamine and (c) from 90 to 50% by weight of a carrier material. The latter comprises a salt optionally containing water of crystallization or urea or mixtures thereof with anhydrous sodium sulfate, wherein the salt containing water of crystallization should not undergo any phase transformation between 1 DEG C. and 45 DEG C. In addition, the mixture may contain up to 15% of detergent constituents, such as surfactant and sequestering agent. The average particle size of the individual component is from 0.1 to 0.6 mm, less than 1% by weight being larger than 1.6 mm in size.

Description

Die Erfindung betrifft ein Bleichmittelgemisch, das vom Verbraucher bei Bedarf einem Waschmittel zugesetzt bzw. zusätzlich einer Waschlauge zugesetzt werden kann, um die Bleichwirkung während der Waschbehandlung, insbesondere im Temperaturbereich zwischen 30 ° C und 60 ° C zu erhöhen.The invention relates to a bleaching agent mixture which, if required, can be added to a detergent by the consumer or additionally added to a wash liquor in order to increase the bleaching effect during the washing treatment, in particular in the temperature range between 30 ° C and 60 ° C.

Es sind Bleichmittel bekannt, die aus einer Kombination eines Perhydrates, insbesondere Natriumperborat, mit einem Bleichaktivator bestehen, wobei unter einem Bleichaktivator solche hydrolysierbaren Verbindungen zu verstehen sind, die mit dem Perhydrat in wäßriger Lösung Persäuren bilden. Da Gemische der beiden Komponenten bereits in Gegenwart geringer Mengen von Luftfeuchtigkeit miteinander reagieren und somit Aktivitätsverluste erleiden, ist es erforderlich, die Pulverpartikel der Einzelkomponenten möglichst räumlich voneinander zu trennen, was durch Vermischen mit größeren Anteilen an pulverförmigen Verschnitt- bzw. Verdünnungsmitteln und/oder Umhüllen einer der beiden Komponenten erfolgen kann. Sofern die Komponenten einem Waschmittel zugesetzt werden, kann dieses bereits als Trenn- und Verschnittmittel wirken. Es besteht dann jedoch für den Verbraucher nicht mehr die Möglichkeit, die Bleichkomponente individuell nach den jeweiligen Erfordernissen zu dosieren oder, beispielsweise beim Waschen hochempfindlicher Textilien, ganz auf eine Bleichkomponente zu verzichten.Bleaching agents are known which consist of a combination of a perhydrate, in particular sodium perborate, with a bleach activator, a bleach activator being understood to mean those hydrolyzable compounds which form peracids with the perhydrate in aqueous solution. Since mixtures of the two components already react with one another in the presence of small amounts of atmospheric moisture and thus suffer loss of activity, it is necessary to separate the powder particles of the individual components as spatially as possible, which is achieved by mixing with larger proportions of powdered blending or diluting agents and / or envelopes one of the two components can be done. If the components are added to a detergent, this can already act as a separating and blending agent. However, there is then no longer any possibility for the consumer to dose the bleaching component individually according to the respective requirements or, for example when washing highly sensitive textiles, to dispense entirely with a bleaching component.

Das Umhüllen einer der Bleichkomponenten ist ein verhältnismäßig aufwendiges Verfahren. Außerdem können einzelne Hüllmittel die Auflösung und Freisetzung der Bleichkomponente in kaltem oder mäßig warmem Wasser verzögern oder erschweren. Weiterhin hat sich gezeigt, daß übliche Trenn- und Verschnittmittel, beispielsweise Natriumsulfat, Natriumcarbonat oder Dinatriumhydrogenphosphat, erhebliche Nachteile aufweisen, unabhängig davon, ob sie in wasserfreier, teilhydratisierter oder vollständig hydratisierter Form vorliegen. Die kristallwasserhaltigen Salzgemische neigen zum Verklumpen, wenn bei der Lagerung oder dem Transport Temperaturen von 30 ° C bis 35 ° C erreicht bzw. überschritten werden. Kristallwasserfreie Gemische sind zwar lagerstabil, neigen aber in den Einspülkästen übicher Haushaltswaschmaschinen zu Anbackungen und Klumpenbildung mit der Folge, daß diese Anteile in den Einspülkammern verbleiben.Wrapping one of the bleaching components is a relatively complex process. In addition, individual enveloping agents can delay or complicate the dissolution and release of the bleaching component in cold or moderately warm water. Furthermore, it has been shown that conventional release agents and blending agents, for example sodium sulfate, sodium carbonate or disodium hydrogenphosphate, have considerable disadvantages, regardless of whether they are in anhydrous, partially hydrated or fully hydrated form. The salt mixtures containing water of crystallization tend to clump when temperatures of 30 ° C to 35 ° C are reached or exceeded during storage or transport. Mixtures free of water of crystallization are stable in storage, but tend to cake and form lumps in the induction boxes of conventional household washing machines, with the result that these portions remain in the induction chambers.

