EP0741776B1 - Cogranulate und daraus geformte reinigungsmittel-tabletten - Google Patents

Cogranulate und daraus geformte reinigungsmittel-tabletten Download PDF

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Publication number
EP0741776B1
EP0741776B1 EP95907583A EP95907583A EP0741776B1 EP 0741776 B1 EP0741776 B1 EP 0741776B1 EP 95907583 A EP95907583 A EP 95907583A EP 95907583 A EP95907583 A EP 95907583A EP 0741776 B1 EP0741776 B1 EP 0741776B1
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EP
European Patent Office
Prior art keywords
acid
alkali metal
granule
granules
detergent
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EP95907583A
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English (en)
French (fr)
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EP0741776A1 (de
EP0741776B2 (de
Inventor
François Delwel
James William Gordon
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Unilever PLC
Unilever NV
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Unilever PLC
Unilever NV
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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
    • C11D11/00—Special methods for preparing compositions containing mixtures of detergents
    • C11D11/02—Preparation in the form of powder by spray drying
    • 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
    • C11D17/0047—Detergents in the form of bars or tablets
    • C11D17/0065—Solid detergents containing builders
    • C11D17/0073—Tablets
    • C11D17/0091—Dishwashing tablets
    • 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
    • C11D17/06—Powder; Flakes; Free-flowing mixtures; Sheets
    • C11D17/065—High-density particulate detergent compositions
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/20—Organic compounds containing oxygen
    • C11D3/2075—Carboxylic acids-salts thereof
    • C11D3/2082—Polycarboxylic acids-salts thereof
    • 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
    • C11D3/2075—Carboxylic acids-salts thereof
    • C11D3/2086—Hydroxy carboxylic acids-salts thereof
    • 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
    • C11D3/3703—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • C11D3/3719—Polyamides or polyimides
    • 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
    • C11D3/3757—(Co)polymerised carboxylic acids, -anhydrides, -esters in solid and liquid compositions
    • C11D3/3761—(Co)polymerised carboxylic acids, -anhydrides, -esters in solid and liquid compositions in solid compositions
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/37—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

Definitions

  • This invention relates to co-granules useful in detergent compositions, and to the preparation of such co-granules.
  • the invention further relates to compacted forms of product produced from the granules, e.g. detergent tablets. More particularly, the invention relates to co-granules and tablets formed therefrom, especially of and for the use in automatic dishwashing compositions.
  • co-granules means granules comprising more than one compound or component of an overall cleaning system.
  • granule is to be interpreted broadly and is intended to embrace various particulate forms such as granulate, coarse powder, tablets and noodles.
  • tablette is to be construed as meaning a discretely shaped solid body of material, of which the shape and dimensions may vary with the application envisaged, and which may for example have a weight in the range of from about 1 to about 100 grams, preferably from about 10 to about 50 grams.
  • Dishwashing compositions are frequently made up from granules of one particular inorganic compound such as e.g. alkali silicate and these compositions often contain other ingredients, especially organic compounds for example, in the form of different particles.
  • the silicate granules for instance often dissolve only with difficulty and they lead to the formation of fines (dust).
  • the dissolution problem is aggravated by the fact that silicate granules having a SiO 2 :Na 2 O molar ratio between 1.8 and 3.0 and a moisture content of below about 18% dissolve only with considerable difficulty.
  • alkali silicate granules with a homogeneous distribution of moisture are difficult to obtain, often as a consequence of the drying process, since less moisture tends to be present in the outer skin and more in the inside of the granules. This also reduces the solubility of the granules during use.
  • the preparation of granules of builder materials e.g. phosphate-replacing builders like di-, tri- or tetracarboxylic acid and salts thereof, is difficult and therefore relatively expensive. The economics of granule manufacturing processes are therefore important.
  • Co-granules useful in detergent compositions are known inter alia from EP-A-0421664 (Rohm and Haas Company), which discloses a polymer-containing granulate containing at least 20% by weight of polymer and at least 20% by weight of a water-soluble inorganic compound. Such compounds are preferably sulphates, carbonates or silicates.
  • other phosphate-replacing builders may also be present, such as zeolites, carbonates, nitrilotriacetic acid, citric acid, tartaric acid, salts thereof, phosphonates etc.
  • the examples in the reference disclose granules containing polymer and sodium sulphate or sodium carbonate.
  • EP-A-0561452 discloses phosphate-free machine dishwashing compositions comprising a polyamino acid and an anti-scaling agent.
  • Various builder salts may be included in the disclosed compositions, including preferably citrates, alkenylsuccinates, carbonates, bicarbonates, zeolites and mixtures thereof, but the amount of a carbonate and/or bicarbonate builder in the composition is limited to 50% by weight.
  • CH-A-673033 discloses phosphate- and trisodiumnitriloacetate-freealkalinemachinedishwashing compositions comprising sodium citrate, at least one sodium salt of hydroxyethanediphosphonic acid and at least one sodium silicate.
  • JP-A-49076905 discloses spray-dried powder detergents comprising, inter alia, inorganic and organic builder salts.
  • a salt selected from a polyphosphate, carbonate, sulphate, silicate and/or sodium citrate.
  • JP-A-54106509 discloses the preparation of spray-dried granulated detergent compositions comprising a surfactant, an alkali metal silicate salt and a phosphate salt.
  • a surfactant an alkali metal silicate salt
  • a phosphate salt a surfactant that is added to the silicate.
  • the SiO 2 :M 2 O molar ratio in the silicate is controlled using an acid type surfactant or an organic acid such as citric acid.
  • EP-A-0526978 for instance is disclosed the simultaneous drying and granulation of silicates in a turbine dryer, e.g. a turbogranulation dryer ex. Vomm-Turbo Technology, VOMM IMPIANTI E PROCESSI S.r.l., Milan, Italy.
