EP0979863A1 - Mehrschichtwaschmitteltablette mit unterschiedlicher Elastizität - Google Patents

Mehrschichtwaschmitteltablette mit unterschiedlicher Elastizität Download PDF

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Publication number
EP0979863A1
EP0979863A1 EP98202712A EP98202712A EP0979863A1 EP 0979863 A1 EP0979863 A1 EP 0979863A1 EP 98202712 A EP98202712 A EP 98202712A EP 98202712 A EP98202712 A EP 98202712A EP 0979863 A1 EP0979863 A1 EP 0979863A1
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EP
European Patent Office
Prior art keywords
tablet
layer
acid
tablets
detergent
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.)
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Application number
EP98202712A
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English (en)
French (fr)
Inventor
Serge Eric Salager
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Procter and Gamble Co
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Procter and Gamble Co
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Publication date
Application filed by Procter and Gamble Co filed Critical Procter and Gamble Co
Priority to EP98202712A priority Critical patent/EP0979863A1/de
Priority to CN 99811915 priority patent/CN1322240A/zh
Priority to CA002338793A priority patent/CA2338793A1/en
Priority to PCT/US1999/018190 priority patent/WO2000009645A1/en
Priority to JP2000565082A priority patent/JP2002522630A/ja
Priority to BR9912936-1A priority patent/BR9912936A/pt
Priority to AU54762/99A priority patent/AU5476299A/en
Publication of EP0979863A1 publication Critical patent/EP0979863A1/de
Withdrawn legal-status Critical Current

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    • 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
    • C11D17/0078—Multilayered tablets

Definitions

  • the present invention relates to detergent tablets, especially those adapted for use in washing.
  • cleaning compositions in tablet form have often been proposed, these have not (with the exception of soap bars for personal washing) gained any substantial success, despite the several advantages of products in a unit dispensing form.
  • One of the reasons for this may be that detergent tablets usually dissolve slower than the constituent powders from which they are made, simply because the constituent powders are forced close together in the tablet, with comparatively little opportunity for water to permeate between them. This gives rise to the problem that slow dissolving tablets cause residues which may for example be visible through the door of the washing machine during the wash cycle, or which stick to the fabrics at the end of the wash cycle, or both. This may be compensated by using low compression forces to keep high porosity and good dissolution profile. However, such tablets are typically softer and have mechanical characteristics such that breakage is likely to occur during production or handling.
  • the object of the present invention is to provide detergent tablets typically formed by compressing a particulate material, the tablet being suitable for storing, shipping and handling without breakage while dissolving easily and rapidly in wash solution, releasing the active ingredients into the wash solution and completely disintegrating and dispersing in alkaline or surfactant-rich solutions such as the wash liquor.
  • the object of the invention is achieved by providing a detergent tablet having at least a first and a second layer, whereby the first layer is less elastic than the second layer, and if said tablet has more than two layers, the tablet is such that a less elastic layer is situated at an end of the tablet.
  • the invention relates to a detergent tablet.
  • detergent it is meant that the tablet comprises surfactants.
  • a tablet is defined as having a height along a main axis and a cross section normal to the main axis, the cross section being preferably substantially constant when travelling along the main axis, the tablet having two ends, each end being situated at each end of the main axis and having a surface area substantially equal to the cross section of the tablet.
  • the tablet is such that it comprises at least a first and a second layer. Normally, these layers are produced by compression of particulate materials. Composition of these layers may be similar or different, and compression force used for forming these layers may also be similar or different. It should be noted that a preferred embodiment of a tablet according to the invention comprises only two layers, but tablets with more layers may be considered.
  • a layer is preferably a part of a tablet made from compressing particulate materials, this part of the tablet having a height along the main axis of the tablet and a cross section corresponding to the cross section of the tablet, such that the composition or the physical and mechanical characteristics of this part differs from the rest of the tablet.
  • a tablet according to the invention is made by piling up layers along the main axis to form the tablet, this layers adhering to each other to form the tablet, adhesion between layers being provided by mechanical or chemical means.
  • each layer may be considered as a mono-layer tablet, as far as composition is concerned, for example.
  • the first layer is less elastic than the second layer.
  • the elasticity is lower than the elasticity of the second layer.
  • a less elastic layer is simply a layer such that there is another layer in the tablet which is more elastic.
  • the least elastic layer is the layer most brittle among all layers in the tablet. Brittle should be understood as contrary to elastic for the purpose of the invention. Same applies for more elastic, i.e. less brittle, or most elastic, i.e. least brittle.
  • the less elastic layer has an elasticity 10% lower than the elasticity of a more elastic layer part of the same tablet, preferably 20% lower, more preferably 30% lower, even more preferably 40% lower and most preferably 50% lower.
  • the elasticity-brittleness scale is measured by the elasticity E of the tablet.
  • the tablet if said tablet has more than two layers, the tablet is such that a less elastic layer is situated at an end of the tablet.
  • the less elastic layer is not necessarily the least elastic layer.
  • the least elastic layer is situated at one end. This is beneficial to dissolution because the surface activity of this less elastic layer is high because it is exposed as it is situated at one end.
  • the mechanical properties and the dissolution properties of a single tablet can be rendered more independent the ones from the others, so that a more elastic layer will more specifically provide mechanical integrity and protection while a less elastic layer will more specifically favour fast and efficient dissolution. Indeed, a less elastic layer, thereby more brittle, will disperse readily in solution.
  • the level of elasticity of different layers may be set using different parameters, such as different chemical composition, or different compression force.
  • a layer may comprise more binders than another one to be made more elastic, i.e. less brittle.
  • a less elastic layer comprises higher levels of surfactant per weight. Indeed, a less elastic layer will more readily dissolve, and therefore will compensate gelling of surfactants by its brittleness. Indeed, gelling of surfactant is hindering fast and effective dissolution, which can be compensated by concentrating such surfactants in a less elastic layer. This can be advantageously combined with use of highly soluble compounds, hydrotrope compounds, and compounds providing high cohesive effect at lower compression force, for example.
  • the tablet is such that the more elastic layer is situated at an end of the tablet. Indeed, it was found sufficient to obtain good mechanical characteristics to have one less brittle layer at one end of the tablet.
  • Such mechanical resistance was found to be improved when using a tablet having a substantially rectangular cross section. Indeed, solidity of the tablet could be improved at constant compression value by using a rectangular tablet.
  • rectangular tablet At equal weight, equal compression force, equal composition, equal height and equal volume, rectangular tablet have a mechanical resistance significantly improved when compared to round tablets. This particularly applies to square tablets.
  • a layer may preferably have a height varying between 5 and 95% of the total tablet height. More preferably, the more elastic the layer is, the thinner it is to have a minimum impact on the overall dissolution of the entire tablet.
  • a tablet according to the invention will comprise layers having different hardness (or softness), whereby their tensile strength will be different.
