EP0075818B2 - Activateur de blanchiment granulaire - Google Patents

Activateur de blanchiment granulaire Download PDF

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Publication number
EP0075818B2
EP0075818B2 EP82108646A EP82108646A EP0075818B2 EP 0075818 B2 EP0075818 B2 EP 0075818B2 EP 82108646 A EP82108646 A EP 82108646A EP 82108646 A EP82108646 A EP 82108646A EP 0075818 B2 EP0075818 B2 EP 0075818B2
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EP
European Patent Office
Prior art keywords
water
activator
bleach activator
weight
bleach
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
EP82108646A
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German (de)
English (en)
Other versions
EP0075818B1 (fr
EP0075818A2 (fr
EP0075818A3 (en
Inventor
Karl Prof. Dr. Sommer
Robert Heinz
Albert Dr. Hettche
Johannes Dr. Perner
Werner Schuster
Wolfgang Dr. Trieselt
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.)
BASF SE
Original Assignee
BASF SE
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Publication date
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Priority claimed from DE19813138551 external-priority patent/DE3138551A1/de
Priority claimed from DE19823208216 external-priority patent/DE3208216A1/de
Application filed by BASF SE filed Critical BASF SE
Priority to AT82108646T priority Critical patent/ATE17021T1/de
Publication of EP0075818A2 publication Critical patent/EP0075818A2/fr
Publication of EP0075818A3 publication Critical patent/EP0075818A3/de
Publication of EP0075818B1 publication Critical patent/EP0075818B1/fr
Application granted granted Critical
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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
    • C11D3/3935—Bleach activators or bleach catalysts granulated, coated or protected
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/20—Organic compounds containing oxygen
    • C11D3/22—Carbohydrates or derivatives thereof
    • C11D3/222—Natural or synthetic polysaccharides, e.g. cellulose, starch, gum, alginic acid or cyclodextrin
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/20—Organic compounds containing oxygen
    • C11D3/22—Carbohydrates or derivatives thereof
    • C11D3/222—Natural or synthetic polysaccharides, e.g. cellulose, starch, gum, alginic acid or cyclodextrin
    • C11D3/225—Natural or synthetic polysaccharides, e.g. cellulose, starch, gum, alginic acid or cyclodextrin etherified, e.g. CMC
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/37—Polymers
    • C11D3/3746—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • C11D3/3769—(Co)polymerised monomers containing nitrogen, e.g. carbonamides, nitriles or amines
    • C11D3/3776—Heterocyclic compounds, e.g. lactam
    • 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