Gegenstand der Erfindung, mit der diese Nachteile vermieden werden können, ist ein lagerbeständiges, pulverförmiges Bleichmittelgemisch mit verbessertem Lösungsvermögen, enthaltend eine Peroxo-Verbindung, einen als Persäurevorläufer wirkenden Bleichaktivator und ein wasserlösliches Trenn- und Verschnittmittel, dadurch gekennzeichnet, daß es aus einem innigen Gemisch folgender Inhaltsstoffe besteht:

  • a) 5 bis 35 Gew.-% Natriumperborat in Form des Monohydrats oder Tetrahydrats,
  • b) 5 bis 30 Gew.-% Tetraacetylethylendiamin,
  • c) 90 bis 50 Gew.-% mindestens einer der folgenden wasserlöslichen phosphatfreien Verbindungen:
  • i) ein kristallwasserfreies oder kristallwasserhaltiges Salz, das keine Phasenumwandlung im Bereich von + 1 ° C bis + 45 ° C erleidet,
  • ii) Harnstoff,
  • iii) ein Gemisch der unter (i) und (ii) bezeichneten Stoffe mit wasserfreiem Natriumsulfat bis zu einem Gewichtsverhältnis von mehr als 3 : 2,
  • d) 0 bis 15 Gew.-% an Waschmittelbestandteilen aus der Klasse der synthetischen Tenside und/oder
The invention, with which these disadvantages can be avoided, is a storage-stable, powdery bleach mixture with improved solubility, containing a peroxo compound, a bleach activator acting as a peracid precursor and a water-soluble separating and blending agent, characterized in that it consists of an intimate mixture The following ingredients exist:
  • a) 5 to 35% by weight sodium perborate in the form of the monohydrate or tetrahydrate,
  • b) 5 to 30% by weight of tetraacetylethylenediamine,
  • c) 90 to 50% by weight of at least one of the following water-soluble phosphate-free compounds:
  • i) a crystal water-free or crystal water-containing salt which does not undergo a phase change in the range from + 1 ° C to + 45 ° C,
  • ii) urea,
  • iii) a mixture of the substances described under (i) and (ii) with anhydrous sodium sulfate up to a weight ratio of more than 3: 2,
  • d) 0 to 15% by weight of detergent components from the class of synthetic surfactants and / or

Sequestrierungsmittel,
mit der Maßgabe, daß die mittlere Korngröße der Bestandteile (a) bis (c) 0,1 bis 0,6 mm beträgt und der Anteil an Partikeln mit einer Korngröße von mehr als 1,6 mm weniger als 1 Gew.-% beträgt.Sequestrant,
with the proviso that the average grain size of the components (a) to (c) is 0.1 to 0.6 mm and the proportion of particles with a grain size of more than 1.6 mm is less than 1% by weight.

Das Natriumperborat liegt bevorzugt als Monohydrat vor und ist vorzugsweise in Mengen von 10 bis 30 Gew.-% und insbesondere von 15 bis 25 Gew.-% anwesend. Seine mittlere Korngröße beträgt im allgemeinen 0,2 bis 0,6 mm, wobei der Anteil an staubförmigem bis feinkörnigem Perborat mit einer Teilchengröße von unter 0,1 mm weniger als 5 Gew.-%, vorzugsweise weniger als 1 Gew.-% betragen soll. Ferner soll der Gehalt des eingesetzten Perborats an Partikeln mit einer Korngröße von mehr als 0,8 mm nicht mehr als 10 Gew-% und mit mehr als 1,6 mm nicht mehr als 1 Gew.-% betragen. Gut geeignete Kornfraktionen bestehen zu 85 bis 100 % aus Teilchen der Größe 0,1 bis 0,8 mm.The sodium perborate is preferably present as a monohydrate and is preferably present in amounts of 10 to 30% by weight and in particular 15 to 25% by weight. Its average grain size is generally 0.2 to 0.6 mm, the proportion of dusty to fine-grained perborate with a particle size of less than 0.1 mm should be less than 5% by weight, preferably less than 1% by weight . Furthermore, the content of the perborate used in particles with a grain size of more than 0.8 mm should not be more than 10% by weight and with more than 1.6 mm should not be more than 1% by weight. Suitable grain fractions consist of 85 to 100% particles 0.1 to 0.8 mm in size.