  • a turbine dryer e.g. a turbogranulation dryer ex. Vomm-Turbo Technology, VOMM IMPIANTI E PROCESSI S.r.l., Milan, Italy.
  • this dryer is less suited for the combined drying and granulation to produce co-granules containing substantial quantities of organic ingredients in conjunction with silicate. Due to the high attrition between the rotating blades and the film formed on the wall during the granulation phase, local overheating can cause partial decomposition of the organic ingredients, leading to (local-) colouring.
  • Drying can also conveniently be achieved by spray drying a slurry by a conventional technique using a spray tower in which the slurry is atomized and dried in a hot air stream.
  • spray drying must be followed by a granulation step (e.g. using a Lödige Ploughshare mixer), optionally after milling.
  • a granulation step e.g. using a Lödige Ploughshare mixer
  • For granulation usually a small amount of moisture is added.
  • the powders obtained in a turbine dryer generally have a wider particle size distribution as part of the product gathers at the walls, creating larger particles. Furthermore powder particles obtained in a turbine dryer are less homogeneously dried as a result of the larger particles being more effectively dried at the outside than on the inside and as a result of the difference in residence time between particles remaining in the gas stream and those sticking on the (heated) wall of the dryer.
  • Dishwashing tablets are frequently produced from a mixture containing granules of one particular inorganic compound, such as e.g. alkali metal silicate, and additionally other ingredients, such as organic builder salts, as separate particles.
  • one particular inorganic compound such as e.g. alkali metal silicate
  • other ingredients such as organic builder salts, as separate particles.
  • binder material that can hold the tablet ingredients together so as to obtain stronger tablets.
  • binding material has a negative influence on the rate of tablet dissolution such that cleaning performance during the washing cycle may be deteriorated.
  • detergent tablets can more easily be formed if a fine grade or powder-form builder salt, such as sodium citrate, is used instead of the granular grades of sodium citrate that are normally used in machine dishwashing powders.
  • a fine grade or powder-form builder salt such as sodium citrate
  • increasing the level of fine citrate leads to poor flow properties of the base powder and, thus to poor die filling during the tabletting process. As a consequence of this, a large variation in individual tablet weights is obtained.
  • the present invention provides.
  • a homogeneous co-granule comprising:
  • the invention also provides a process for the preparation of the above-defined co-granules, comprising preparing a slurry or solution of the ingredients of the co-granules, drying the mixture using any of various suitable known techniques, and granulating the resulting material.
  • the present invention provides a detergent composition comprising at least 25% by weight, preferably at least 40% by weight, more preferably at least 50% by weight, of co-granules according to the first aspect of the invention.
  • the detergent composition comprises a bleach system and/or an enzyme system.
  • the detergent composition is formed from the co-granules, with or without other ingredients.
  • the present invention provides a detergent tablet comprising from about 25 to about 100% by weight, preferably from about 25 to about 90% by weight, of co-granules according to the first aspect of the invention.
  • the tablet includes a bleaching system and/or an enzyme system.
  • the present invention further provides the use of a co-granule containing granular detergent composition or detergent tablet according to the invention, in a machine dishwashing process.
  • the salt of a di-, tri- or tetracarboxylic acid is an alkali metal salt of citric acid, mellitic acid, oxydisuccinic acid, carboxymethoxysuccinic acid, malonic acid, dipicolinic acid or alkenyl succinic acid.
  • Part of the di-, tri- and tetracarboxylic acid component e.g. up to about 30%, may if desired be replaced by a lower hydroxy monocarboxylic acid, e.g. lactic acid.
  • Partial salts of the di-, tri- or tetracarboxylic acid in which one or more of the hydrogen ions of the carboxylic groups are replaced by metal ions are particularly useful. Especially sodium and potassium salts can be used with good results for the purpose of the invention. Potassium salts are sometimes preferred because of their higher solubility.
  • alkali metal citrate, especially sodium citrate, in the co-granules according to the present invention is preferred.
  • the use of sodium oxydisuccinate is also preferred.
  • the inorganic salt component of the co-granule of the invention is selected from alkali metal silicate, alkali metal carbonate or bicarbonate, alkali metal sesquicarbonate, alkali metal sulphate, alkali metal tripolyphosphate and mixtures thereof.
  • Alkali metal disilicates, in particular sodium disilicate, are especially preferred.
  • the co-granule material also comprises at least one polymeric compound, being either acid and/or salt, selected from the group consisting of polycarboxylic acid polymers and polypeptides.
  • Suitable polycarboxylic acid polymers comprise e.g. a water-soluble homopolymer or copolymer having a molecular weight of at least 500. It may be derived from a monocarboxylic acid or from a di-, tri- or polycarboxylic acid. The polymer will normally be used in the form of its water-soluble alkali metal salt.
  • One group of polymer materials found to be of value comprises homopolymers derived from a monomer of the formula: wherein R 1 is hydrogen, hydroxyl, C 1 -C 4 alkyl or alkoxy, acetoxy, or -CH 2 COOM; R 2 is hydrogen, C 1 -C 4 alkyl or -COOM and M is an alkali metal.
  • R 1 is hydrogen, hydroxyl, C 1 -C 4 alkyl or alkoxy, acetoxy, or -CH 2 COOM
  • R 2 is hydrogen, C 1 -C 4 alkyl or -COOM
  • M is an alkali metal.
  • this group include the sodium and potassium salts of polyacrylic, polymethacrylic, polyitaconic, polymaleic and polyhydroxyacrylic acids and also the hydrolysis products of the corresponding polymerised acid anhydrides.
  • the polymer obtained by hydrolysis of maleic anhydride falls within this group.
  • a second group of suitable polymeric materials comprises the copolymers of two or more carboxylic monomers of the above formula.