Definitions

  • the invention relates to granular bleach activators with a certain grain size for use in detergents or bleaches which contain water-swellable substances as auxiliaries, and to a process for producing these activators.
  • activators which include N- and O-acyl compounds, such as anhydrides or acid amides, and nitriles - a more detailed list is given below - are highly sensitive to hydrolysis, especially in the presence of alkalis which are common in detergents. This problem is exacerbated by the fact that the activators are often poorly soluble in water, which is why they had to be used in finely powdered form for faster dispersibility. It is precisely this finely divided form which, because of the enlarged surface, enables the activators to be hydrolysed during storage.
  • an organic substance or a mixture of organic substances is used as a binding or coating agent, e.g. nonionic surfactants, fatty acids, polymeric materials or detergent.
  • DE-A-26 57 042 discloses a detergent mixture which contains tetraacetylethylene diamine in the form of granulated particles. These particles consist e.g. from said activator and a smaller amount of a nonionic surfactant, which has a melting point of at least 35 ° C.
  • Inorganic substances have also already been used for the purpose in question.
  • GB-A-1 360 427 teaches activator particles which are produced with sodium triphosphate with granulation, and DE-A-28 55 777 granulates activator particles which are composed of a larger proportion of the activator itself and a small proportion of a hydratable salt mixture Combine sodium triphosphate and another salt.
  • granules still have insufficient properties. If they are not yet coated, their storage stability (hydrolysis) is unsatisfactory.
  • the coating limits the rapid dispersibility required in the wash liquor.
  • the use of water as one of the auxiliary substances and the at least partial remaining water in the activator granulate made it very sensitive to temperature and hydrolysis.
  • the water bound in the crystal is e.g. released spontaneously when the transition point is exceeded and leads to the decomposition of the activator granules, as described on page 7 in DE-A-28 55 777.
  • the use of excipients that are readily water-soluble and have the properties of water-hydration binding is justified with the statement that this is the only way to achieve satisfactory, rapid dispersion of the agglomerates under washing conditions.
  • Water-soluble cellulose ethers, starch and starch ethers are described as pelletizing aids for bleach activators in EP-A-0 037 026.
  • DE-A-28 55 777 i.a. water used as an auxiliary for granulating.
  • a small amount of water that has been brought in by the preparation remains in the granulate and immediately destroys part of the stabilization intended by the granulation process.
  • Every suitable method for assembling a bleach activator has two goals. On the one hand, there is an improvement in the hydrolysis stability of the activators, which, regardless of the chemical individual, all have an easily saponifiable active group which must be protected during storage in alkaline washing powder. On the other hand, any suitable method for protecting the bleach activator from the environment must allow the activator to be rapidly dispersed in the wash liquor, i.e. The release of the activator in the finest distribution must take place within a period of time well before the end of the washing cycle so that the bleaching effect can be optimal.
  • the aim of the invention is to arrive at agglomerates composed of ⁇ 300 ⁇ m particles without using water and without using highly water-soluble, highly hydratable compounds, which have the smallest possible inner surface from which no residual water has to be evaporated, and despite these parameters, which were previously known to be prohibitive for good dispersion, spontaneously disperse finely in the wash liquor and during storage compared to the state technology to achieve significantly better storage stability.
  • a further goal was a process which was as simple and economical as possible for producing such granular activators with a coarse particle size which corresponds to that of the other ingredients customary in dry detergents and which is generally 0.5 to 3 mm.
  • the particles generally have a particle size of 0.5 to 3 mm, preferably 0.5 to 2 mm, and are composed of 75 to 95% by weight of a bleach activator substance for per-compounds and 5-25% by weight of at least one water-swellable auxiliary together.