Das Tetraacetylethylendiamin (TAED) ist in Mengen von 5 bis 30 Gew.-%, vorzugsweise 10 bis 25 Gew.-% und insbesondere 15 bis 23 Gew.-% anwesend. Sofern das Perborat als Tetrahydrat eingesetzt wird, beträgt das Gewichstverhältnis TAED zu Perborat zweckmäßigerweise 1 : 1 bis 1 : 5. Das Gewichtsverhältnis von TAED zu Perborat-monohydrat beträgt zweckmäßigerweise 5 : 3 bis 1 : 2, vorzugsweise 1,5 : 1 bis 1 : 1,5. Die mittlere Teilchengröße des TAED soll vorzugsweise nicht mehr als 0,5 mm, insbesondere nicht mehr als 0,4 mm betragen. Vorzugsweise enthält das eingesetzte TAED weniger als 10 Gew.-% an Teilchen mit einer Korngröße über 0,6 mm und weniger als 1 Gew.-% an Teilchen mit einer Korngröße über 0,8 mm. Hinsichtlich des Gehalts an Feinanteilen, d. h. solchen mit weniger als 0,1 mm, bestehen keine engen Grenzen, vielmehr ergeben sich diese lediglich hinsichtlich der Verarbeitbarkeit derartiger feinteiliger Produkte. Hierin ist ein besonderer Vorteil der erfindungsgemäßen Produkte zu sehen. Es lassen sich auf diese Weise auch staubförmige bzw. aus technischen Produkten durch Absieben der Feinanteile gewonnene Chargen verwenden. Es galt bisher, daß für die Stabilität TAED-haltiger Bleichmittelgemische der Aktivator vorteilhaft in granulierter, grobkörniger Provenienz vorliegen müsse, um eine möglichst hohe Lagerstabilität zu erzielen. Überraschend hat sich gezeigt, daß es im Falle der erfindungsgemäßen Gemische weder einer Granulierung noch einer Abtrennung staubförmiger TAED-Anteile bedarf. Hinzu kommt, daß sich das sehr feinteilige TAED leicht in der Waschlauge verteilt und nicht, wie im Falle grobkörniger Teilchen, auf den Boden des Waschbehälters bzw. der Außentrommel der Waschmaschine absinkt und somit nicht mehr für den Bleichprozeß zur Verfügung steht.The tetraacetylethylenediamine (TAED) is present in amounts of 5 to 30% by weight, preferably 10 to 25% by weight and in particular 15 to 23% by weight. If the perborate is used as tetrahydrate, the weight ratio of TAED to perborate is advantageously 1: 1 to 1: 5. The weight ratio of TAED to perborate monohydrate is advantageously 5: 3 to 1: 2, preferably 1.5: 1 to 1: 1.5. The average particle size of the TAED should preferably not be more than 0.5 mm, in particular not more than 0.4 mm. The TAED used preferably contains less than 10% by weight of particles with a particle size greater than 0.6 mm and less than 1% by weight of particles with a particle size greater than 0.8 mm. With regard to the content of fine fractions, ie those with less than 0.1 mm, there are no narrow limits, rather these only arise with regard to the processability of such fine fractions Products. This is a particular advantage of the products according to the invention. In this way, it is also possible to use dusty batches or batches obtained from technical products by screening off the fines. It was previously the case that for the stability of bleach mixtures containing TAED, the activator must advantageously be in granulated, coarse-grained provenance in order to achieve the best possible storage stability. Surprisingly, it has been shown that, in the case of the mixtures according to the invention, neither granulation nor removal of dust-like TAED fractions is required. In addition, the very finely divided TAED is easily distributed in the wash liquor and does not, as in the case of coarse-grained particles, sink to the bottom of the wash container or the outer drum of the washing machine and is therefore no longer available for the bleaching process.

Das TAED kann auch in granulierter Form vorliegen, sofern diese Granulate aus entsprechend feinkörnigem TAED und einem in Wasser leicht löslichen Granuliermittel besteht, so wie dies z. B. in der EP-C 0 037 026 beschrieben ist. Das Granuliermittel besteht in diesem Falle aus Celluloseethern in Anteilen von unter 10 %, bezogen auf TAED-Granulat. Mit Vorteil wird in diesem Falle ein TAED-Granulat eingesetzt, das aus Agglomeraten mit einer Größe von 0,01 mm bis 0,8 mm, vorzugsweise 0,05 mm bis 0,6 mm besteht.The TAED can also be in granulated form, provided that these granules consist of a correspondingly fine-grained TAED and a water-soluble granulating agent, as is the case, for. B. is described in EP-C 0 037 026. In this case, the granulating agent consists of cellulose ethers in proportions of less than 10%, based on TAED granules. In this case, it is advantageous to use TAED granules which consist of agglomerates with a size of 0.01 mm to 0.8 mm, preferably 0.05 mm to 0.6 mm.