  • the tablet will comprise a more soft layer having a tensile strength between 5 and 100 kPa, as well as a more hard layer having a tensile strength comprised between 5.5 and 150 kPa.
  • the tablet comprises at least two layers having a different hardness, the more hard layer being more resistant to mechanical shocks, the more soft layer having better dissolution characteristics.
  • a more brittle layer is also a softer layer, and a more elastic layer is also harder. However, this may not be the case.
  • the elasticity of a tablet or of a layer from a tablet is evaluated as follows:
  • the tablet preferably comprises a highly soluble compound. More preferably, this compound is comprised or is present at higher levels per weight in the relatively elastic layer of the tablet, i.e. the less brittle layer, in order to further favour dissolution. Indeed, it may be preferred to aid dissolution of the more elastic layer, as this layer will for example be more compressed than a more brittle layer.
  • a highly soluble compound is defined as follow: A solution is prepared as follows comprising de-ionised water as well as 20 grams per litre of a specific compound:
  • the tablet preferably comprises a compound having a Cohesive Effect on the particulate material of a detergent matrix forming the tablet. More preferably, this compound is comprised or is present at higher levels per weight in the relatively elastic layer of the tablet, i.e. the less brittle layer, in order to obtain satisfactory elasticity without need for high compression.
  • the Cohesive Effect on the particulate material of a detergent matrix forming the tablet or a layer of the tablet is characterised by the force required to break a tablet or layer based on the examined detergent matrix pressed under controlled compression conditions. For a given compression force, a high tablet or layer strength indicates that the granules stuck highly together when they were compressed, so that a strong cohesive effect is taking place.
  • the cohesive effect is measured by comparing the tablet or layer strength of the original base powder without compound having a cohesive effect with the tablet or layer strength of a powder mix which comprises 97 parts of the original base powder and 3 parts of the compound having a cohesive effect.
  • the compound having a cohesive effect is preferably added to the matrix in a form in which it is substantially free of water (water content below 10% (pref. below 5%)).
  • the temperature of the addition is between 10 and 80C, more pref. between 10 and 40C.
  • a compound is defined as having a cohesive effect on the particulate material according to the invention when at a given compacting force of 3000N, tablets with a weight of 50g of detergent particulate material and a diameter of 55mm have their tablet tensile strength increased by over 30% (preferably 60 and more preferably 100%) by means of the presence of 3% of the compound having a cohesive effect in the base particulate material.
  • An example of a compond having a cohesive effect is Sodium di isoalkylbenzene sulphonate.
  • the dissolution of the tablet or layer in an aqueous solution is significantly increased.
  • at least 1% per weight of a tablet or layer is formed from the highly soluble compound, more preferably at least 2%, even more preferably at lest 3% and most preferably at least 5% per weight of the tablet or layer being formed from the highly soluble compound having a cohesive effect on the particulate material.
  • compositions comprising a highly soluble compound as well as a surfactant is disclosed in EP-A-0 524 075, this composition being a liquid composition.
  • a highly soluble compound having a cohesive effect on the particulate material allows to obtain a tablet having a higher tensile strength at constant compacting force or an equal tensile strength at lower compacting force when compared to traditional tablets.
  • a whole tablet will have a tensile strength of more than 5kPa, preferably of more than 10kPa, more preferably, in particular for use in laundry applications, of more than 15kPa, even more preferably of more than 30 kPa and most preferably of more than 50 kPa, in particular for use in dish washing or auto dish washing applications; and a tensile strength of less than 300 kPa, preferably of less than 200 kPa, more preferably of less than 100 kPa, even more preferably of less than 80 kPa and most preferably of less than 60 kPa.
  • the tablets should be less compressed than in case of auto dish washing applications for example, whereby the dissolution is more readily achieved, so that in a laundry application, the tensile strength is preferably of less than 30 kPa.
  • the tensile strength is preferably of less than 30 kPa.
  • the layer may be considered as a tablet itself.
  • Detergent tablets of the present invention can be prepared simply by mixing the solid ingredients together and compressing the mixture in a conventional tablet press as used, for example, in the pharmaceutical industry.
  • the principal ingredients in particular gelling surfactants, are used in particulate form.
  • Any liquid ingredients, for example surfactant or suds suppressor, can be incorporated in a conventional manner into the solid particulate ingredients.
  • the ingredients such as builder and surfactant can be spray-dried in a conventional manner and then compacted at a suitable pressure.
  • the tablets according to the invention are compressed using a force of less than 100000N, more preferably of less than 50000N, even more preferably of less than 5000N and most preferably of less than 3000 N.
  • the most preferred embodiment is a tablet suitable for laundry compressed using a force of less than 2500N, but tablets for auto dish washing may also be considered for example, whereby such auto dish washing tablets are usually more compressed than laundry tablets.
  • the particulate material used for making the tablet of this invention can be made by any particulation or granulation process. An example of such a process is spray drying (in a co-current or counter current spray drying tower) which typically gives low bulk densities 600g/l or lower.
  • Particulate materials of higher density can be prepared by granulation and densification in a high shear batch mixer/granulator or by a continuous granulation and densification process (e.g. using Lodige® CB and/or Lodige® KM mixers).
  • Other suitable processes include fluid bed processes, compaction processes (e.g. roll compaction), extrusion, as well as any particulate material made by any chemical process like flocculation, crystallisation sentering, etc.
  • Individual particles can also be any other particle, granule, sphere or grain.
  • the components of the particulate material may be mixed together by any conventional means.
  • Batch is suitable in, for example, a concrete mixer, Nauta mixer, ribbon mixer or any other Alternatively the mixing process may be carried out continuously by metering each component by weight on to a moving belt, and blending them in one or more drum(s) or mixer(s).
  • Non-gelling binder can be sprayed on to the mix of some, or all of, the components of the particulate material.
  • Other liquid ingredients may also be sprayed on to the mix of components either separately or premixed. For example perfume and slurries of optical brighteners may be sprayed.
  • a finely divided flow aid (dusting agent such as zeolites, carbonates, silicas) can be added to the particulate material after spraying the binder, preferably towards the end of the process, to make the mix less sticky.
  • the tablets may be manufactured by using any compacting process, such as tabletting, briquetting, or extrusion, preferably tabletting. Suitable equipment includes a standard single stroke or a rotary press (such as Courtoy®, Korch®, Manesty®, or Bonals®).
  • the tablets prepared according to this invention preferably have a diameter of between 20mm and 60mm, preferably of at least 35 and up to 55 mm, and a weight between 25 and 100 g.
  • the ratio of height to diameter (or width) of the tablets is preferably greater than 1:3, more preferably greater than 1:2.
  • the compaction pressure used for preparing these tablets need not exceed 100000 kN/m 2 , preferably not exceed 30000 kN/m 2 , more preferably not exceed 5000 kN/m 2 , even more preferably not exceed 3000kN/m 2 and most preferably not exceed 1000kN/m 2 .