  • Another granular bleach activator with a particle size of 0.5 to 3 mm richly consists of 75 to 95 wt.% Bleach activator substance for per-compounds, 2.5 to 15 wt.% Of a water-swellable auxiliary and 2.5 to 10 wt.% Of an inorganic or organic odorant and / or dispersant together; the sum of the percentages must of course be 100 each.
  • Bleach activators for per compounds are e.g. 0- and N-acylated compounds, such as pentaacetylglucose (PAG), pentapropionylglucose (PPG), tetraacetylethylenediamine (TAED), tetraacetylglycoluril (TAGU), carboxylic acid anhydrides, such as succinic acid, benzoic acid or phthalic anhydride, or else salts, such as mixed sodium anhydride Magnesium diacetyl phosphate (NA-DAP or MGDAP), as well as phenol esters such as p-carboxylphenylacetate, p-sulfonylphenylacetate, p-cresyl acetate or phenyl acetate.
  • PAG pentaacetylglucose
  • PPG pentapropionylglucose
  • TAED tetraacetylethylenediamine
  • the water-swellable auxiliary substance is a substance that does not or only slowly dissolves in water at washing temperatures of at most 70 ° C, but only swellable, i.e. is able to absorb water with a large increase in volume.
  • the granules which consist of a mixture of dust-fine microparticles of the activator substance and the additive, are torn apart under the influence of the water - it is therefore not a nonionic surfactant as an emulsifier or a readily soluble additive with a high hydrate water binding necessary for the dispersion of the particles.
  • the swellable excipient because it acts as a “disintegrant”, causes immediate dispersion.
  • Auxiliaries in the sense of the invention are high-molecular carbohydrates such as starch, pulverized cellulose, wood pulp, as used in the paper industry, or cross-linked polyvinylpyrrolidone (PVP), which is known to be used in the pharmaceutical industry as a tablet disintegrant.
  • Starch or the crosslinked PVP are preferably used, but also starch ethers such as e.g. Carboxymethyl cellulose.
  • the builders and / or dispersants preferably present in the context of the invention are inorganic, such as sodium sulfate, sodium carbonate, then preferably alkali or alkaline earth metal salts of phosphoric acid, oligomeric or polymeric phosphoric acids and organic, such as the alkali metal or alkaline earth metal salts of nitrilotriacetic acid, ethylenediaminetetraacetic acid, Polyacrylic acid, of copolymers of maleic acid with acrylic acid or vinyl ether and carboxymethyl cellulose.
  • the organic acids mentioned can also be used in free form.
  • Nitrilotriacetate, ethylenediamine triacetate, tripolyphosphate, maleic acid-acrylic acid copolymers as sodium salt and carboxymethyl cellulose (CMC) are particularly recommended as dispersants. Mixtures of the substances mentioned can also be used.
  • CMC can be used both as auxiliary b and as component c, i.e. the bleach activator can only contain CMC in addition to the activator substance.
  • the amount of CMC is then to be measured in such a way that the defined percentages for components a and b are taken into account, i.e. In this case, 5 to 25% by weight of CMC is contained in the bleach activator.
  • the combination also results in a compact that is easily dispersed in the wash liquor within a few minutes.
  • the particle size of the dispersed particles is in the same size arrangement; Surprisingly, the coarse proportion even drops significantly compared to that of the fine powder used in the compaction.
  • the granular activator is produced by compacting the mixture of the individual components.
  • the method of pelletizing or granulating build-up fails in this case because no binder and no water is present, which, for. B. when using the above-mentioned phosphates - they are sprayed in an aqueous solution onto the material to be granulated - or is also required when using starch or cellulose ethers.
  • the granular activator is produced in detail, for example, in such a way that a homogeneous mixture of the powdered auxiliary, the powdered activator substance and possibly the powdered builders and / or dispersant, in which the activator particles generally have a particle size of approx. Have 10 to 300 microns, manufactures and compacted.
  • the compacting can be carried out in such a way that the aforementioned powder mixture by means of a stuffing screw into the gap between two rollers rotating against each other and pressed between the rollers.