  • this group include the sodium and potassium salts of copolymers of maleic anhydride with acrylic acid, methacrylic acid, crotonic acids, itaconic acid and its anhydride and/or aconitic acid.
  • a third group of suitable polymeric materials comprises the copolymers of one carboxylic monomer of the above formula and two or more non-carboxylic acid monomers such as ethylene, propylene, styrene, alpha-methylstyrene, acrylonitrile, acrylamide, vinylacetate, methylvinylketone, acrolein and esters of carboxylic acid monomers such as ethyl acrylate and methacrylate.
  • non-carboxylic acid monomers such as ethylene, propylene, styrene, alpha-methylstyrene, acrylonitrile, acrylamide, vinylacetate, methylvinylketone, acrolein and esters of carboxylic acid monomers such as ethyl acrylate and methacrylate.
  • Suitable polypeptides which can be incorporated in the co-granules according to the present invention include for example poly-aspartate and polyglutamate.
  • One of the advantages of incorporating such an inorganic salt as mentioned above into the co-granule of the invention is that it increases the solubility of the co-granule, especially if the co-granule contains silicates with SiO 2 :Na 2 O >2.4, because these salts dissolve rapidly and thereby convert the co-granule into an open sponge-like structure so that the surface area of the co-granule is increased. This leads to an increase of the solubility of the remaining solid material of the co-granule.
  • Most of the salts also act as a builder, reinforcing detergent activity.
  • Non-phosphate inorganic salts such as various carbonates, especially alkali metal carbonate/bicarbonate/sesquicarbonate are preferred.
  • the inorganic salts are usually present in the form of their lower stable hydrate(s).
  • the co-granule has the following composition (I) or alternatively the following compositions (II) or (III) (all amounts being approximate):
  • the organic phosphonates which can be present in the co-granule include for example those of the Dequest R range, which are especially added as builders to phosphate-free machine dishwashing compositions.
  • a drawback of these polymers however is that some of them are not quite biodegradable and are therefore environmentally less acceptable. Therefore some of the polyphosphonates, whilst being effective, are less acceptable as being P-containing products.
  • adjunct materials commonly found in cleaning compositions, such as: enzyme stabilizers, such as the poly-alcohols, e.g. glycerol, and borax; anti-scaling agents; corrosion inhibitors, e.g. zinc salts, aluminium salts, benzotriazole, etc; crystal-growth inhibitors; threshold agents; thickening agents; anionic surfactants; perfumes and dyestuffs; preservatives.
  • enzyme stabilizers such as the poly-alcohols, e.g. glycerol, and borax
  • anti-scaling agents such as the poly-alcohols, e.g. glycerol, and borax
  • corrosion inhibitors e.g. zinc salts, aluminium salts, benzotriazole, etc
  • crystal-growth inhibitors e.g. zinc salts, aluminium salts, benzotriazole, etc
  • threshold agents e.g. zinc salts, aluminium salts, benzotriazole, etc
  • a small amount of preferably low- to non-foaming nonionic surfactant which includes any alkoxylated nonionic surface-active agent wherein the alkoxy moiety is selected from the group consisting of ethylene oxide, propylene oxide and mixtures thereof, is preferably used to improve the detergency and to suppress excessive foaming due to protein soil.
  • an excessive proportion of nonionic surfactant should be avoided.
  • an amount of up to 7% by weight e.g. 0.1 to 5% by weight, preferably from 0.5 to 4% by weight, is quite sufficient.
  • nonionic surfactants for use in the co-granule material of the invention are the low- and non-foaming ethoxylated straight-chain alcohols of the Plurafac R RA series, supplied by the Eurane Company; of the Lutensol R LF series, supplied by the BASF Company and of the Triton R DF series, supplied by the Rohm & Haas Company.
  • co-granules are preferred which have an average particle size of from about 100 to about 1500 ⁇ m. More particularly there is a preference for co-granules having an average particle size of from about 300 to about 900 ⁇ m especially from about 500 to about 700 ⁇ m, and a Rosen Rammler N-value above about 2.5. Particle size determination and the definition and determination of the Rosen Rammler N-value are described in detail in "Small Particle Statistics" by Herdan, E; second revised edition; Butterworth, London 1960, in particular pp 86-101. Graph paper according to DIN 1171 (new) is often used to determine the N-value.
  • the present invention also provides, within its first aspect, a process for the preparation of the co-granules, which process comprises preparing a slurry of the ingredients of the co-granule and drying the mixture by means of suitable equipment, e.g. a turbine dryer such as a turbogranulation drier ex Vomm-Turbo Technology, Vomm Impianti E Processi S.r.l., Milan, Italy.
  • suitable equipment e.g. a turbine dryer such as a turbogranulation drier ex Vomm-Turbo Technology, Vomm Impianti E Processi S.r.l., Milan, Italy.
  • An alternative to drying using a turbine drier, and especially preferred, is spray-drying the slurry by a conventional technique using a spray tower in which the slurry is atomized and dried in a hot air stream.
  • the resulting particles may be milled and/or restructured, for example in a granulation process, e.g. using a Lödige recycler, a Lödige plough share mixer, or any other suitable apparatus, such as a twin roll compactor. Any restructuring stage does not need to be limited to the material produced by spray-drying and optionally then milled, which is used as an example only.
  • the granulation process involves combining fine solid particles like citrate, carbonates, sulphate, silicates, tripolyphosphate or co-granules as described above.
  • Heat sensitive components of the granules e.g. sodium bicarbonate
  • Minor ingredients that are used in the final powder or granulate formulation that are available in liquid or fine powder form e.g. surfactant, perfume, dyes, organic phosphonate, corrosion inhibitors, may also be added as required.
  • Turbine driers usually operate at around 300°C.
  • the slurry is sprayed onto fine (recycled) particles and dried to form gradually growing co-granules.