  • the tablet has a density of at least 0.9 g/cc, more preferably of at least 1.0 g/cc, and preferably of less than 2.0 g/cc, more preferably of less than 1.5 g/cc, even more preferably of less than 1.25 g/cc and most preferably of less than 1.1 g/cc.
  • Multi layered tablets are typically formed in rotating presses by placing the matrices of each layer, one after the other in matrix force feeding flasks. As the process continues, the matrix layers are then pressed together in the pre-compression and compression stages stations to form the multilayer layer tablet. With some rotating presses it is also possible to compress the first feed layer before compressing the whole tablet.
  • a highly soluble compound having a cohesive effect is integrated to the tablet of the invention, whereby this compound is also a hydrotrope compound.
  • Such hydrotrope compound may be generally used to favour surfactant dissolution by avoiding gelling, so that they may be for example advantageously comprised a less elastic layer
  • a specific compound is defined as being hydrotrope as follows (see S.E. Friberg and M. Chiu, J. Dispersion Science and Technology, 9(5&6), pages 443 to 457, (1988-1989)):
  • Solidity of the tablet according to the invention may be further improved by making a coated tablet, the coating covering a non-coated tablet according to the invention, thereby further improving the mechanical characteristics of the tablet while maintaining or further improving dissolution.
  • This very advantageously applies to multi-layer tablets according to the invention, whereby the mechanical characteristics of a more elastic layer can be transmitted via the coating to the rest of the tablet, thus combining the advantage of the coating with the advantage of the more elastic layer. Indeed, mechanical constraints will be transmitted through the coating, thus improving mechanical integrity of the tablet.
  • the tablets may then be coated so that the tablet does not absorb moisture, or absorbs moisture at only a very slow rate.
  • the coating is also strong so that moderate mechanical shocks to which the tablets are subjected during handling, packing and shipping result in no more than very low levels of breakage or attrition.
  • the coating is preferably brittle so that the tablet breaks up when subjected to stronger mechanical shock.
  • the coating material is dissolved under alkaline conditions, or is readily emulsified by surfactants. This contributes to avoiding the problem of visible residue in the window of a front-loading washing machine during the wash cycle, and also avoids deposition of undissolved particles or lumps of coating material on the laundry load. Water solubility is measured following the test protocol of ASTM E1148-87 entitled, "Standard Test Method for Measurements of Aqueous Solubility".
  • Suitable coating materials are dicarboxylic acids. Particularly suitable dicarboxylic acids are selected from the group consisting of oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, undecanedioic acid, dodecanedioic acid, tridecanedioic acid and mixtures thereof.
  • the coating material has a melting point preferably of from 40 °C to 200 °C
  • Two preferred coating methods are a) coating with a molten material and b) coating with a solution of the material.
  • the coating material is applied at a temperature above its melting point, and solidifies on the tablet.
  • the coating is applied as a solution, the solvent being dried to leave a coherent coating.
  • the substantially insoluble material can be applied to the tablet by, for example, spraying or dipping. Normally when the molten material is sprayed on to the tablet, it will rapidly solidify to form a coherent coating. When tablets are dipped into the molten material and then removed, the rapid cooling again causes rapid solidification of the coating material.
  • substantially insoluble materials having a melting point below 40 °C are not sufficiently solid at ambient temperatures and it has been found that materials having a melting point above about 200 °C are not practicable to use.
  • the materials melt in the range from 60 °C to 160 °C, more preferably from 70 °C to 120 °C.
  • melting point is meant the temperature at which the material when heated slowly in, for example, a capillary tube becomes a clear liquid.
  • a coating of any desired thickness can be applied according to the present invention.
  • the coating forms from 1% to 10%, preferably from 1.5% to 5%, of the tablet weight.
  • the tablet coatings of the present invention are very hard and provide extra strength to the tablet.
  • the fracture of the coating in the wash is improved by adding a disintegrant in the coating. This disintegrant will swell once in contact with water and break the coating in small pieces.
  • the disintegrant is suspended in the coating melt at a level of up to 30%, preferably between 5% and 20%, most preferably between 5 and 10% by weight. Possible disintegrants are described in Handbook of Pharmaceutical Excipients (1986).
  • Suitable disintegrants include starch: natural, modified or pregelatinized starch, sodium starch gluconate; gum: agar gum, guar gum, locust bean gum, karaya gum, pectin gum, tragacanth gum; croscarmylose Sodium, crospovidone, cellulose, carboxymethyl cellulose, algenic acid and its salts including sodium alginate, silicone dioxide, clay, polyvinylpyrrolidone, soy polysacharides, ion exchange resins and mixtures thereof.
  • the layer may be considered as a tablet itself.
  • the used compacting force may be adjusted to not affect the tensile strength, and the disintegration time in the washing machine. This process may be used to prepare homogenous or layered tablets of any size or shape.
  • a tablet having a diametral fracture stress of less than 20 kPa is considered to be fragile and is likely to result in some broken tablets being delivered to the consumer.
  • a diametral fracture stress of at least 25 kPa is preferred. This applies similarly to non cylindrical tablets, to define the tensile strength, whereby the cross section normal to the height of the tablet is non round, and whereby the force is applied along a direction perpendicular to the direction of the height of the tablet and normal to the side of the tablet, the side being perpendicular to the non round cross section.
  • the tablets further comprises an effervescent.
  • Effervescency as defined herein means the evolution of bubbles of gas from a liquid, as the result of a chemical reaction between a soluble acid source and an alkali metal carbonate, to produce carbon dioxide gas, i.e. C 6 H 8 O 7 + 3NaHCO 3 ⁇ Na 3 C 6 H 5 O 7 + 3CO 2 ⁇ + 3H 2 O
  • acid and carbonate sources and other effervescent systems may be found in : (Pharmaceutical Dosage Forms : Tablets Volume 1 Page 287 to 291).
  • An effervescent may be added to the tablet mix in addition to the detergent ingredients.
  • this effervescent improves the disintegration time of the tablet.
  • the amount will preferably be between 5 and 20 % and most preferably between 10 and 20% by weight of the tablet.
  • the effervescent should be added as an agglomerate of the different particles or as a compact, and not as separated particles.
  • the tablet Due to the gas created by the effervescency in the tablet, the tablet can have a higher D.F.S. and still have the same disintegration time as a tablet without effervescency. When the D.F.S. of the tablet with effervescency is kept the same as a tablet without, the disintegration of the tablet with effervescency will be faster.
  • Further dissolution aid could be provided by using compounds such as sodium acetate or urea. A list of suitable dissolution aid may also be found in Pharmaceutical Dosage Forms: Tablets, Volume 1, Second edition, Edited by H.A. Lieberman et all, ISBN 0-8247-8044-2.
  • Surfactant are comprised in the tablet according to the invention.
  • the dissolution of surfactants is favoured by the addition of the highly soluble compound.