  • the resulting band (“Schülpe") is broken on a shredder and limited to the desired grain size (0.5 to 3 mm) on a sieve shredder.
  • the material, the particle size of which lies outside the desired limits, is separated off and returned to the compactor together with another mixture to be compacted.
  • the resulting granular activator is surprisingly very stable in storage, as we have been able to determine, which could not be expected, since the insoluble and only water-swellable auxiliaries do not have any protective functions (coating) against the activator substances in the sense as described in the previous ones Publications should be the case.
  • the storage stability is in many cases even better, which was shown by the improved bleaching effect of the activators according to the invention which have been stored for a long time compared to activators of the prior art which have been stored for the same time. Even an increased activity can be achieved by adding component c.
  • the test washing powder has the following composition:
  • the degrees of whiteness were measured with the Zeiss ELREPHO device with filter 8, xenon lamp with FL 46.
  • Examples 1-7 relate to washing powders W ° , W 100 , W 3 , W 4 ... W 7
  • a test washing powder is produced by mixing a tower powder with 10% perborate and so much calf bleach activator that 8% activator is 100% contained in the detergent. Make up to 100% detergent with 33% sodium sulfate. When using ready-made cold bleach activator, the dispersant is offset against the 33% sodium sulfate.
  • test washing powder has the following composition:
  • each of the washing powder mixtures W x thus produced are stored in open petri dishes in a climate controlled cabinet at 40 ° C. and 7 6% relative atmospheric humidity.
  • the bleaching effect is determined immediately after mixing and after 21, 42 and 84 days of storage.
  • the three different test fabrics each washed for 30 min at room temperature, 25 to 45 ° C and 35 to 60 ° C give 9 values after whiteness measurement, which are added up. Through this sum formation and through double determination, the values achieve a sufficient degree of reliability.
  • the degrees of whiteness were measured with the ELREPHO device from Zeiss with filter 8, xenon lamp with FL 46.
  • the difference in the sums of whiteness from W 100 and Wo corresponds to 100% activation.
  • the activation in% of a mixture is calculated according to the following formula ⁇ W x should be the sum of the degrees of whiteness of the detergent mixture W x , ⁇ W ° and ⁇ W 100 are the sums of the degrees of whiteness of the two previously described mixtures with zero and 100% activation.
  • a mixture of 90 parts of tetraacetylethylene diamine (TAED) with a special particle size distribution1, 5 parts of corn starch and 5 parts of sodium tripolyphosphate is homogenized in a continuously running Lödige mixer, fed to a roller press by means of a feed screw and compacted into flakes. The scoop is crushed in a hammer mill. Subsequent fractionation leads to a useful fraction with a particle size between 0.5 and 2 mm in diameter. Oversize and undersize granules are used for grinding or compacting.
  • TAED tetraacetylethylene diamine
  • the grit granules described in Examples 12 to 15 were then incorporated into a test washing powder according to the test method described and tested for its activating effect. As a result, the washing results were evaluated in the degree of whiteness of the different soiled fabrics washed at different temperatures. The whiteness which was obtained with a detergent (tower powder + perborate) + TAED, example 20 and PAG, example 21 was evaluated as 100% whiteness. The% activation after storage was calculated according to the formula given above.
  • Coarse cold bleach activators have a surface that is too small, moreover they can lead to fiber damage together with perborate even in unfavorable cases if they are deposited in the laundry. For all these reasons, the spontaneous dispensing of the agglomerates, be they mixer granules or compactates, in the wash liquor is required.
  • the compactates described here behave just as favorably as the mixer granules when dispersing. They even have an advantage.
  • the bulk of the output activator, which has a diameter of> 200 ⁇ m, is still crushed by the compacting, ie it becomes smaller.
  • Table IV shows the dispersion times and the particle size distribution of some examples.

