EP1072717A1 - Abgabevorrichtung für Waschmitteltabletten - Google Patents

Abgabevorrichtung für Waschmitteltabletten Download PDF

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Publication number
EP1072717A1
EP1072717A1 EP99202368A EP99202368A EP1072717A1 EP 1072717 A1 EP1072717 A1 EP 1072717A1 EP 99202368 A EP99202368 A EP 99202368A EP 99202368 A EP99202368 A EP 99202368A EP 1072717 A1 EP1072717 A1 EP 1072717A1
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EP
European Patent Office
Prior art keywords
tablet
detergent
acid
flap
preferred
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.)
Withdrawn
Application number
EP99202368A
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English (en)
French (fr)
Inventor
Jacky Pierre Duquet
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Procter and Gamble Co
Original Assignee
Procter and Gamble Co
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Procter and Gamble Co filed Critical Procter and Gamble Co
Priority to EP99202368A priority Critical patent/EP1072717A1/de
Priority to NL1013169A priority patent/NL1013169C1/nl
Priority to DE29917230U priority patent/DE29917230U1/de
Priority to GB9923310A priority patent/GB2339579A/en
Priority to ES009903010U priority patent/ES1044629U/es
Publication of EP1072717A1 publication Critical patent/EP1072717A1/de
Withdrawn legal-status Critical Current

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Classifications

    • A—HUMAN NECESSITIES
    • A47—FURNITURE; DOMESTIC ARTICLES OR APPLIANCES; COFFEE MILLS; SPICE MILLS; SUCTION CLEANERS IN GENERAL
    • A47L—DOMESTIC WASHING OR CLEANING; SUCTION CLEANERS IN GENERAL
    • A47L15/00—Washing or rinsing machines for crockery or tableware
    • A47L15/42—Details
    • A47L15/44—Devices for adding cleaning agents; Devices for dispensing cleaning agents, rinsing aids or deodorants
    • A47L15/4445—Detachable devices
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06F—LAUNDERING, DRYING, IRONING, PRESSING OR FOLDING TEXTILE ARTICLES
    • D06F39/00—Details of washing machines not specific to a single type of machines covered by groups D06F9/00 - D06F27/00 
    • D06F39/02—Devices for adding soap or other washing agents
    • D06F39/024—Devices for adding soap or other washing agents mounted on the agitator or the rotating drum; Free body dispensers

Definitions

  • the present invention relates to devices for delivering a detergent composition in tablet form.
  • Tablets are used in particular in the field of automatic dish washing or in the field of machine washing of laundry to facilitate handling of a detergent composition compared to alternative forms such as powder, granules, liquids or paste.
  • alternative forms such as powder, granules, liquids or paste.
  • a dispensing device for a detergent tablet the device being at least partially formed from a flexible water permeable material, the device comprising at least one wall, the wall comprising an opening to insert the tablet.
  • devices to disperse a detergent tablet have disadvantages.
  • such devices typically comprise closing means in order to prevent the tablet from escaping from the device during the wash, such closing means rendering the manufacture of the device more complex, and more difficult to use.
  • the invention seeks to provide a device of the above mentioned kind which allows to prevent the tablet from escaping from the device during the wash, and which is less complex to manufacture and easier to use.
  • this object is accomplished in a device of the above mentioned kind characterised in that the device further comprises a flap, the flap being pleated over the opening, the flap being retained pleated over the opening.
  • a device formed in accordance with the invention has a number of advantages. Due to the flap being pleated and retained over the opening, the tablet can remain in the device during the wash. This simple arrangement removes the need to add complex closing means to the device.
  • the invention relates to a dispensing device for a detergent tablet.
  • dispensing device it should be understood a device which is used for dispensing the tablet in an aqueous solution, whereby the dispensing is usually facilitated by the use of the dispensing device.
  • Dispensing devices already exist for detergent powder, as proposed example in EP-A-343069 or EP-A-343070.
  • Dispensing devices also exist for liquid detergent, as proposed for example in FR-A-2563250. Depending on the form of the detergent, the dispensing devices have different specifics.
  • the dispensing device according to the invention relates to a detergent tablet.
  • a detergent tablet is typically obtained by compression of a detergent powder.
  • a detergent tablet may be coated or not, and have one or more layers. Detergent tablets are being sold currently. Typical detergent tablets are described for example in EP-A-846755.
  • the device of the invention is at least partially formed from a flexible water permeable material. By flexible, it should be understood that the material is not rigid. Typically, a material is hereby considered as flexible when it collapses when submitted to its own weight.