  • Nonlimiting examples of surfactants useful herein typically at levels from about 1% to about 55%, by weight, include the conventional C 11 -C 18 alkyl benzene sulfonates ("LAS") and primary, branched-chain and random C 10 -C 20 alkyl sulfates (“AS”), the C 10 -C 18 secondary (2,3) alkyl sulfates of the formula CH 3 (CH 2 ) x (CHOSO 3- M + ) CH 3 and CH 3 (CH 2 ) y (CHOSO 3- M + ) CH 2 CH 3 where x and (y + 1) are integers of at least about 7, preferably at least about 9, and M is a water-solubilizing cation, especially sodium, unsaturated sulfates such as oleyl sulfate, the C 10 -C 18 alkyl alkoxy
  • the conventional nonionic and amphoteric surfactants such as the C 12- C 18 alkyl ethoxylates ("AE") including the so-called narrow peaked alkyl ethoxylates and C 6 -C 12 alkyl phenol alkoxylates (especially ethoxylates and mixed ethoxy/propoxy), C 12- C 18 betaines and sulfobetaines ("sultaines"), C 10- C 18 amine oxides, and the like, can also be included in the overall compositions.
  • the C 10 -C 18 N-alkyl polyhydroxy fatty acid amides can also be used. Typical examples include the C 12 -C 18 N-methylglucamides. See WO 9,206,154.
  • sugar-derived surfactants include the N-alkoxy polyhydroxy fatty acid amides, such as C 10 -C 18 N-(3-methoxypropyl) glucamide.
  • the N-propyl through N-hexyl C 12 -C 18 glucamides can be used for low sudsing.
  • C 10 -C 20 conventional soaps may also be used. If high sudsing is desired, the branched-chain C 10 -C 16 soaps may be used. Mixtures of anionic and nonionic surfactants are especially useful.
  • the tablet comprises at least 5% per weight of surfactant, more preferably at least 15% per weight, even more preferably at least 25% per weight, and most preferably between 35% and 45% per weight of surfactant.
  • Non gelling binders can be integrated to the particles forming the tablet in order to further facilitate dissolution. If non gelling binders are used, suitable non-gelling binders include synthetic organic polymers such as polyethylene glycols, polyvinylpyrrolidones, polyacrylates and water-soluble acrylate copolymers.
  • binders classification Acacia, Alginic Acid, Carbomer, Carboxymethylcellulose sodium, Dextrin, Ethylcellulose, Gelatin, Guar gum, Hydrogenated vegetable oil type l, Hydroxyethyl cellulose, Hydroxypropyl methylcellulose, Liquid glucose, Magnesium aluminum silicate, Maltodextrin, Methylcellulose, polymethacrylates, povidone, sodium alginate, starch and zein. Most preferable binders also have an active cleaning function in the laundry wash such as cationic polymers, i.e.
  • Non-gelling binder materials are preferably sprayed on and hence have an appropriate melting point temperature below 90°C, preferably below 70°C and even more preferably below 50°C so as not to damage or degrade the other active ingredients in the matrix.
  • non-aqueous liquid binders i.e. not in aqueous solution
  • they may also be solid binders incorporated into the matrix by dry addition but which have binding properties within the tablet.
  • Non-gelling binder materials are preferably used in an amount within the range from 0.1 to 15% of the composition, more preferably below 5% and especially if it is a non laundry active material below 2% by weight of the tablet. It is preferred that gelling binders, such as nonionic surfactants are avoided in their liquid or molten form. Nonionic surfactants and other gelling binders are not excluded from the compositions, but it is preferred that they be processed into the detergent tablets as components of particulate materials, and not as liquids.
  • Detergent builders can optionally be included in the compositions herein to assist in controlling mineral hardness.
  • Inorganic as well as organic builders can be used. Builders are typically used in fabric laundering compositions to assist in the removal of particulate soils. The level of builder can vary widely depending upon the end use of the composition.
  • Inorganic or P-containing detergent builders include, but are not limited to, the alkali metal, ammonium and alkanolammonium salts of polyphosphates (exemplified by the tripolyphosphates, pyrophosphates, and glassy polymeric meta-phosphates), phosphonates, phytic acid, silicates, carbonates (including bicarbonates and sesquicarbonates), sulphates, and aluminosilicates.
  • non-phosphate builders are required in some locales.
  • the compositions herein function surprisingly well even in the presence of the so-called "weak” builders (as compared with phosphates) such as citrate, or in the so-called "underbuilt” situation that may occur with zeolite or layered silicate builders.
  • silicate builders are the alkali metal silicates, particularly those having a SiO 2 :Na 2 O ratio in the range 1.6:1 to 3.2:1 and layered silicates, such as the layered sodium silicates described in U.S. Patent 4,664,839, issued May 12, 1987 to H. P. Rieck.
  • NaSKS-6 is the trademark for a crystalline layered silicate marketed by Hoechst (commonly abbreviated herein as "SKS-6"). Unlike zeolite builders, the Na SKS-6 silicate builder does not contain aluminum. NaSKS-6 has the delta-Na 2 SiO 5 morphology form of layered silicate. It can be prepared by methods such as those described in German DE-A-3,417,649 and DE-A-3,742,043.
  • SKS-6 is a highly preferred layered silicate for use herein, but other such layered silicates, such as those having the general formula NaMSi x O 2x+1 ⁇ yH 2 O wherein M is sodium or hydrogen, x is a number from 1.9 to 4, preferably 2, and y is a number from 0 to 20, preferably 0 can be used herein.
  • Various other layered silicates from Hoechst include NaSKS-5, NaSKS-7 and NaSKS-11, as the alpha, beta and gamma forms. As noted above, the delta-Na 2 SiO 5 (NaSKS-6 form) is most preferred for use herein.
  • silicates may also be useful such as for example magnesium silicate, which can serve as a crispening agent in granular formulations, as a stabilizing agent for oxygen bleaches, and as a component of suds control systems.
  • carbonate builders are the alkaline earth and alkali metal carbonates as disclosed in German Patent Application No. 2,321,001 published on November 15, 1973.
  • Aluminosilicate builders are useful in the present invention. Aluminosilicate builders are of great importance in most currently marketed heavy duty granular detergent compositions, and can also be a significant builder ingredient in liquid detergent formulations.
  • Aluminosilicate builders include those having the empirical formula: M z (zAlO 2 ) y ] ⁇ xH 2 O wherein z and y are integers of at least 6, the molar ratio of z to y is in the range from 1.0 to about 0.5, and x is an integer from about 15 to about 264.
  • Useful aluminosilicate ion exchange materials are commercially available. These aluminosilicates can be crystalline or amorphous in structure and can be naturally-occurring aluminosilicates or synthetically derived.
  • a method for producing aluminosilicate ion exchange materials is disclosed in U.S. Patent 3,985,669, Krummel, et al, issued October 12, 1976.
  • the aluminosilicate has a particle size of about 0.1-10 microns in diameter.