  • Particularly favoured are processes that separate fine particles from the coarser ones, preferably continuously, and recirculate the fines to the fluidized bed for further spraying-on. Particles of the desired size can then be separated from the process at the appropriate time.
  • Suitable equipment for continuous drying and granulation is e.g. an AGT-unit ex Glatt-GmbH/Process Technology, Binzen, Lorrach, Germany.
  • the co-granules of this aspect of the invention have a bulk density of at least about 700 g/dm 3 , more preferably above about 800 g/dm 3 , and most preferably a bulk density between about 900 g/dm 3 and about 1200 g/dm 3 .
  • High bulk densities are desirable at present, to be able to provide final detergent compositions with a relatively high specific weight.
  • the present invention also provides, in a second aspect, a detergent composition which comprises at least about 25% by weight, preferably at least about 40% by weight, more preferably at least about 50% by weight of co-granules according to the first aspect of the invention.
  • the composition includes a bleach system and/or an enzyme system, which usually may be added to the co-granules in the form of separate particles which may have the same particle size distribution as the co-granules. Also it is usually advantageous if the bulk density of the bleach/enzyme particles is comparable to that of the co-granules.
  • Preferred forms of detergent composition consist of at least about 50% by weight of the co-granules and less than about 30% by weight of a bleach system and an enzyme system.
  • the detergent composition is non-irritant.
  • Enzymes are used for many purposes in various fields where biochemical reactions occur.
  • an enzyme can be described as a catalyst capable of permitting a biochemical reaction to quickly occur and can be classified according to the type of reaction they catalyze.
  • Enzymes are characterized by high specificity; that is to say, each enzyme can catalyze a single reaction of one substance or a very small number of closely related substances.
  • enzymes suitable for use in the cleaning compositions of this invention include lipases, peptidases, amylases (amylolytic enzymes) and others which degrade, alter or facilitate the degradation or alteration of biochemical soils and stains encountered in cleansing situations so as to remove more easily the soil or stain from the object being washed or to make the soil or stain more removable in a subsequent cleansing step. Both degradation and alteration can improve soil removability.
  • lipases are classified as EC class 3, hydrolases subclass EC 3.1, preferably carboxylic ester hydrolases EC 3.1.1.
  • lipases EC 3.1.1.3 with the systematic name glycerol ester hydrolases are lipases EC 3.1.1.3 with the systematic name glycerol ester hydrolases.
  • Amylases belong to the same general class as lipases, subclass EC 3.2, especially EC 3.2.1 glycose hydrolases such as 3.2.1.1. alpha-amylase with the systematic name alpha-1,4-glucan-4-glucanohydrolase; and also 3.2.1.2, beta-amylase with the systematic name alpha-1,4-glucan maltohydrolase.
  • Proteases belong to the same class as lipases and amylases, subclass EC 3.4, particularly EC 3.4.4 peptide peptido-hydrolases such as EC 3.4.4.16 with the systematic name subtilopeptidase A.
  • enzyme-containing embodiments of compositions according to the invention Enzymes serving different functions can also be used in the practice of this aspect of the invention, the selection depending upon the composition of biochemical soil, intended purpose of a particular composition, and the availability of an enzyme to degrade or alter the soil.
  • Lipases sometimes called esterases, hydrolyze fatty soils.
  • Lipases suitable for use herein include those of animal, plant and microbiological origin. Suitable lipases are also found in many strain of bacteria and fungi.
  • lipases suitable for use herein can be derived from Pseudomonas, Aspergillus, Pneumococcus, Staphylococcus, Toxins, Mycobacterium Tuberculosis, Mycotorula Lipolytica, and Sclerotinia microorganisms, and can be made using recombinant DNA manufacturing techniques.
  • Suitable animal lipases are found in the body fluids and organs of many species.
  • a preferred class of animal lipase herein is the pancreatic lipase.
  • Lipase may be employed in the present cleaning compositions in an amount of from about 0.005% to about 10%, preferably from about 0.01 to about 5% by weight of the composition, on a pure enzyme basis.
  • the enzyme most commonly used in machine dishwashing compositions are amylolytic enzymes.
  • amyloltic enzymes for use in the present invention can be those derived from bacteria or fungi.
  • Preferred amylolytic enzymes are those prepared and described in GB-A-1,296,839, cultivated from the strains of Bacillus licheniformis NCIB 8061, NCIB 8059, ATCC 6334, ATCC 6598, ATCC 11 945, ATCC 8480 and ATCC 9945 A.
  • Examples of such amylolytic enzymes are amylolytic enzymes produced and distributed under the trade name of SO-95 R or Termamyl R by Novo Industria A/S, Copenhagen, Denmark. These amylolytic enzymes are generally presented as granules and may have enzyme activities of from about 2 to 10 Maltose units/milligram.
  • amylolytic activity can be determined by the method as described by P.Bernfeld in "Method of Enzymology", Vol. I (1955), page 149.
  • composition of this aspect of the invention preferably also contains a proteolytic enzyme.
  • subtilisins which are obtained from particular strains of B. subtilis and B. licheniformis, such as the commercially available subtilisins Maxatase R , supplied by Gist-Brocades N.V., Delft, Holland, and Alcalase R , supplied by Novo Industri A/S, Copenhagen, Denmark.
  • protease obtained from a strain of Bacillus having maximum activity throughout the pH range of 8-12, being commercially available from Novo Industri A/S under the registered trade names of Esperase R and Savinase R .
  • the preparation of these and analogous enzymes is described in GB-A-1243784.
  • protease useful herein is a fairly recent commercial product sold by Novo Industri A/S under the trade name Durazym R , as described in WO-A-89/06279.
  • the enzymes are generally presented as granules, e.g. marumes, prills, T-granules etc., and may have enzyme activities of from about 500 to 1700 glycine units/milligram.