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  • Chemical & Material Sciences (AREA)
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  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Wood Science & Technology (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Molecular Biology (AREA)
  • Emergency Medicine (AREA)
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  • Detergent Compositions (AREA)

Claims (6)

1. Activateur du blanchiment granulaire pour utilisation dans une composition de lavage ou de blanchiment, dont les particules possèdent une granulométrie de 0,5 à 3 mm, sont composées de
a) 75 à 95% en poids d'au moins une substance d'activation du blanchiment pour per-composés et
b) 5 à 25% en poids d'au moins un adjuvant gonflable au contact de l'eau, et sont préparées en mélangeant, de façon homogène, sans addition d'eau, les composants a) et b), sous forme pulvérulente, dans laquelle les particules d'activateur (a) ont une grosseur d'environ 10 à 300 pm, en compactant le mélange, sans introduction d'eau, entre deux cylindres tournant en sens inverse et en broyant ensuite la masse compactée.
2. Activateur du blanchiment granulaire pour utilisation dans une composition de lavage ou de blanchiment, dont les particules possèdent une granulométrie de 0,5 à 3 mm, sont composées de
a) 75 à 95% en poids d'au moins une substance d'activation du blanchiment pour per-composés
b) 2,5 à 15% en poids d'au moins un adjuvant gonflable à l'eau et
c) 2,5 à 10% en poids d'au moins un produit de soutien et/ou agent dispersant, inorganique ou organique et préparé en mélangeant, de façon homogène, sans addition d'eau, les composants a), b) et c), sous forme pulvérulente, dans laquelle les particules d'activateur (a) ont une grosseur d'environ 10 à 300 m, en compactant le mélange, sans introduction d'eau, entre deux cylindres tournant en sens inverses et en broyant ensuite la masse compactée.
3. Activateur du blanchiment suivant la revendication 1 ou 2, dans lequel l'adjuvant b) est de la polyvinylpyrrolidone réticulée ou un hydrate de carbon à poids moléculaire élevé.
4. Activateur du blanchiment suivant les revendications 2 ou 3, dans lequel le composant c est choisi parmi les sels de métaux alcalins et alcalino-terreux de l'acide phosphorique, les acides phosphoriques oligomères et polymères, les sels de métaux alcalins et alcalinoterreux de l'acide nitrilo-triacétique, de l'acide éthylène-diamine-tétracétique, de l'acide poly-acrylique, de copolymères de l'acide maléique et de l'acide acrylique ou d'éther vinylique, les acides organiques libres eux-mêmes et la carboxyméthyl- cellulose.
5. Procédé de préparation d'activateurs du blanchiment granulaires selon les revendications 1 ou 3 pour utilisation dans une composition de lavage ou de blanchiment, dont les particules possèdent une granulométrie de 0,5 à 3 mm et sont composées de:
a) 75 à 95% en poids d'une substance d'activation du blanchiment pour per-composés et
b) 5 à 25% en poids d'au moins un adjuvant gonflable à l'eau, caractérisé par le fait que l'on mélange, de façon homogène, sans addition d'eau, les composants a), b), c), sous forme pulvérulente, dans laquelle les particules d'activateur (a) ont une grosseur d'environ 10 à 300 m, qu'on compacte le mélange, sans introduction d'eau, entre deux cylindres tournant en sens inverses, qu'on broie ensuite la masse compactée et qu'on sépare, de manière connue en soi, la partie ayant une grosseur de particules de 0,5 à 3 mm.
6. Procédé de préparation d'activateurs du blanchiment granulaires selon les revendications 2, 3 et 4 pour utilisation dans une composition de lavage ou de blanchiment, dont les particules possèdent une granulométrie de 0,5 à 3 mm et sont composées de:
a) 75 à 95% en poids d'une substance d'activation du blanchiment pour per-composés et
b) 2,5 à 15% en poids d'un adjuvant gonflable à l'eau
c) 2,5 à 10% en poids d'un produit de soutien inorganique ou organique et/ou un agent dispersant, caractérisé par le fait que l'on mélange, de façon homogène, sans addition d'eau, les composants a), b), c), sous forme pulvérulente, dans laquelle les particules d'activateur (a) ont une grosseur d'environ 10 à 300 um, qu'on compacte le mélange, sans introduction d'eau, entre deux cylindres tournant en sens inverses, qu'on broie ensuite la masse compactée et qu'on sépare, de manière connue en soi, la partie ayant une grosseur de particules de 0,5 à 3 mm.
EP82108646A 1981-09-28 1982-09-18 Activateur de blanchiment granulaire Expired - Lifetime EP0075818B2 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AT82108646T ATE17021T1 (de) 1981-09-28 1982-09-18 Koerniger bleichaktivator.