  • Organic detergent builders suitable for the purposes of the present invention include, but are not restricted to, a wide variety of polycarboxylate compounds.
  • polycarboxylate refers to compounds having a plurality of carboxylate groups, preferably at least 3 carboxylates.
  • Polycarboxylate builder can generally be added to the composition in acid form, but can also be added in the form of a neutralized salt. When utilized in salt form, alkali metals, such as sodium, potassium, and lithium, or alkanolammonium salts are preferred. Included among the polycarboxylate builders are a variety of categories of useful materials.
  • polycarboxylate builders encompasses the ether polycarboxylates, including oxydisuccinate, as disclosed in Berg, U.S. Patent 3,128,287, issued April 7, 1964, and Lamberti et al, U.S. Patent 3,635,830, issued January 18, 1972. See also "TMS/TDS" builders of U.S. Patent 4,663,071, issued to Bush et at, on May 5, 1987.
  • Suitable ether polycarboxylates also include cyclic compounds, particularly alicyclic compounds, such as those described in U.S. Patents 3,923,679; 3,835,163; 4,158,635; 4,120,874 and 4,102,903.
  • ether hydroxypolycarboxylates copolymers of maleic anhydride with ethylene or vinyl methyl ether, 1, 3, 5-trihydroxy benzene-2, 4, 6-trisulphonic acid, and carboxymethyloxysuccinic acid
  • various alkali metal, ammonium and substituted ammonium salts of polyacetic acids such as ethylenediamine tetraacetic acid and nitrilotriacetic acid
  • polycarboxylates such as mellitic acid, succinic acid, oxydisuccinic acid, polymaleic acid, benzene 1,3,5-tricarboxylic acid, carboxymethyloxysuccinic acid, and soluble salts thereof.
  • Citrate builders e.g., citric acid and soluble salts thereof (particularly sodium salt), are polycarboxylate builders of particular importance for heavy duty liquid detergent formulations due to their availability from renewable resources and their biodegradability. Citrates can also be used in granular compositions, especially in combination with zeolite and/or layered silicate builders. Oxydisuccinates are also especially useful in such compositions and combinations. Also suitable in the detergent compositions of the present invention are the 3,3-dicarboxy-4-oxa-1,6-hexanedioates and the related compounds disclosed in U.S. Patent 4,566,984, Bush, issued January 28, 1986.
  • succinic acid builders include the C 5 -C 20 alkyl and alkenyl succinic acids and salts thereof A particularly preferred compound of this type is dodecenylsuccinic acid.
  • succinate builders include: laurylsuccinate, myristylsuccinate, palmitylsuccinate, 2-dodecenylsuccinate (preferred), 2-pentadecenylsuccinate, and the like. Laurylsuccinates are the preferred builders of this group, and are described in European Patent Application 86200690.5/0,200,263, published November 5, 1986.
  • the various alkali metal phosphates such as the well-known sodium tripolyphosphates, sodium pyrophosphate and sodium orthophosphate can be used.
  • Phosphonate builders such as ethane-1-hydroxy-1,1-diphosphonate and other known phosphonates (see, for example, U.S. Patents 3,159,581; 3,213,030; 3,422,021; 3,400,148 and 3,422,137) can also be used.
  • the detergent compositions herein may optionally contain bleaching agents or bleaching compositions containing a bleaching agent and one or more bleach activators.
  • bleaching agents will typically be at levels of from about 1% to about 30%, more typically from about 5% to about 20%, of the detergent composition, especially for fabric laundering.
  • the amount of bleach activators will typically be from about 0.1% to about 60%, more typically from about 0.5% to about 40% of the bleaching composition comprising the bleaching agent-plus-bleach activator.
  • the bleaching agents used herein can be any of the bleaching agents useful for detergent compositions in textile cleaning, hard surface cleaning, or other cleaning purposes that are now known or become known. These include oxygen bleaches as well as other bleaching agents.
  • Perborate bleaches e.g., sodium perborate (e.g., mono- or tetra-hydrate) can be used herein.
  • Another category of bleaching agent that can be used without restriction encompasses percarboxylic acid bleaching agents and salts thereof. Suitable examples of this class of agents include magnesium monoperoxyphthalate hexahydrate, the magnesium salt of metachloro perbenzoic acid, 4-nonylamino-4-oxoperoxybutyric acid and diperoxydodecanedioic acid.
  • Such bleaching agents are disclosed in U.S. Patent 4,483,781, Hartman, issued November 20, 1984, U.S.
  • Highly preferred bleaching agents also include 6-nonylamino-6-oxoperoxycaproic acid as described in U.S. Patent 4,634,551, issued January 6, 1987 to Burns et al.
  • Peroxygen bleaching agents can also be used. Suitable peroxygen bleaching compounds include sodium carbonate peroxyhydrate and equivalent "percarbonate" bleaches, sodium pyrophosphate peroxyhydrate, urea peroxyhydrate, and sodium peroxide.
  • Persulfate bleach (e.g., OXONE, manufactured commercially by DuPont) can also be used.
  • a preferred percarbonate bleach comprises dry particles having an average particle size in the range from about 500 micrometers to about 1,000 micrometers, not more than about 10% by weight of said particles being smaller than about 200 micrometers and not more than about 10% by weight of said particles being larger than about 1,250 micrometers.
  • the percarbonate can be coated with silicate, borate or water-soluble surfactants.
  • Percarbonate is available from various commercial sources such as FMC, Solvay and Tokai Denka. Mixtures of bleaching agents can also be used.
  • Peroxygen bleaching agents, the perborates, the percarbonates, etc. are preferably combined with bleach activators, which lead to the in situ production in aqueous solution (i.e., during the washing process) of the peroxy acid corresponding to the bleach activator.
  • bleach activators Various nonlimiting examples of activators are disclosed in U.S. Patent 4,915,854, issued April 10, 1990 to Mao et al, and U.S. Patent 4,412,934.
  • NOBS nonanoyloxybenzene sulfonate
  • TAED tetraacetyl ethylene diamine
  • amido-derived bleach activators are those of the formulae: R 1 N(R 5 )C(O)R 2 C(O)L or R 1 C(O)N(R 5 )R 2 C(O)L wherein R 1 is an alkyl group containing from about 6 to about 12 carbon atoms, R 2 is an alkylene containing from 1 to about 6 carbon atoms, R 5 is H or alkyl, aryl, or alkaryl containing from about 1 to about 10 carbon atoms, and L is any suitable leaving group.
  • a leaving group is any group that is displaced from the bleach activator as a consequence of the nucleophilic attack on the bleach activator by the perhydrolysis anion.
  • a preferred leaving group is phenyl sulfonate.
  • bleach activators of the above formulae include (6-octanamido-caproyl)oxybenzenesulfonate, (6-nonanamidocaproyl)oxybenzenesulfonate, (6-decanamido-caproyl)oxybenzenesulfonate, and mixtures thereof as described in U.S. Patent 4,634,551, incorporated herein by reference.