  • All of these enzymes may each be present in a weight percentage amount of from about 0.2 to about 5% by weight, such that for amylolytic enzymes the final composition may have amylolytic activity of from about 10 2 to about 10 6 Maltose units/kg, and for proteolytic enzymes the final composition may have proteolytic enzyme activity of from about 10 6 to about 10 9 Glycine Units/kg.
  • enzyme material is present in the compositions of the invention in a total amount of up to about 10% by weight.
  • the detergent composition may also comprise a bleach system, which may or may not be encapsulated.
  • the bleach system may be a chlorine- or bromine-releasing agent or a peroxygen compound.
  • a peroxygen-based bleaching system is preferred.
  • Suitable peroxygen compounds may be selected from alkali metal peroxides, organic peroxides such as urea peroxide, and inorganic persalts such as the alkali metal perborates, percarbonate, perphosphates, persilicates and persulphates. Mixtures of two or more such compounds may also be suitable.
  • Particularly preferred peroxygen compounds are sodium perborate tetrahydrate and, especially, sodium perborate monohydrate.
  • Sodium perborate monhydrate is preferred because of its high active oxygen content.
  • Sodium percarbonate may also be preferred for environmental reasons.
  • peroxyacids usable in the present invention are solid and, preferably, substantially water-insoluble compounds.
  • substantially water-insoluble is meant herein a water-solubility of less than about 1% by weight at ambient temperature.
  • peroxyacids containing at least about 7 carbon atoms are sufficiently insoluble in water for use herein.
  • Typical monoperoxy acids useful herein include alkyl peroxy acids and aryl peroxyacids such as:
  • Typical diperoxy acids useful herein include alkyl diperoxy acids and aryldiperoxy acids, such as:
  • Peroxyacid bleach precursors are well known in the art. As non-limiting examples can be named N,N,N'N'-tetraacetyl ethylene diamine (TAED), sodium nonanoyloxybenzene sulphonate (SNOBS), sodium benzoyloxybenzene sulphonate (SBOBS) and the cationic peroxyacid precursor (SPCC) as described in US-A-4751015.
  • TAED N,N,N'N'-tetraacetyl ethylene diamine
  • SNOBS sodium nonanoyloxybenzene sulphonate
  • SBOBS sodium benzoyloxybenzene sulphonate
  • SPCC cationic peroxyacid precursor
  • suitable reactive chlorine- or bromine-oxidizing materials are heterocyclic N-bromo- and N-chloro imides such as tri-chloroisocyanuric, tribromoisocyanuric, dibromoisocyanuric and dichloroisocyanuric acids, and salts thereof with water-solubilizing cations such as potassium and sodium.
  • Hydantoin compounds such as 1,3-dichloro-5,5- dimethyl-hydantoin are also quite suitable.
  • Dry, particulate, water-soluble anhydrous inorganic salts are likewise suitable for use herein such as lithium, sodium or calcium hypochlorite and hypobromite.
  • Chlorinated trisodium phosphate is another suitable material.
  • Chloroisocyanurates are, however, the preferred bleaching agents.
  • Potassium dichlorosocyanurate is sold by Monsanto Company as ACL-59 R .
  • Sodium dichloroisocyanurates are also available from Monsanto as ACL-60 R , and in the dihydrate form, from the Olin Corporation as Clearon CDB-56 R , available in powder form (particle diameter of less than 150 microns); medium particle size (about 50 to 400 microns); and coarse particle size (150-850 microns). Very large particles (850-1700 microns) are also found to be suitable also for encapsulation.
  • a bleach catalyst such as the manganese complex, e.g. Mn-Me TACN, as described in EP-A-0458397, or the sulphonimines of US Patents 5,041,232 and 5,047,163, may be incorporated in the composition.
  • Such bleach catalysts may suitably be presented in the form of a second encapsulate separately from the bleach capsule component.
  • the amount of encapsulates used in the compositions of the invention may vary preferably within the range of from about 0.1 to about 10%, especially from about 0.5 to about 3% as available chlorine (Av Cl).
  • a suitable preferred range will be from about 0.1 to about 20%, especially from about 0.1 to about 10%, preferably from about 0.5 to about 3 or 5% Av O (available oxygen).
  • the amount of peroxygen bleach, silicate and, carbonate, protease and surfactant taken together is at most about 20% by weight, more especially preferably between about 10 and 19.95% by weight of the composition.
  • a detergent tablet comprising from about 25 to about 100%, preferably from about 25 to about 90% by weight, more preferably from about 40 to about 90% by weight, of co-granules according to the first aspect of the invention.
  • the co-granules used to form the tablet are made by any of the processes described above.
  • the tablet of the invention preferably contains less than 35% by weight, preferably less than 20% by weight, of irritant material selected from peroxygen bleach, silicate, carbonate, protease and surfactant.
  • the strength of the tablet of the invention should preferably be high enough to allow handling without the need for individual wrapping.
  • the tablet strength is defined as the force, expressed in Newtons, needed to break the tablet, as measured using a Chatillon type UTSM (remote 500) instrument in a direction perpendicular to the direction of compression.
  • the tablet strength should preferably be at least about 150 Newton, more preferably at least about 200 Newton, so as to be sufficient for the tablet concerned to survive handling and packing. On the other hand, the tablet strength should not be too high, since in such a case the dissolution characteristics of the tablet concerned may not be adequate.
  • the tablet strength should generally be below about 1000 Newton, preferably below about 800 Newton, more preferably below about 600 Newton, for round tablets. For rectangular tablets, the tablet strength should generally be below about 2000 Newton, preferably below about 1600 Newton, more preferably below about 1400 Newton.
  • the tablets of the invention preferably have a density of at least about 1300 kg/m 3 .
  • the tablets of this aspect of the invention preferably comprise more than about 20% by weight, preferably from about 25 to about 50% by weight, of the salt of di-, tri-, or tetracarboxylic acid, as builder salt.