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
DE19813138551 DE3138551A1 (de) 1981-09-28 1981-09-28 Koerniger bleichaktivator
DE3138551 1981-09-28
DE19823208216 DE3208216A1 (de) 1982-03-06 1982-03-06 Koerniger bleichaktivator
DE3208216 1982-03-06

Publications (4)

Publication Number Publication Date
EP0075818A2 EP0075818A2 (fr) 1983-04-06
EP0075818A3 EP0075818A3 (en) 1984-03-07
EP0075818B1 EP0075818B1 (fr) 1985-12-18
EP0075818B2 true EP0075818B2 (fr) 1990-03-14

Family

ID=25796390

Family Applications (1)

Application Number Title Priority Date Filing Date
EP82108646A Expired - Lifetime EP0075818B2 (fr) 1981-09-28 1982-09-18 Activateur de blanchiment granulaire

Country Status (5)

Country Link
US (1) US4695397A (fr)
EP (1) EP0075818B2 (fr)
CA (1) CA1217301A (fr)
DE (1) DE3268039D1 (fr)
ES (1) ES8501794A1 (fr)

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GB8606804D0 (en) * 1986-03-19 1986-04-23 Warwick International Ltd Particulate bleach activator composition
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US4883833A (en) * 1988-06-15 1989-11-28 Hughes Ronald E Process for producing a dry granular product
US5269962A (en) * 1988-10-14 1993-12-14 The Clorox Company Oxidant composition containing stable bleach activator granules
DE3843195A1 (de) * 1988-12-22 1990-06-28 Hoechst Ag Verfahren zur herstellung eines lagerstabilen, leicht loeslichen bleichaktivator-granulats
KR920703439A (ko) * 1989-08-19 1992-12-17 원본미기재 과 붕산염 일수화물의 과립화 방법
DE4014978A1 (de) * 1990-05-10 1991-11-14 Basf Ag Verfahren zur herstellung einer koernigen bleichaktivatorzusammensetzung
DE4024759A1 (de) * 1990-08-03 1992-02-06 Henkel Kgaa Bleichaktivatoren in granulatform
US5458801A (en) * 1991-09-27 1995-10-17 Kao Corporation Process for producing granular bleach activator composition and granular bleach activator composition
US5259994A (en) * 1992-08-03 1993-11-09 The Procter & Gamble Company Particulate laundry detergent compositions with polyvinyl pyrollidone
DE4242482A1 (de) * 1992-12-16 1994-06-23 Henkel Kgaa Verfahren zur Herstellung von pulverförmigen Waschmitteln
DE4439039A1 (de) * 1994-11-02 1996-05-09 Hoechst Ag Granulierte Bleichaktivatoren und ihre Herstellung
DE19641708A1 (de) 1996-10-10 1998-04-16 Clariant Gmbh Verfahren zur Herstellung eines gecoateten Bleichaktivatorgranulats
DE19651415A1 (de) * 1996-12-11 1998-06-18 Henkel Ecolab Gmbh & Co Ohg Verfahren zur Instrumentendesinfektion
DE19758811B4 (de) 1997-03-11 2008-12-18 Henkel Ag & Co. Kgaa Waschmittelpressling
DE19710254A1 (de) * 1997-03-13 1998-09-17 Henkel Kgaa Wasch- oder reinigungsaktive Formkörper für den Gebrauch im Haushalt
DE19740668A1 (de) 1997-09-16 1999-03-18 Clariant Gmbh Lagerstabiles Bleichaktivator-Granulat
DE19740671A1 (de) * 1997-09-16 1999-03-18 Clariant Gmbh Bleichaktivator-Granulate
GB2345701A (en) * 1999-01-12 2000-07-19 Procter & Gamble Particulate bleaching components
EP1035196B1 (fr) * 1999-03-05 2001-10-31 Rohm And Haas Company Compositions améliorés en forme boulettes
DE19912031A1 (de) * 1999-03-17 2000-09-21 Basf Ag Verwendung von quervernetztem Polyvinylpyrrolidon zur Erhöhung der Zerfallgeschwindigkeit von kompakten teilchenförmigen Wasch- und Reinigungsmitteln
US7765133B1 (en) * 2000-02-16 2010-07-27 Omgeo Llc System for facilitating trade processing and trade management
US7550156B2 (en) 2001-11-23 2009-06-23 Rohm And Haas Company Optimised pellet formulations
GB0710559D0 (en) * 2007-06-02 2007-07-11 Reckitt Benckiser Nv Composition
DE102007059970A1 (de) * 2007-12-11 2009-09-10 Henkel Ag & Co. Kgaa Reinigungsmittel
GB0901207D0 (en) * 2009-01-26 2009-03-11 Innospec Ltd Chelating agents and methods relating thereto

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Publication number Priority date Publication date Assignee Title
DE2048331A1 (de) * 1970-10-01 1972-04-06 Henkel & Cie GmbH, 4000 Dusseldorf Feste, pulverförmige bis kornige Mittel zur Herstellung von kaltwirksamen Bleich flotten, insbesondere von kaltwirksamen blei chenden Waschlaugen, und Verfahren zur Her stellung dieser Mittel
GB1573406A (en) * 1975-12-18 1980-08-20 Unilever Ltd Bleaching detergent compositions
NL180122C (nl) * 1977-12-22 1987-01-02 Unilever Nv Bleekactivator in granulaatvorm.
DE3011998C2 (de) * 1980-03-28 1982-06-16 Henkel KGaA, 4000 Düsseldorf Verfahren zur Herstellung eines lagerstabilen, leichtlöslichen Granulates mit einem Gehalt an Bleichaktivatoren
ATE12517T1 (de) * 1980-12-09 1985-04-15 Unilever Nv Bleichmittelaktivatorgranulate.

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ES515965A0 (es) 1984-12-01
CA1217301A (fr) 1987-02-03
DE3268039D1 (en) 1986-01-30
EP0075818B1 (fr) 1985-12-18
EP0075818A2 (fr) 1983-04-06
ES8501794A1 (es) 1984-12-01
EP0075818A3 (en) 1984-03-07
US4695397A (en) 1987-09-22

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