  • Another class of bleach activators comprises the benzoxazin-type activators disclosed by Hodge et al in U.S. Patent 4,966,723, issued October 30, 1990, incorporated herein by reference.
  • a highly preferred activator of the benzoxazin-type is: Still another class of preferred bleach activators includes the acyl lactam activators, especially acyl caprolactams and acyl valerolactams of the formulae: wherein R 6 is H or an alkyl, aryl, alkoxyaryl, or alkaryl group containing from 1 to about 12 carbon atoms.
  • lactam activators include benzoyl caprolactam, octanoyl caprolactam, 3,5,5-trimethylhexanoyl caprolactam, nonanoyl caprolactam, decanoyl caprolactam, undecenoyl caprolactam, benzoyl valerolactam, octanoyl valerolactam, decanoyl valerolactam, undecenoyl valerolactam, nonanoyl valerolactam, 3,5,5-trimethylhexanoyl valerolactam and mixtures thereof See also U.S.
  • Patent 4,545,784 issued to Sanderson, October 8, 1985, incorporated herein by reference, which discloses acyl caprolactams, including benzoyl caprolactam, adsorbed into sodium perborate.
  • Bleaching agents other than oxygen bleaching agents are also known in the art and can be utilized herein.
  • One type of non-oxygen bleaching agent of particular interest includes photoactivated bleaching agents such as the sulfonated zinc and/or aluminum phthalocyanines. See U.S. Patent 4,033,718, issued July 5, 1977 to Holcombe et al. If used, detergent compositions will typically contain from about 0.025% to about 1.25%, by weight, of such bleaches, especially sulfonate zinc phthalocyanine.
  • the bleaching compounds can be catalyzed by means of a manganese compound.
  • a manganese compound Such compounds are well known in the art and include, for example, the manganese-based catalysts disclosed in U.S. Pat. 5,246,621, U.S. Pat. 5,244,594; U.S. Pat. 5,194,416; U.S. Pat. 5,114,606; and European Pat. App. Pub. Nos.
  • Preferred examples of these catalysts include Mn IV 2 (u-O) 3 (1,4,7-trimethyl-1,4,7-triazacyclononane) 2 (PF 6 ) 2 , Mn III 2 (u-O) 1 (u-OAc) 2 (1,4,7-trimethyl-1,4,7-triazacyclononane) 2- (ClO 4 ) 2 , Mn IV 4 (u-O) 6 (1,4,7-triazacyclononane) 4 (ClO 4 ) 4 , Mn III Mn IV 4 (u-O) 1 (u-OAc) 2- (1,4,7-trimethyl-1,4,7-triazacyclononane) 2 (ClO 4 ) 3 , Mn IV (1,4,7-trimethyl-1,4,7-triazacyclononane)-(OCH 3 ) 3 (PF 6 ), and mixtures thereof.
  • metal-based bleach catalysts include those disclosed in U.S. Pat. 4,430,243 and U.S. Pat. 5,114,611.
  • the use of manganese with various complex ligands to enhance bleaching is also reported in the following United States Patents: 4,728,455; 5,284,944; 5,246,612; 5,256,779; 5,280,117; 5,274,147; 5,153,161; and 5,227,084.
  • compositions and processes herein can be adjusted to provide on the order of at least one part per ten million of the active bleach catalyst species in the aqueous washing liquor, and will preferably provide from about 0.1 ppm to about 700 ppm, more preferably from about I ppm to about 500 ppm, of the catalyst species in the laundry liquor.
  • Enzymes can be included in the formulations herein for a wide variety of fabric laundering purposes, including removal of protein-based, carbohydrate-based, or triglyceride-based stains, for example, and for the prevention of refugee dye transfer, and for fabric restoration.
  • the enzymes to be incorporated include proteases, amylases, lipases, cellulases, and peroxidases, as well as mixtures thereof.
  • Other types of enzymes may also be included. They may be of any suitable origin, such as vegetable, animal, bacterial, fungal and yeast origin. However, their choice is governed by several factors such as pH-activity and/or stability optima, thermostability, stability versus active detergents, builders and so on.
  • bacterial or fungal enzymes are preferred, such as bacterial amylases and proteases, and fungal cellulases.
  • Enzymes are normally incorporated at levels sufficient to provide up to about 5 mg by weight, more typically about 0.01 mg to about 3 mg, of active enzyme per gram of the composition.
  • the compositions herein will typically comprise from about 0.001% to about 5%, preferably 0.01%-1% by weight of a commercial enzyme preparation.
  • Protease enzymes are usually present in such commercial preparations at levels sufficient to provide from 0.005 to 0.1 Anson units (AU) of activity per gram of composition.
  • Suitable examples of proteases are the subtilisins which are obtained from particular strains of B. subtilis and B. licheniforms.
  • protease is obtained from a strain of Bacillus, having maximum activity throughout the pH range of 8-12, developed and sold by Novo Industries A/S under the registered trade name ESPERASE. The preparation of this enzyme and analogous enzymes is described in British Patent Specification No. 1,243,784 of Novo.
  • Proteolytic enzymes suitable for removing protein-based stains include those sold under the tradenames ALCALASE and SAVINASE by Novo Industries A/S (Denmark) and MAXATASE by International Bio-Synthetics, Inc. (The Netherlands).
  • Other proteases include Protease A (see European Patent Application 130,756, published January 9, 1985) and Protease B (see European Patent Application Serial No.
  • Amylases include, for example, ⁇ -amylases described in British Patent Specification No. 1,296,839 (Novo), RAPIDASE, International Bio-Synthetics, Inc. and TERMAMYL, Novo Industries.
  • the cellulase usable in the present invention include both bacterial or fungal cellulase. Preferably, they will have a pH optimum of between 5 and 9.5. Suitable cellulases are disclosed in U.S.
  • Patent 4,435,307, Barbesgoard et al issued March 6, 1984, which discloses fungal cellulase produced from Humicola insolens and Humicola strain DSM1800 or a cellulase 212-producing fungus belonging to the genus Aeromonas, and cellulase extracted from the hepatopancreas of a marine mollusk (Dolabella Auricula Solander).
  • suitable cellulases are also disclosed in GB-A-2.075.028; GB-A-2.095.275 and DE-OS-2.247.832.
  • CAREZYME Novo is especially useful.
  • Suitable lipase enzymes for detergent usage include those produced by microorganisms of the Pseudomonas group, such as Pseudomonas stutzeri ATCC 19.154, as disclosed in British Patent 1,372,034. See also lipases in Japanese Patent Application 53,20487, laid open to public inspection on February 24, 1978. This lipase is available from Amano Pharmaceutical Co. Ltd., Nagoya, Japan, under the trade name Lipase P "Amano,” hereinafter referred to as "Amano-P.” Other commercial lipases include Amano-CES, lipases ex Chromobacter viscosum, e.g. Chromobacter viscosum var.