  • the detergent tablet of this aspect of the present invention comprises (in approximate amounts):
  • the tablet of the invention may be effectively produced by a process involving the steps of mixing the co-granule material with the other ingredients of the tablet, and compacting the resulting detergent mixture using a pressure of at least 10 KN/cm 2 .
  • Example 1 Example 2 Alkaline silicate solution (45%) 302 1209 Sodium hyroxide solution (46%) 190 763 Citric acid solution (48%) 292 1170 Copolymer maleate/acrylate (Sokalan CP-5 ex BASF) solution (40%) 56 225 Nonionic surfactant (Plurafac LF403) 8.5 - Synthetic clay (Laponite powder) 8.5 34
  • the slurries of Examples 1 and 2 had a water content of 55% (w/w), with a low viscosity.
  • the slurries were dried using a laboratory scale spray tower, followed by restructing (milling and spraying-on a few percent of a 45% alkaline silicate solution) and redrying.
  • the co-granules so obtained showed an excellent whiteness due to citrate which was translucent bound up in a white co-granule.
  • the co-granules were easily soluble in water and showed an excellent dish washing performance.
  • a slurry was prepared on a tonne scale having the following composition by adding the ingredients one after another: parts per weight Citric acid solution (48%) 90 Sodium hydroxide solution (45%) 58 Copolymer maleate/acrylate solution (40%) 12.5 Alkaline silicate solution (45%) 75.6
  • the moisture content of the slurry was 55% (w/w). It had a low viscosity.
  • the slurry was dried using a pilot scale spray tower, yielding a powder with a moisture content of 12% (w/w), a bulk density of 400g/l and an average particle diameter of 400 ⁇ m.
  • the powder was partly broken and restructured using a Lödige recycler and plough share mixer, yielding co-granules with a bulk density of 750 g/l and an average particle diameter of 550 ⁇ m.
  • the appearance of the final product was pleasant. It dissolved and dispensed well in automatic dishwashing machines with a dissolution time of 1 minute at 20°C and a dispensing time of 4 minutes at 20°C. When compared with a product of the same composition obtained by dry mixing of components, these data were 3 minutes and 10 minutes, respectively.
  • the strength of detergent tablets produced from a detergent mixture not containing co-granules was compared with the strength of tablets according to the invention produced from a mixture having the same composition but containing co-granules.
  • composition (parts by weight)
  • Example 4A Sodium citrate 40 30
  • Maleate/acrylate copolymer 6 6
  • Sodium disilicate 26.2 5
  • detergent tablets having a weight of 20 grams were made from mixtures containing the co-granules, by compacting these mixtures using a Fette Perfecta 3 tabletting machine fitted with a 41 mm round die and optionally plastic inserts.
  • the compaction pressure was 30 kN/cm 2 .
  • 20 gram tablets (Comparative Examples 4C and 4D, respectively) were also made from mixtures not containing these co-granules but instead comprising the individual, non-co-granulated constituents thereof at concentrations equal to their respective concentrations in the co-granules-containing mixtures.
  • compositions of the mixtures from which the tablets were produced were as follows (in % by weight):
  • Example Example no 4A 4C (Comparative) 4B 4D (Comparative) Co-granules 72.2 - 77.7 - Sodium citrate - 40 - 30
  • Acrylate/maleate copolymer - 6 - 6 Sodium disilicate - 26.2 - 5
  • Nonionic surfactant Plurafac LF403
  • the tablets of the invention took about 8 minutes to dissolve during a dishwashing cycle in a Bauknecht GSF 1161 automatic dishwashing machine.

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Claims (32)

  1. Homogenes Co-Granulat umfassend
    (i) ein Salz einer Di-, Tri- oder Tetracarbonsäure, das ein Alkalisalz von Citronensäure, Mellitsäure, Oxydibernsteinsäure, Carboxymethoxybernsteinsäure, Malonsäure, Dipicolinsäure oder Alkenylbernsteinsäure ist und
    (ii) ein anorganisches Salz ausgewählt aus Alkalisilicat, Alkalicarbonat, Alkalibicarbonat, Alkalisesquicarbonat, Alkalisulfat, Alkalitripolyphosphat und Mischungen davon und
    weiter umfassend mindestens eine polymere Verbindung, die entweder eine Säure und/oder ein Salz ist, ausgewählt aus der Gruppe bestehend aus Polycarbonsäurepolymeren und Polypeptiden.
  2. Co-Granulat nach Anspruch 1, worin bis zu 30% der Di-, Tri- oder Tetracarbonsäuresalzkomponente durch eine niedrigere Hydroxymonocarbonsäure ersetzt sind.
  3. Co-Granulat nach Anspruch 1, worin das anorganische Salz Natriumsilicat ist mit einer Zusammensetzung, die das Verhältnis SiO2:Na2O = 1,0 bis 3,3 aufweist.
  4. Co-Granulat nach Anspruch 3, worin das Natriumsilicat eine Zusammensetzung hat mit SiO2:Na2O = 1,8 bis 2,8.
  5. Co-Granulat nach Anspruch 1, worin das anorganische Salz Natriumdisilicat ist.
  6. Co-Granulat nach Anspruch 1, worin die polymere Verbindung ein Alkalisalz eines wasserlöslichen Homopolymers oder Copolymers mit einem Molekulargewicht von mindestens 500 ist und von einer Mono-, Di-, Tri- oder Polycarbonsäure abgeleitet ist.