  • Such a characteristic of the material normally leads to improved tablet disintegration due to the mechanical squeezing effect incurred by the deformation of the flexible material during a normal wash, such deformation being for example due to collisions between the device and the laundry to be washed, or to collisions between the device a wall of a washing machine.
  • flexible material include for example synthetic polymeric (nylon, poly-olefin) materials or vegetal (cotton, cellulosic) materials.
  • the flexible material is also water permeable. This should be understood as meaning that liquid water is not prevented from flowing through the material. This characteristic allows to facilitate dispersion of a tablet by allowing ingress or egress of the aqueous solution in which the tablet disperses.
  • Tablet dispersion is used here as a generic wording encompassing equivalent expressions such as tablet disintegration or tablet dissolution for example.
  • the device comprises at least one wall. Indeed, the device comprises a part typically in the form of a pocket, the pocket being suited to contain one or more detergent tablets.
  • the device comprises at least one wall, but may also comprises more than one wall, in order to be made more resistant, for example.
  • the wall comprising an opening to insert the tablet. What is meant by "opening to insert the tablet” is an opening which has dimensions allowing insertion of a tablet without involving permanent deformation of the device. It is preferred that the device comprises only one opening to insert the tablet. It should be noted that this preferred device may also comprise other apertures, whereby such other apertures are typically smaller than the opening to insert the tablet, so that the other apertures are not openings as far as the tablet itself is concerned.
  • the device of the invention further comprises a flap.
  • a flap should be understood as a flat part hinged onto another part of the device.
  • the flap is pleated over the opening, so that it covers the opening when in its default position. This means that the part of the wall of the device which directly surrounds the opening is covered by an extra wall formed by the flap. Furthermore, the flap is retained pleated over the opening. In this manner, the flap is such that the opening remains substantially closed by the flap, thus preventing a tablet which is in the device to exit from the device through the opening.
  • the flap may be permanently retained pleated over the opening, for example by means of a thread, or by welding or sealing.
  • permanently retained it should be understood that the flap cannot be removed from the retained position without significant effort (such as un-sewing the thread for example).
  • the flap is retained pleated in such a manner that a tablet may be inserted under the flap while the flap is retained pleated over the opening. This may be obtained for example by threading the flap onto the opening except along a length, this length free of thread constituting an opening towards the region covered by the flap and allowing insertion of the tablet in the region covered by the flap.
  • the opening towards the region covered by the flap is not located directly over the opening in the wall of the device, so that the flap still covers the opening in the wall of the device, thus acting according to the invention.
  • the flap may alternatively be removeably retained pleated over the opening.
  • a tablet may be inserted in the region covered by the flap by lifting up the flap, after which the flap may be fixed again to be retained pleated over the opening.
  • Such removeability may be obtained for example by using a button arrangement.
  • the device is formed from folding a single piece of the flexible material. This allows to produce a device according to the invention with a simple process.
  • the flexible water permeable material is a net material.
  • Such material may be woven, extruded or non-woven for example.
  • the material should be resistant to the high temperature of machine washing, to detergent compositions, and to use through several cycles. Further, it is preferred that the material is not abrasive to avoid damaging fabrics.
  • the device is partially formed from a flexible water impermeable material.
  • a water impermeable material is sift-proof such that liquid water cannot pass through such a material.
  • the presence of such a sift-proof material allows to prevent passage of even the thinnest solid particles which may be separated from the tablet for example by friction.
  • the device has a part opposed to the opening, whereby the part opposed to the opening is formed from the flexible water impermeable material.
  • a part opposed to the opening it should be understood a part which is on the bottom of the device if the opening is on the top of the device. It is preferred that the part opposed to the opening is formed from the flexible water impermeable material in order to prevent the thinnest solid particles which may be separated from the tablet for example by friction to sieve through and to be deposited on a support for the device prior to inserting the device in a washing machine.
  • the part of the device being formed from flexible water impermeable material is in the form of a band.
  • a band is placed around the device allowing a potential user to place the fingers onto the band when holding the device, thus in particular minimising potential direct skin contact with the detergent tablet.
  • the device is at least partially formed from a flexible water permeable material and also partially formed from a flexible water impermeable material. Substantially, the device is preferably completely formed of the addition of the flexible water permeable material and of the flexible water impermeable material, although it may comprise addition optional elements such as closing means or such as structural means.
  • the flexible material forming the device has a total surface area. The total surface area of the flexible material is preferably formed of more than 50% of the permeable material and of less than 50% of the impermeable material. More preferably, the total surface area of the flexible material is formed of more than 60% of the permeable material and of less than 40% of the impermeable material.