  • lipolyticum NRRLB 3673 commercially available from Toyo Jozo Co., Tagata, Japan; and further Chromobacter viscosum lipases from U.S. Biochemical Corp., U.S.A. and Disoynth Co., The Netherlands, and lipases ex Pseudomonas gladioli.
  • the LIPOLASE enzyme derived from Humicola lanuginosa and commercially available from Novo is a preferred lipase for use herein.
  • Peroxidase enzymes are used in combination with oxygen sources, e.g., percarbonate, perborate, persulfate, hydrogen peroxide, etc. They are used for "solution bleaching," i.e.
  • Peroxidase enzymes are known in the art, and include, for example, horseradish peroxidase, ligninase, and haloperoxidase such as chloro- and bromo-peroxidase.
  • Peroxidase-containing detergent compositions are disclosed, for example, in PCT International Application WO 89/099813, published October 19, 1989, by O. Kirk, assigned to Novo Industries A/S.
  • a wide range of enzyme materials and means for their incorporation into synthetic detergent compositions are also disclosed in U.S. Patent 3,553,139, issued January 5, 1971 to McCarty et al. Enzymes are further disclosed in U.S.
  • compositions which are commonly used in detergent compositions and which may be incorporated into the detergent tablets of the present invention include chelating agents, soil release agents, soil antiredeposition agents, dispersing agents, brighteners, suds suppressors, fabric softeners, dye transfer inhibition agents and perfumes.
  • the tablet according to the invention may be used according to a method of washing which significantly avoids this problem.
  • the new method comprises preparing an aqueous solution of a laundry detergent for use in a washing machine, wherein the aqueous solution of laundry detergent is formed by dissolving in water a tablet according to the invention.
  • a preferred method more specifically relates to the preparation of an aqueous solution of a laundry detergent for use in a front-loading washing machine, the front-loading washing machine having a dispensing drawer and a washing drum, wherein the aqueous solution of laundry detergent is formed by dissolving a detergent tablet according to the invention in water, characterised in that the detergent tablet is placed in the dispensing drawer and water is passed through the dispensing drawer so that the tablet is dispensed as an aqueous solution of a laundry detergent, the aqueous solution subsequently being passed in the washing drum.
  • composition A (% per weight) Anionic Agglomerates 1 21.45 Anionic Agglomerates 2 13.00 Cationic Agglomerate 5.45 Layered Silicate 10.8 Sodium percarbonate 14.19 Bleach activator agglomerates 5.49 Sodium carbonate 13.82 EDDS/Sulphate particle 0.47 Tetrasodium salt of Hydroxyethane Diphosphonic acid 0.73 Soil Release Polymer 0.33 Fluorescer 0.18 Zinc Phthalocyanide sulphonate encapsulate 0.025 Soap powder 1.40 Suds Suppressor 1.87 Citric acid 7.10 Protease 0.79 Lipase 0.28 Cellulase 0.22 Amylase 1.08 Binder Spray-on-system 1.325 TOTAL 100.00 Anionic agglomerates 1 comprise of 40%
  • Anionic agglomerates 2 comprise of 40% anionic surfactant, 28% zeolite and 32% carbonate.
  • Cationic agglomerates comprise of 20% cationic surfactant, 56% zeolite and 24% sulphate.
  • Layered silicate comprises of 95% SKS 6 and 5% silicate.
  • Bleach activator agglomerates comprise of 81% TAED, 17% acrylic/maleic copolymer (acid form) and 2% water.
  • Ethylene diamine N,N-disuccinic acid sodium salt/Sulphate particle comprise of 58% of Ethylene diamine N,N-disuccinic acid sodium salt, 23% of sulphate and 19% water.
  • Zinc phthalocyanine sulphonate encapsulates are 10% active. Suds suppressor comprises of 11.5% silicone oil (ex Dow Corning); 59% of zeolite and 29.5% of water. Binder spray-on system comprises of 50% Lutensit K-HD 96 and 50% PEG (polyethylene glycol).
  • Composition B (% per weight) Anionic Agglomerates 1 21.45 Anionic Agglomerates 2 13.00 Cationic Agglomerate 5.45 Layered Silicate 10.8 Sodium percarbonate 14.19 Bleach activator agglomerates 5.49 Sodium carbonate 12.645 EDDS/Sulphate particle 0.47 Tetrasodium salt of Hydroxyethane Diphosphonic acid 0.73 Soil Release Polymer 0.33 Fluorescer 0.18 Zinc Phthalocyanide sulphonate encapsulate 0.025 Soap powder 1.40 Suds Suppressor 1.87 Citric acid 7.10 Protease 0.79 Lipase 0.28 Cellulase 0.22 Amylase 1.08 Binder Spray-on-system 2.5 TOTAL 100.00 Anionic agglomerates 1 comprise of 40% anionic surfactant, 27% zeolite and 33% carbonate.
  • Anionic agglomerates 2 comprise of 40% anionic surfactant, 28% zeolite and 32% carbonate.
  • Cationic agglomerates comprise of 20% cationic surfactant, 56% zeolite and 24% sulphate.
  • Layered silicate comprises of 95% SKS 6 and 5% silicate.
  • Bleach activator agglomerates comprise of 81% TAED, 17% acrylic/maleic copolymer (acid form) and 2% water.
  • Ethylene diamine N,N-disuccinic acid sodium salt/Sulphate particle comprise of 58% of Ethylene diamine N,N-disuccinic acid sodium salt, 23% of sulphate and 19% water.
  • Zinc phthalocyanine sulphonate encapsulates are 10% active. Suds suppressor comprises of 11.5% silicone oil (ex Dow Corning); 59% of zeolite and 29.5% of water. Binder spray-on system comprises of 50% Lutensit K-HD 96 and 50% PEG (polyethylene glycol).
  • Composition C (%) Anionic agglomerates 1 9.1 Anionic agglomerates 2 22.5 Nonionic agglomerates 9.1 Cationic agglomerates 4.6 Layered silicate 9.7 Sodium percarbonate 12.2 Bleach activator agglomerates 6.1 Sodium carbonate 7.27 EDDS/Sulphate particle 0.5 Tetrasodium salt of Hydroxyethane Diphosphonic acid 0.6 Soil Release Polymer 0.3 Fluorescer 0.2 Zinc Phthalocyanine sulphonate encapsulate 0.03 Soap powder 1.2 Suds suppressor 2.8 Citric acid 5.5 Protease 1 Lipase 0.35 Cellulase 0.2 Amylase 1.1 Binder spray-on system 3.05 Perfume spray-on 0.5 DIBS 2.1 Anionic agglomerates 1 comprise of 40% anionic surfactant, 27% zeolite and 33% carbonate Anionic agglomerates 2 comprise of 40% anionic surfactant, 28% zeolite and 32% carbonate Non
  • Cationic agglomerates comprise of 20% cationic surfactant, 56% zeolite and 24% sulphate
  • Layered silicate comprises of 95% SKS 6 and 5% silicate
  • Bleach activator agglomerates comprise of 81% TAED, 17% acrylic/maleic copolymer (acid form) and 2% water.