  7. Co-Granulat nach Anspruch 6, worin die polymere Verbindung ausgewählt ist aus der Gruppe bestehend aus:
    (i) Homopolymeren abgeleitet von einem Monomer der Formel:
    Figure 00390001
    worin R1 Wasserstoff, ein Hydroxyl-, C1-C4-Alkyl- oder Alkoxy-, Acetoxyrest oder -CH2COOM ist; R2 Wasserstoff, ein C1-C4-Alkylrest oder -COOM ist und M ein Alkalimetall ist;
    (ii) Copolymeren von zwei oder mehr Carbonsäuremonomeren der obigen Formel (i) und
    (iii) Copolymeren von einem Carbonsäuremonomer der obigen Formel (i) und zwei oder mehr Nichtcarbonsäuremonomeren ausgewählt aus Ethylen, Propylen, Styrol, α-Methylstyrol, Acrylnitril, Acrylamid, Vinylacetat, Methylvinylketon, Acrolein und Estern von Carbonsäuremonomeren.
  8. Co-Granulat nach einem der vorhergehenden Ansprüche, das weiterhin bis zu 7 Gew.-% eines wenig oder nicht schäumenden nichtionischen Tensids enthält.
  9. Co-Granulat nach einem der vorhergehenden Ansprüche, das die folgende Zusammensetzung (II) hat:
    20 bis 75% (G/G) Alkalisilicat, Carbonat, Bicarbonat oder Sesquicarbonat;
    25 bis 75% (G/G) Alkalialz einer Di-, Tri- oder Tetracarbonsäure;
    1 bis 9% (G/G) Polymer;
    1 bis 36% (G/G) Alkalitripolyphosphat;
    0 bis 60% (G/G) Alkalisulfat;
    0 bis 9% (G/G) organisches Phosphonat;
    0 bis 5% (G/G) Inhaltsstoffe in geringeren Anteilen;
    3 bis 20% (G/G) Feuchtigkeit.
  10. Co-Granulat nach einem der vorhergehenden Ansprüche, das eine durchschnittliche Teilchengröße von 100 bis 1500 µm hat.
  11. Co-Granulat nach Anspruch 10, das eine durchschnittliche Teilchengröße von 500 bis 700 µm und einen Rosen-Rammler-N-Wert von mehr als 2,5 hat.
  12. Co-Granulat nach einem der vorhergehenden Ansprüche, das eine Schüttdichte von mindestens 700 g/dm3 hat.
  13. Verfahren zur Herstellung eines Co-Granulats nach einem der vorhergehenden Ansprüche, wobei das Verfahren umfaßt, daß man eine Aufschlämmung oder Lösung der Inhaltsstoffe des Co-Granulats herstellt, die Mischung trocknet und das entstehende Material granuliert.
  14. Verfahren nach Anspruch 13, worin die Trocknungsstufe durchgeführt wird unter Verwendung eines Turbinentrockners oder einer Sprühtrocknungsvorrichtung.
  15. Verfahren zur Herstellung eines Co-Granulats nach einem der Ansprüche 1 bis 12, worin Material, das mit dem Verfahren von Anspruch 13 oder Anspruch 14 hergestellt wurde, oder feines festes Ausgangsmaterial, das die Inhaltsstoffe des Co-Granulats enthält, umstrukturiert wird.
  16. Verfahren nach einem der Ansprüche 13 bis 15, wobei das Verfahren umfaßt, daß man eine Aufschlämmung oder Lösung herstellt, indem man die Di-, Tri- oder Tetracarbonsäure mit Alkali neutralisiert, das anorganische Salz zugibt, gegebenenfalls weitere Inhaltsstoffe zugibt, um eine Aufschlämmung mit einem Wassergehalt von 30 bis 60% (G/G) zu erhalten, und die Aufschlämmung in Co-Granulate umwandelt.
  17. Reinigungszusammensetzung enthaltend mindestens 25% der Co-Granulate nach einem der Ansprüche 1 bis 12.
  18. Reinigungszusammensetzung nach Anspruch 17, die weiterhin ein Bleichsystem und/oder ein Enzymsystem enthält.
  19. Reinigungszusammensetzung nach Anspruch 18, die mindestens 50% der Co-Granulate und weniger als 30% des Bleichsystems und/oder Enzymsystems enthält.
  20. Reinigungszusammensetzung nach Anspruch 18 oder Anspruch 19, worin das Bleichsystem ein Persauerstoffbleichsystem ist.
  21. Reinigungszusammensetzung nach Anspruch 20, worin die Menge an Persauerstoffbleichmittel, Silicat, Carbonat, Protease und Tensid zusammen in der Zusammensetzung höchstens 30%, bevorzugt höchstens 20 Gew.-% ist.
  22. Verfahren zur Herstellung einer Reinigungszusammensetzung nach einem der Ansprüche 17 bis 21, worin die Zusammensetzung einem Tablettierverfahren in einer Tablettiervorrichtung unterzogen wird.
  23. Reinigungstablette enthaltend 25 bis 100 Gew.-% Co-Granulate gemäß einem der Ansprüche 1 bis 12.
  24. Reinigungstablette nach Anspruch 23 enthaltend 40 bis 90 Gew.-% des Co-Granulatmaterials.
  25. Reinigungstablette nach Anspruch 23 oder 24, die weiterhin ein Bleichsystem und/oder ein Enzymsystem enthält.
  26. Reinigungstablette nach Anspruch 25, die weniger als 35%, bevorzugt weniger als 20 Gew.-% eines reizenden Materials ausgewählt aus Persauerstoffbleichmittel, Silicat, Carbonat, Protease und Tensid enthält.
  27. Reinigungstablette nach einem der Ansprüche 23 bis 26, die eine Festigkeit von 150 bis 2000 Newton hat, wobei dies die Kraft ist, die erforderlich ist, um die Tablette zu zerbrechen, gemessen unter Verwendung eines UTSM-Gerätes des Typs Chatillon (Remote 500) in einer Richtung senkrecht zur Richtung der Verdichtung.