Als Komponente (c) kommen wasserlösliche, phosphatfreie Salze in Frage, die im Bereich von + 1 ° C bis + 45 ° C kein Kristallwasser binden oder abgeben bzw. in diesem Bereich nicht schmelzen. Hierzu zählen Natriumchlorid, Natriumnitrat, Natriumacetat-trihydrat, Borax und deren Gemische. Als weiteres gut geeignetes Verschnittmittel kommt Harnstoff in Frage. Weiterhin können die genannten Stoffe bis zu einem Gehalt von höchstens 40 Gew.-%, vorzugsweise bis höchstens 30 Gew.-% (bezogen auf das Gemisch der Trenn- und Verschnittmittel) mit wasserfreiem Natriumsulfat verschnitten werden. Höhere Gehalte an wasserfreiem Natriumsulfat führen zu einem sehr schlecht einspülbaren Produkt und sind daher zu vermeiden. Ebenso führen kristallwasserhaltige Salze, die in dem angegebenen Temperaturbereich eine Phasenumwandlung erleiden, wie kristallisiertes Natriumsulfat und kristallisierte Soda, zu verschlechterten Pulvereigenschaften und sind daher als Zusätze zu vermeiden.Possible components (c) are water-soluble, phosphate-free salts which do not bind or give off crystal water in the range from + 1 ° C. to + 45 ° C. or do not melt in this range. These include sodium chloride, sodium nitrate, sodium acetate trihydrate, borax and their mixtures. Another suitable cutting agent is urea. Furthermore, the substances mentioned can be blended with anhydrous sodium sulfate up to a content of at most 40% by weight, preferably up to at most 30% by weight (based on the mixture of the separating and blending agents). Higher levels of anhydrous sodium sulfate lead to a product that is very difficult to wash in and should therefore be avoided. Likewise, salts containing water of crystallization, which undergo a phase change in the specified temperature range, such as crystallized sodium sulfate and crystallized soda, lead to deteriorated powder properties and are therefore to be avoided as additives.

Als besonders geeignete Trennmittel haben sich solche erwiesen, die im Temperaturbereich von 5 ° C bis 20 ° C eine Löslichkeit von mehr als 30 g/100 g Waser besitzen. Hierzu zählen insbesondere Harnstoff und Natriumacetat-trihydrat sowie Natriumchlorid.Particularly suitable release agents have been found to be those which have a solubility of more than 30 g / 100 g of water in the temperature range from 5 ° C. to 20 ° C. These include in particular urea and sodium acetate trihydrate as well as sodium chloride.

Die mittlere Korngröße der Komponente (c) liegt vorteilhaft zwischen 0,1 mm und 0,6 mm, wobei der Anteil von Teilchen mit einer Korngröße von über 1,6 mm weniger als 1 Gew.-% beträgt. Der Anteil von Teilchen mit einer Korngröße von unter 0,01 mm beträgt vorteilhaft weniger als 2 Gew.-%, vorzugsweise weniger als 1 Gew.-%.The average grain size of component (c) is advantageously between 0.1 mm and 0.6 mm, the proportion of particles with a grain size of over 1.6 mm being less than 1% by weight. The proportion of particles with a grain size of less than 0.01 mm is advantageously less than 2% by weight, preferably less than 1% by weight.

Die Herstellung der Mittel erfolgt durch einfaches Vermischen der Bestandteile, wobei es vorteilhaft ist, daß TAED und Perboratmonohydrat nicht ohne Anwesenheit des Trenn- und Verschnittmittels unmittelbar mit einander vermischt werden. Zweckmäßigerweise geht man so vor, daß man die 3 Komponenten in einem Arbeitsgang gleichzeitig vermischt oder daß man entweder eine der Komponenten (a) und (b) mit der Komponente (c) vermischt und dann die fehlende Komponente hinzufügt. Das Mischen kann unter Zuhilfenahme üblicher mechanischer Mischvorrichtungen kontinuierlich oder chargenweise erfolgen.The agents are prepared by simply mixing the constituents, it being advantageous that TAED and perborate monohydrate are not mixed directly with one another without the presence of the separating and blending agent. Appropriately, the procedure is to mix the 3 components simultaneously in one operation or to either mix one of components (a) and (b) with component (c) and then add the missing component. Mixing can be carried out continuously or in batches with the aid of conventional mechanical mixing devices.