  • Ethylene diamine N,N-disuccinic acid sodium salt/Sulphate particle comprise of 58% of Ethylene diamine N,N-disuccinic acid sodium salt, 23% of sulphate and 19% water.
  • Zinc phthalocyanine sulphonate encapsulates are 10% active.
  • Suds suppressor comprises of 11.5% silicone oil (ex Dow Corning); 59% of zeolite and 29.5% of water.
  • Binder spray-on system comprises of 0.5 parts of Lutensit K-HD 96 and 2.5 parts of PEGs Composition D (%) Anionic agglomerates 1 32 Cationic agglomerates 5 Layered silicate 11.5 Sodium percarbonate 16.2 Bleach activator agglomerates 4.7 Sodium carbonate 3.76 Sodium bicarbonate 2.0 Sodium sulphate 2.4 EDDS/Sulphate particle 0.5 Tetrasodium salt of Hydroxyethane 0.8 Diphosphonic acid Soil Release Polymer 0.3 Fluorescer 0.1 Zinc Phthalocyanine sulphonate encapsulate 0.02 Suds suppressor 2.1 Citric acid 2 Protease 0.7 Lipase 0.2 Cellulase 0.2 Amylase 0.6 Perfume encapsulates 0.2 Polymer particle 3 Perfume spray-on 0.35 Nonionic spray-on system 5.17 Zeolite
  • Ethylene diamine N,N-disuccinic acid sodium salt/Sulphate particle comprise of 58% of Ethylene diamine N,N-disuccinic acid sodium salt, 23% of sulphate and 19% water.
  • Zinc phthalocyanine sulphonate encapsulates are 10% active. Suds suppressor comprises of 11.5% silicone oil (ex Dow Corning); 59% of zeolite and 29.5% of water.
  • Perfume encapsulates comprise 50% perfume and 50% starch.
  • Polymer particle comprises 36%, 54% zeolite and 10% water
  • the Nonionic spray-on system comprises of 67% C12-C15 AE5 (alcohol with an average of 5 ethoxy groups per molecule), 24% N-methyl glucose amide and 9% water.
EP98202712A 1998-08-13 1998-08-13 Mehrschichtwaschmitteltablette mit unterschiedlicher Elastizität Withdrawn EP0979863A1 (de)

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EP98202712A EP0979863A1 (de) 1998-08-13 1998-08-13 Mehrschichtwaschmitteltablette mit unterschiedlicher Elastizität
CN 99811915 CN1322240A (zh) 1998-08-13 1999-08-11 具有不同弹性的多层片状洗涤剂
CA002338793A CA2338793A1 (en) 1998-08-13 1999-08-11 Multilayer detergent tablet with different elasticities
PCT/US1999/018190 WO2000009645A1 (en) 1998-08-13 1999-08-11 Multilayer detergent tablet with different elasticities
JP2000565082A JP2002522630A (ja) 1998-08-13 1999-08-11 異なる弾性を有する複数層洗剤タブレット
BR9912936-1A BR9912936A (pt) 1998-08-13 1999-08-11 Tablete detergente com camadas múltiplas com diferentes elasticidades
AU54762/99A AU5476299A (en) 1998-08-13 1999-08-11 Multilayer detergent tablet with different elasticities

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Cited By (2)

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Publication number Priority date Publication date Assignee Title
WO2001021756A1 (en) * 1999-09-23 2001-03-29 Unilever N.V. Cleaning compositions
US10260025B2 (en) 2008-02-11 2019-04-16 Ecolab Usa Inc. Use of activator complexes to enhance lower temperature cleaning in alkaline peroxide cleaning systems

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JP2001081651A (ja) * 1999-09-06 2001-03-27 Tsudakoma Corp 水噴射式織機の水噴射ポンプ用チェックバルブ
CN102965223B (zh) * 2012-11-26 2014-01-08 吴金龙 纳米多功能洗涤片
CN114635241A (zh) * 2022-03-24 2022-06-17 薛强 一种纺织长纱漂洗工艺

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EP0224128A2 (de) * 1985-11-21 1987-06-03 Henkel Kommanditgesellschaft auf Aktien Mehrschichtige Reinigungsmitteltabletten für das maschinelle Geschirrspülen
EP0466485A2 (de) * 1990-07-13 1992-01-15 Unilever Plc Detergenszusammensetzungen
EP0481547A1 (de) * 1990-10-17 1992-04-22 Unilever N.V. Detergenstabletten für Geschirrspülmaschinen
DE4404279A1 (de) * 1994-02-10 1995-08-17 Henkel Kgaa Tablette mit Buildersubstanzen
EP0711827A2 (de) * 1994-11-14 1996-05-15 Unilever Plc Detergenszusammensetzungen in Tablettenform
WO1997003177A1 (de) * 1995-07-13 1997-01-30 Joh. A. Benckiser Gmbh Geschirrwaschmaschinenspülmittel in form einer tablette
EP0851025A2 (de) * 1996-12-23 1998-07-01 Unilever N.V. Sauerstoffbleichsystem enthaltende automatische Geschirrspülmitteltabletten

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DE2207633A1 (de) * 1972-02-18 1973-08-30 Boehringer Mannheim Gmbh Reagenztabletten und verfahren zur herstellung derselben
EP0224128A2 (de) * 1985-11-21 1987-06-03 Henkel Kommanditgesellschaft auf Aktien Mehrschichtige Reinigungsmitteltabletten für das maschinelle Geschirrspülen
EP0466485A2 (de) * 1990-07-13 1992-01-15 Unilever Plc Detergenszusammensetzungen
EP0481547A1 (de) * 1990-10-17 1992-04-22 Unilever N.V. Detergenstabletten für Geschirrspülmaschinen
DE4404279A1 (de) * 1994-02-10 1995-08-17 Henkel Kgaa Tablette mit Buildersubstanzen
EP0711827A2 (de) * 1994-11-14 1996-05-15 Unilever Plc Detergenszusammensetzungen in Tablettenform
WO1997003177A1 (de) * 1995-07-13 1997-01-30 Joh. A. Benckiser Gmbh Geschirrwaschmaschinenspülmittel in form einer tablette
EP0851025A2 (de) * 1996-12-23 1998-07-01 Unilever N.V. Sauerstoffbleichsystem enthaltende automatische Geschirrspülmitteltabletten

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Publication number Priority date Publication date Assignee Title
WO2001021756A1 (en) * 1999-09-23 2001-03-29 Unilever N.V. Cleaning compositions
US10260025B2 (en) 2008-02-11 2019-04-16 Ecolab Usa Inc. Use of activator complexes to enhance lower temperature cleaning in alkaline peroxide cleaning systems

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AU5476299A (en) 2000-03-06
BR9912936A (pt) 2001-09-25

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