  28. Reinigungstablette nach einem der Ansprüche 23 bis 27, die eine Dichte von mindestens 1300 kg/m3 hat.
  29. Reinigungstablette nach einem der Ansprüche 23 bis 28, die mehr als 20 Gew.-% des Salzes einer Di-, Tri- oder Tetracarbonsäure enthält.
  30. Reinigungstablette nach einem der Ansprüche 23 bis 29, die die folgende Zusammensetzung hat:
    25 bis 90 Gew.-% Co-Granulatmaterial;
    5 bis 20 Gew.-% einer Wasserstoffperoxidquelle ausgewählt aus Alkaliperoxiden, organischen Peroxiden, anorganischen Persalzen und Mischungen davon;
    0 bis 5 Gew.-% eines Bleichkatalysators;
    0 bis 10 Gew.- Enzymmaterial;
    0 bis 5 Gew.-% Tablettierhilfsmittel;
    0 bis 10 Gew.-% Bestandteile in geringeren Anteilen.
  31. Verfahren zur Herstellung einer Reinigungstablette nach einem der Ansprüche 23 bis 30, wobei das Verfahren die Stufen umfaßt, daß man das Co-Granulatmaterial mit den anderen Inhaltsstoffen der Tablette vermischt und die entstehende Mischung bei einem Druck von mindestens 10 kN/cm2 verdichtet.
  32. Verwendung eines Co-Granulats nach einem der Ansprüche 1 bis 12 oder einer Reinigungszusammensetzung nach einem der Ansprüche 17 bis 21 oder einer Reinigungstablette nach einem der Ansprüche 23 bis 30 für ein Spülmaschinenverfahren.
EP95907583A 1994-01-25 1995-01-23 Verfahren zur herstellung von reinigungsmitteltabletten Expired - Lifetime EP0741776B2 (de)

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US11015151B2 (en) 2008-03-28 2021-05-25 Ecolab Usa Inc. Sulfoperoxycarboxylic acids, their preparation and methods of use as bleaching and antimicrobial agents
US9676711B2 (en) 2008-03-28 2017-06-13 Ecolab Usa Inc. Sulfoperoxycarboxylic acids, their preparation and methods of use as bleaching and antimicrobial agents
US10669512B2 (en) 2008-03-28 2020-06-02 Ecolab Usa Inc. Sulfoperoxycarboxylic acids, their preparation and methods of use as bleaching and antimicrobial agents
US11827867B2 (en) 2008-03-28 2023-11-28 Ecolab Usa Inc. Sulfoperoxycarboxylic acids, their preparation and methods of use as bleaching and antimicrobial agents
US9242879B2 (en) 2012-03-30 2016-01-26 Ecolab Usa Inc. Use of peracetic acid/hydrogen peroxide and peroxide-reducing agents for treatment of drilling fluids, frac fluids, flowback water and disposal water
US9926214B2 (en) 2012-03-30 2018-03-27 Ecolab Usa Inc. Use of peracetic acid/hydrogen peroxide and peroxide-reducing agents for treatment of drilling fluids, frac fluids, flowback water and disposal water
US10017403B2 (en) 2012-03-30 2018-07-10 Ecolab Usa Inc. Use of peracetic acid/hydrogen peroxide and peroxide-reducing enzymes for treatment of drilling fluids, frac fluids, flowback water and disposal water
US10023484B2 (en) 2012-03-30 2018-07-17 Ecolab Usa Inc. Use of peracetic acid/hydrogen peroxide and peroxide-reducing agents for treatment of drilling fluids, frac fluids, flowback water and disposal water
US11939241B2 (en) 2012-10-05 2024-03-26 Ecolab Usa Inc. Stable percarboxylic acid compositions and uses thereof
US10893674B2 (en) 2013-03-05 2021-01-19 Ecolab Usa Inc. Efficient stabilizer in controlling self accelerated decomposition temperature of peroxycarboxylic acid compositions with mineral acids
US11026421B2 (en) 2013-03-05 2021-06-08 Ecolab Usa Inc. Efficient stabilizer in controlling self accelerated decomposition temperature of peroxycarboxylic acid compositions with mineral acids
US11206826B2 (en) 2013-03-05 2021-12-28 Ecolab Usa Inc. Defoamer useful in a peracid composition with anionic surfactants
US8822719B1 (en) 2013-03-05 2014-09-02 Ecolab Usa Inc. Peroxycarboxylic acid compositions suitable for inline optical or conductivity monitoring
US10165774B2 (en) 2013-03-05 2019-01-01 Ecolab Usa Inc. Defoamer useful in a peracid composition with anionic surfactants
US12465048B2 (en) 2013-03-05 2025-11-11 Ecolab Usa Inc. Defoamer useful in a peracid composition with anionic surfactants
US12058999B2 (en) 2018-08-22 2024-08-13 Ecolab Usa Inc. Hydrogen peroxide and peracid stabilization with molecules based on a pyridine carboxylic acid
US12558713B2 (en) 2019-05-31 2026-02-24 Ecolab Usa Inc. Peracid compositions with conductivity monitoring capability
EP4077615A1 (de) * 2019-12-18 2022-10-26 Basf Se Pulver und granulate sowie verfahren zum herstellen solcher pulver und granulate
US12545868B2 (en) 2019-12-18 2026-02-10 Basf Se Powders and granules and process for making such powders and granules

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AU1575695A (en) 1995-08-08
ES2118561T5 (es) 2002-03-16
AU702040B2 (en) 1999-02-11
EP0741776A1 (de) 1996-11-13
ES2118561T3 (es) 1998-09-16
DE69502701T3 (de) 2002-05-29
DE69502701D1 (de) 1998-07-02
EP0741776B2 (de) 2001-10-24
BR9506561A (pt) 1997-10-28
WO1995020030A1 (en) 1995-07-27
CA2180433A1 (en) 1995-07-27
DE69502701T2 (de) 1998-11-26
CA2180433C (en) 2000-04-25

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