Als fakultative Komponente (d) eignen sich bekannte anionische und nichtionische Tenside vom Typ der Sulfonate, Sulfate und Polyglykoletheraddukte, beispielsweise Alkylbenzolsulfonate mit linearen Cio-13-Alkylresten, Alphasulfofettsäuren und -säureester mit 12 bis 18 C-Atomen im Fettsäurerest, Alkansulfonate mit 12 bis 18 C-Atomen sowie Ethoxylate von linearen oder methylverzweigten Alkoholen mit 12 bis 18 C-Atomen und 2 bis 20 Ethylenglykolethergruppen. Als Sequestrierungsmittel kommen insbesondere Aminogruppen enthaltende Phosphonsäuren in Form der wasserlöslichen Salze, wie Aminotri-(methylenphosphonsäure), Ethylendiamintetra-(methylenphosphonsäure), Diethylentriaminpenta-(methylenphosphonsäure) sowie deren höhere Homologen in Frage. Sie liegen üblicherweise als Natriumsalze vor. Weitere geeignete Sequestrierungsmittel sind Homo- und Copolymere der Acryl-, Methacryl- und Maleinsäure, beispielsweise ein Acrylsäure-Maleinsäure-Copolymer im Verhältnis 5 : 1 bis 1 : 1, die ebenfalls im allgemeinen in Form der Na-Salze vorliegen. Der Anteil der Tenside kann beispielsweise 0 bis 12 Gew.-% und der Anteil der Sequestrierungsmittel 1 bis 3 Gew.-% betragen. Die mittlere Korngröße der fakultativen Bestandteile entspricht zweckmäßigerweise der mittleren Korngröße der Bestandteile (a) bis (c). Diese Zusätze können das Reinigungsvermögen und im Falle der Sequestrierungsmittel in gewissem Maße auch die Lagerbeständigkeit der Mittel steigern. Auf das Einspülverhalten sind sie ohne nennenswerten Einfluß.Known anionic and nonionic surfactants of the sulfonate, sulfate and polyglycol ether adduct type are suitable as optional component (d), for example alkylbenzenesulfonates with linear Cio- 13- alkyl residues, alpha-sulfo fatty acids and acid esters with 12 to 18 C atoms in the fatty acid residue, alkane sulfonates with 12 to 18 carbon atoms and ethoxylates of linear or methyl-branched alcohols with 12 to 18 carbon atoms and 2 to 20 ethylene glycol ether groups. Particularly suitable sequestering agents are amino group-containing phosphonic acids in the form of the water-soluble salts, such as aminotri- (methylenephosphonic acid), ethylenediaminetetra- (methylenephosphonic acid), diethylenetriaminepenta- (methylenephosphonic acid) and their higher homologues. They are usually in the form of sodium salts. Other suitable sequestering agents are homo- and copolymers of acrylic, methacrylic and maleic acid, for example an acrylic acid-maleic acid copolymer in a ratio of 5: 1 to 1: 1, which are also generally in the form of the Na salts. The proportion of surfactants can be, for example, 0 to 12% by weight and the proportion of sequestering agents can be 1 to 3% by weight. The average grain size of the optional components suitably corresponds to the average grain size of components (a) to (c). These additives can increase the cleaning ability and in the case of the sequestering agents to a certain extent also the shelf life of the agents. They have no appreciable influence on the induction behavior.

Die erfindungsgemäßen Gemische zeichnen sich durch eine gute Lagerbeständigkeit und insbesondere ein sehr gutes und rückstandfreies Einspülvermögen in üblichen Haushaltswaschmaschinen aus. Der eingespülte Bleichaktivator verteilt und löst sich schnell und gleichmäßig in der Waschflotte und garantiert somit ein gutes Bleichergebnis.The mixtures according to the invention are notable for good storage stability and, in particular, for a very good and residue-free detergent capacity in conventional household washing machines. The washed-in bleach activator distributes and dissolves quickly and evenly in the wash liquor and thus guarantees a good bleaching result.

BeispieleExamples

In einem mit rotierenden Pflugschaufeln ausgerüsteten Mischer wurden folgende Bestandteile zusammengemischt (in Gew.-%):

Figure imgb0001
The following components were mixed together (in% by weight) in a mixer equipped with rotating plow blades:
Figure imgb0001

Die Gemische wiesen folgende Schüttgewichte auf:

  • Beispiel 1 = 645 g/I; Beispiel 2 = 640 g/I; Vergleich A = 600 g/I; Vergleich B = 590 g/I.
The mixtures had the following bulk densities:
  • Example 1 = 645 g / l; Example 2 = 640 g / l; Comparison A = 600 g / l; Comparison B = 590 g / l.