  • the total surface area of the flexible material is formed of more than 75% of the permeable material and of less than 25% of the impermeable material. Most preferably, the total surface area of the flexible material is formed of more than 90% of the permeable material and of less than 10% of the impermeable material. Further, the flexible impermeable material should preferably cover a surface area of at least half of the total external surface of a laundry detergent tablet. Typically, the flexible impermeable material should have a surface area of at least 10 cm 2 , more preferably of at least 15 cm 2 , even more preferably of at least 20 cm 2 and most preferably of at least 30 cm 2 .
  • the invention also relates to a process of dispersing a detergent tablet in an aqueous solution in a washing machine comprising the first step of providing a detergent tablet and a device according to the invention, a second step of inserting the tablet in the device, and a third step of inserting the device containing the tablet into the washing machine.
  • the process of the invention is particularly advantageous with a tablet having a tensile strength of at least 30 KPa. Indeed, it was found that a tablet having a high tensile strength will require improved dispersion by means of a device when compared to a tablet having a low tensile strength. More preferably, the invention applies to a tablet having a tensile strength of at least 40 KPa, even more preferably of at least 50KPa.
  • the process is preferred when two or more tablets are inserted into the device. Indeed, the insertion of more than one tablet may increase disintegration due to mechanical friction between the different tablets. Further, at equivalent total product quantity, the surface activity of two tablets will normally be higher than the surface activity of one tablet only.
  • a kit comprising a device according to the invention and further comprising a plurality of detergent tablets, the device and the plurality of detergent tablets being provided in a package.
  • the package is a carton box, the carton box containing the detergent tablets which may be contained into secondary packages such as flow-wraps, the device being preferably collapsible and placed on the top part of the box.
  • the tablets may comprise components such as fragrance, surfactants, enzymes, detergent etc....
  • Typical tablet compositions for the preferred embodiment of the present invention are disclosed in the pending European applications of the Applicant n° 96203471.6, 96203462.5, 96203473.2 and 96203464.1 for example.
  • Elements typically entering in the composition of detergent tablets or of other forms of detergents such as liquids or granules are detailed in the following paragraphs.
  • the tablet may comprise a highly soluble compound.
  • 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 may comprise a compound having a Cohesive Effect on the particulate material of a detergent matrix forming the tablet.
  • 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.
  • Means to assess tablet or layer strength are given in Pharmaceutical dosage forms : tablets volume 1 Ed. H.A. Lieberman et al, published in 1989.
  • 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 compound 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 0.5% per weight of a tablet or layer is formed from the highly soluble compound, more preferably at least 0.75%, even more preferably at least 2% and most preferably at least 4% per weight of the tablet or layer being formed from the highly soluble compound having a cohesive effect on the particulate material.
  • a composition 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 tablet may comprise several layers.
  • the layer may be considered as a tablet itself.
  • Detergent tablets 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 a tablet 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.
  • 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.
  • perfume and slurries of optical brighteners may be sprayed.
  • a finely divided flow aid dustting agent such as zeolites, carbonates, silicas
  • 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 tablets have a square cross-section of 45 mm by 45 mm and are 25 mm high.
  • 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 1.15 g/cc.
  • Multi layered tablets are typically formed in rotating presses by placing the particulate material of each layer, one after the other in force feeding flasks. As the process continues, the particulate material layers are then pressed together in the pre-compression and compression stages stations to form the multilayer 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 may be integrated to a detergent tablet, whereby this compound is also a hydrotrope compound.
  • Such hydrotrope compound may be generally used to favour surfactant dissolution by avoiding gelling.
  • 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)):
  • 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.
  • Detergent tablets may further comprise 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. 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.
  • dissolution aid could be provided by using compounds such as sodium acetate or urea.
  • 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.
  • Solidity of a tablet may be improved by making a coated tablet, the coating covering a non-coated tablet, thereby improving the mechanical characteristics 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 quickly when subjected to stronger mechanical shock. Furthermore it is advantageous if 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". The coating material has a melting point preferably of from 40 °C to 200 °C. The coating can be applied in a number of ways.
  • 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. During the solidification phase, the coating undergoes some internal stress (e.g. shrinkage upon cooling) and external stress (e.g.
  • the coating comprises a component which is liquid at 25°C. It is believed that this liquid component will allow the coating to better withstand and absorb mechanical stress by rendering the coating structure more flexible.
  • the component which is liquid at 25°C is preferably added to the coating materials in proportions of less than 10% by weight of the coating, more preferably less than 5% by weight, and most preferably of less than 3% by weight.