Die trockenen Gemische waren gut rieselfähig und erlitten in abgepacktem Zustand bei Lagertemperaturen zwischen 20 ° C und 35 ° C innerhalb von 6 Wochen keinen Aktivitätsverlust.The dry mixtures were free-flowing and did not suffer any loss of activity within 6 weeks when packaged at storage temperatures between 20 ° C and 35 ° C.

Das Einspülverhalten des Bleichmittels wurde mittels einer Haushaltswaschmaschine (ZANUSSI 285) getestet, und zwar wurden abgemessene Mengen des Bleichgemisches bzw. eines pulverförmigen Haushaltswaschmittel in verschiedener Reihenfolge in den Einspülkasten überführt und die Maschine gestartet. Der Wasserzulauf betrug 10 Liter (7,5 Liter pro Minute). Danach wurde das im Einspülkasten verbliebene Material entfernt und zurückgewogen.

  • Versuchsreihe A: 100 g Haushaltswaschmittel eingefüllt
  • Versuchsreihe B: 100 g Bleichmittel eingefüllt
  • Versuchsreihe C: zuerst 100 g Waschmittel, dann 33 g Bleichmittel eingefüllt
  • Versuchsreihe D: zuerst 33 g Bleichmittel, dann 100 g Waschmittel eingefüllt.
The bleaching-in behavior of the bleaching agent was tested using a household washing machine (ZANUSSI 285), namely measured quantities of the bleaching mixture or a powdered household detergent were transferred to the dispenser box in different orders and the machine started. The water supply was 10 liters (7.5 liters per minute). The material remaining in the dispenser drawer was then removed and weighed back.
  • Trial series A: 100 g of household detergent filled
  • Trial series B: 100 g of bleach added
  • Test series C: first 100 g of detergent, then 33 g of bleach added
  • Test series D: first 33 g of bleach, then 100 g of detergent.

In der folgenden Tabelle ist angegeben, nach welchen Mengen an einlaufendem Wasser bereits eine vollständige Einspülung erfolgt war bzw. wieviel Gramm an Substanz im Einspülkasten nach Zulauf von 10 Liter Wasser zurückgeblieben waren. Jeder Versuch wurde 5mal durchgeführt und der Mittelwert gebildet. Die Ergebnisse belegen die Überlegenheit der erfindungsgemäßen Gemische.

Figure imgb0002
The following table shows the amounts of water that have been taken in after a complete flushing or how many grams of substance were left in the dispenser after 10 liters of water had been added. Each test was carried out 5 times and the mean was formed. The results demonstrate the superiority of the mixtures according to the invention.
Figure imgb0002

Claims (6)

1. A storable, powder-form bleach mixture having improved dissolving power which contains a peroxo compound, a bleach activator acting as a peracid precursor and, optionally, urea, surfactants or sequestrants, characterized in that it consists of an intimate mixture of the following constituents:
a) 5 to 35% by weight of sodium perborate in the form of the monohydrate or tetrahydrate,
b) 5 to 30% by weight of tetraacetyl ethylene diamine,
c) 90 to 50% by weight of at least one of the following water-soluble phosphate-free compounds:
i) a salt free from or containing water of crystallization which does not undergo any phase transition in the temperature range from + 1 ° C to + 45 ° C,
ii) urea,
iii) a mixture of the substances mentioned in (i) or (ii) with anhydrous sodium sulfate in a ratio by weight of at least 3:2,
d) 0 to 15% by weight of detergent constituents from the group comprising synthetic surfactants and/or sequestering agents,
with the proviso that the average particle size of constituents (a) to (c) is from 0.1 to 0.6 mm and the proportion of particles larger than 1.6 mm in size is less than 1 % by weight.
2. A mixture as claimed in claim 1, characterized in that constituent (a) consists of perborate monohydrate.
3. A mixture as claimed in claims 1 and 2, characterized in that constituent (a) is present in quantities of 10 to 30% by weight and more especially in quantities of 15 to 25% by weight.
4. A mixture as claimed in claims 1 and 2, characterized in that constituent (b) is present in quantities of 10 to 25% by weight and more especially in quantities of 15 to 23% to weight.
5. A mixture as claimed in claims 1 to 4, characterized in that the ratio by weight of sodium perborate monohydrate to constituent (b) is from 5:3 to 1:2 and preferably from 1.5:1 to 1:1.5.
6. A mixture as claimed in claim 1, characterized in that constituent (c) consists of urea and mixtures thereof with anhydrous sodium sulfate in which the maximum sodium sulfate content is 30% by weight, based on constituent (c).
EP87116481A 1986-11-15 1987-11-07 Bleaching composition with a constant shelf-life and with improved solution ability Expired - Lifetime EP0268170B2 (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AT87116481T ATE92519T1 (en) 1986-11-15 1987-11-07 SHELF-STABLE BLEACH MIX WITH ENHANCED SOLVING POWER.

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE3639115 1986-11-15
DE19863639115 DE3639115A1 (en) 1986-11-15 1986-11-15 STORAGE BLENDER MIXTURE WITH IMPROVED SOLUTION

Publications (4)

Publication Number Publication Date
EP0268170A2 EP0268170A2 (en) 1988-05-25
EP0268170A3 EP0268170A3 (en) 1990-01-31
EP0268170B1 true EP0268170B1 (en) 1993-08-04
EP0268170B2 EP0268170B2 (en) 1996-10-02

Family

ID=6314051

Family Applications (1)

Application Number Title Priority Date Filing Date
EP87116481A Expired - Lifetime EP0268170B2 (en) 1986-11-15 1987-11-07 Bleaching composition with a constant shelf-life and with improved solution ability

Country Status (5)

Country Link
US (1) US4938889A (en)
EP (1) EP0268170B2 (en)
JP (1) JPS63137999A (en)
AT (1) ATE92519T1 (en)
DE (2) DE3639115A1 (en)

Families Citing this family (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5411673A (en) * 1991-02-06 1995-05-02 The Procter & Gamble Company Peroxyacid bleach precursor compositions
GB9102507D0 (en) * 1991-02-06 1991-03-27 Procter & Gamble Peroxyacid bleach precursor compositions
US5534195A (en) * 1993-12-23 1996-07-09 The Procter & Gamble Co. Process for making particles comprising lactam bleach activators
US5534196A (en) * 1993-12-23 1996-07-09 The Procter & Gamble Co. Process for making lactam bleach activator containing particles
DE19619646A1 (en) * 1996-05-15 1997-11-20 Henkel Kgaa Stabilization of alkali percarbonate
GB2318575A (en) * 1996-10-22 1998-04-29 Unilever Plc Detergent tablet
EP1064845B1 (en) * 1999-06-30 2003-09-10 Kao Corporation Virucidal and sporicidal composition
WO2002096547A2 (en) * 2001-05-25 2002-12-05 Henkel Kommanditgesellschaft Auf Aktien Granules containing one or more highly active substances and method for producing the same
DE10214750A1 (en) * 2002-04-03 2003-10-16 Ecolab Gmbh & Co Ohg Instrument disinfection
US20050168749A1 (en) * 2002-07-08 2005-08-04 Hongke Ye Optical olfactory sensor with holographic readout
US20080087390A1 (en) * 2006-10-11 2008-04-17 Fort James Corporation Multi-step pulp bleaching
US8845860B2 (en) 2010-09-16 2014-09-30 Georgia-Pacific Consumer Products Lp High brightness pulps from lignin rich waste papers

Family Cites Families (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4064062A (en) * 1975-12-15 1977-12-20 Colgate-Palmolive Stabilized activated percompound bleaching compositions and methods for manufacture thereof
NL180122C (en) * 1977-12-22 1987-01-02 Unilever Nv BLEACH ACTIVATOR IN GRANULATE FORM.
DE2963842D1 (en) * 1978-06-26 1982-11-18 Procter & Gamble Particulate detergent additive product
US4259200A (en) * 1979-04-06 1981-03-31 Lever Brothers Company Bleaching and cleaning compositions
IE49996B1 (en) * 1979-07-06 1986-01-22 Unilever Ltd Particulate bleach compositions
ZA804930B (en) * 1979-08-16 1982-03-31 Unilever Ltd Bleach composition
US4412934A (en) * 1982-06-30 1983-11-01 The Procter & Gamble Company Bleaching compositions
GB8607388D0 (en) * 1986-03-25 1986-04-30 Unilever Plc Activator compositions

Also Published As

Publication number Publication date
DE3639115A1 (en) 1988-05-19
US4938889A (en) 1990-07-03
EP0268170A2 (en) 1988-05-25
DE3786882D1 (en) 1993-09-09
ATE92519T1 (en) 1993-08-15
JPS63137999A (en) 1988-06-09
EP0268170A3 (en) 1990-01-31
EP0268170B2 (en) 1996-10-02

Similar Documents

Publication Publication Date Title
DE2820990C2 (en)
DE2338412C2 (en) Bleaching aid suitable for use in detergents and bleaching agents and a process for its production
DE69216191T3 (en) Detergent powder and process for its preparation
DE3885956T2 (en) Composition of bleach activators.
EP0268170B1 (en) Bleaching composition with a constant shelf-life and with improved solution ability
EP0536110B1 (en) Process for manufacturing tenside-containing granulates
EP0191396A1 (en) Process for the production of free-flowing granulates
DE2138584C3 (en) Shelf-life bleach suitable for use in detergents and process for making same
DE68921858T2 (en) Process for the production of bleach granules.
DE4116701A1 (en) BLEACHING CLEANER COMPOSITION
DE69425534T2 (en) Mixing process for the formulation of detergents
DE3518100A1 (en) FABRIC SOFTENING POWDERED DETERGENT
EP0013028B1 (en) Detergent with a polydimethyl-siloxane content possessing an anti-foaming activity, and process for its production
AT394864B (en) IN ESSENTIAL WATER-FREE, LIQUID GROWTH DETERGENT AND METHOD FOR THE PRODUCTION THEREOF
DE69227311T2 (en) Detergent compositions
DE2825218A1 (en) LIQUID WASHING OR CLEANING SUPPLIES
EP0560802B1 (en) Process for the production of granular zeolites
EP0623593A2 (en) Process for neutralising the acid form of anionic surfactant, agglomerates and detergent thereby obtained
EP0578659A1 (en) Low-alkaline, chlorine and phosphate-free dishwasher detergents in the form of heavy powders and granulates
EP0354331A1 (en) Detergent additive with improved flushing property
DE19654780B4 (en) bleach activator
DE3518656A1 (en) BLEACHING DETERGENT
DE2535183A1 (en) PROCESS FOR COVERING AND GRANULATING TETRAACETYLGLYCOLURIL AND TETRAACETYLAETHYLENEDIAMINE
EP0473622B1 (en) Granular, phosphate-free additive for detergents, containing non-ionic tensides
DE3644808A1 (en) PHOSPHATE-FREE DETERGENT WITH REDUCED FOAM PRIORITY

Legal Events

Date Code Title Description
PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

AK Designated contracting states

Kind code of ref document: A2

Designated state(s): AT BE CH DE ES FR GB GR IT LI NL

PUAL Search report despatched

Free format text: ORIGINAL CODE: 0009013

AK Designated contracting states

Kind code of ref document: A3

Designated state(s): AT BE CH DE ES FR GB GR IT LI NL

17P Request for examination filed

Effective date: 19900710

17Q First examination report despatched

Effective date: 19920205

GRAA (expected) grant

Free format text: ORIGINAL CODE: 0009210

AK Designated contracting states

Kind code of ref document: B1

Designated state(s): AT BE CH DE ES FR GB GR IT LI NL

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: IT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRE;WARNING: LAPSES OF ITALIAN PATENTS WITH EFFECTIVE DATE BEFORE 2007 MAY HAVE OCCURRED AT ANY TIME BEFORE 2007. THE CORRECT EFFECTIVE DATE MAY BE DIFFERENT FROM THE ONE RECORDED.SCRIBED TIME-LIMIT

Effective date: 19930804

Ref country code: NL

Effective date: 19930804

Ref country code: FR

Effective date: 19930804

Ref country code: BE

Effective date: 19930804

Ref country code: GB

Effective date: 19930804

Ref country code: GR

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 19930804

REF Corresponds to:

Ref document number: 92519

Country of ref document: AT

Date of ref document: 19930815

Kind code of ref document: T

REF Corresponds to:

Ref document number: 3786882

Country of ref document: DE

Date of ref document: 19930909

EN Fr: translation not filed
NLV1 Nl: lapsed or annulled due to failure to fulfill the requirements of art. 29p and 29m of the patents act
GBV Gb: ep patent (uk) treated as always having been void in accordance with gb section 77(7)/1977 [no translation filed]

Effective date: 19930804

PLBI Opposition filed

Free format text: ORIGINAL CODE: 0009260

26 Opposition filed

Opponent name: THE PROCTER & GAMBLE COMPANY

Effective date: 19940504

PLAW Interlocutory decision in opposition

Free format text: ORIGINAL CODE: EPIDOS IDOP

PUAH Patent maintained in amended form

Free format text: ORIGINAL CODE: 0009272

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: PATENT MAINTAINED AS AMENDED

27A Patent maintained in amended form

Effective date: 19961002

AK Designated contracting states

Kind code of ref document: B2

Designated state(s): AT BE CH DE ES FR GB GR IT LI NL

REG Reference to a national code

Ref country code: CH

Ref legal event code: AEN

Free format text: AUFRECHTERHALTUNG DES PATENTES IN GEAENDERTER FORM

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: ES

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 19970113

EN Fr: translation not filed
PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: DE

Payment date: 20061102

Year of fee payment: 20

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: AT

Payment date: 20061113

Year of fee payment: 20

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: CH

Payment date: 20061115

Year of fee payment: 20

REG Reference to a national code

Ref country code: CH

Ref legal event code: PL

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: ES

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 19931130