  • the component which is liquid at 25°C is preferably added to the coating materials in proportions of more than 0.1% by weight of the coating, more preferably more than 0.3% by weight, and most preferably of more than 0.5% by weight. Further preferred is the addition of reinforcing fibres to the coating in order to further reinforce the structure.
  • the coating comprises a crystallised structure.
  • crystallised it should be understood that the coating comprises a material which is solid at ambient temperature (25°C) and has a structure exhibiting some order. This can be detected typically by usual crystallography techniques e.g. X-ray analysis, on the material itself.
  • the material forming the crystallised structure does not co-crystallised or only partially with the optional component which is liquid at 25°C mentioned above. Indeed, it is preferred that the optional component remains in the liquid state at 25°C in the coating crystalline structure in order to provide flexibility to the structure and resistance to mechanical stress.
  • the optional component which is liquid at 25°C may advantageously have a functionality in the washing of laundry, for example silicone oil which provides suds suppression benefits or perfume oil.
  • the coating may also comprise other optional components. Suitable coating materials are for example 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. Most preferred is adipic acid.
  • oxalic acid malonic acid
  • succinic acid glutaric acid
  • adipic acid pimelic acid
  • suberic acid azelaic acid
  • sebacic acid undecanedioic acid
  • dodecanedioic acid dodecanedioic acid
  • tridecanedioic acid tridecanedioic acid and mixtures thereof.
  • adipic acid Clearly substantially insoluble materials having a melting point below 40 °C are often not sufficiently solid at ambient temperatures and it has been found that materials having a melting point
  • an acid having a melting point of more than 90°C such as azelaic, sebacic acid, dodecanedioic acid is used. It is even more preferred to use an acid having a melting point of more than 145°C such as adipic acid.
  • 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. For most purposes, the coating forms from 1% to 10%, preferably from 1.5% to 5%, of the tablet weight. Tablet coatings are very hard and provide extra strength to the tablet.
  • optional components which are liquid at 25° are including PolyEthylene Glycols, thermal oil, silicon oil, esters of dicarboxylic acids, mono carboxylic acids, parafin, triacetin, perfumes or alkaline solutions. It is preferred that the structure of the components which is liquid at 25°C is close to the material forming the crystallised structure, so that the structure is not excessively disrupted. In a most preferred embodiment, the crystallised structure is made of adipic acid, the component which is liquid at 25°C being available under the name CoasolTM from Chemoxy International, being a blend of the di-isobutyl esters of the glutaric, succinic and adipic acid.
  • this component is the good dispersion in the adipic acid to provide flexibility. It should be noted that disintegration of the adipic acid is further improved by the adipate content of CoasolTM. Fracture of the coating in the wash can be improved by adding a disintegrant in the coating. This disintegrant will swell once in contact with water and break the coating in small pieces. This will improve the dissolution of the coating in the wash solution. 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, polymers containing cationic (e.g.
  • the coating comprises an acid having a melting temperature of at least 145°C, such as adipic acid for example, as well as a clay, such as a bentonite clay for example, whereby the clay is used as a disintegrant and also to render the structure of adipic acid more favourable for water penetration, thus improving the dispersion of the adipic acid in a aqueous medium.
  • an acid having a melting temperature of at least 145°C such as adipic acid for example, as well as a clay, such as a bentonite clay for example, whereby the clay is used as a disintegrant and also to render the structure of adipic acid more favourable for water penetration, thus improving the dispersion of the adipic acid in a aqueous medium.
  • the coating further comprises reinforcing fibres. Such fibres have been found to improve further the resistance of the coating to mechanical stress and minimise the splitting defect occurence.
  • Such fibres are preferably having a length of at least 100 ⁇ m, more preferably of at least 200 ⁇ m and most preferably of at least 250 ⁇ m to allow structure reinforcement. Such fibres are preferably having a length of at less than 500 ⁇ m, more preferably of less than 400 ⁇ m and most preferably of less than 350 ⁇ m in order not to impact onto dispersion of the coating in an aqueous medium.
  • Materials which may be used for these fibres include viscose rayon, natural nylon, synthetic nylon (polyamides types 6 and 6,6), acrylic, polyester, cotton and derivatives of cellulose such as CMCs. Most preferred is a cellulosic material available under the trade mark Solka-FlocTM from Fibers Sales & Development.
  • Such fibres do not normally need pre-compression for reinforcing the coating structure.
  • Such fibres are preferably added at a level of less than 5% by weight of the coating, more preferably less than 3% by weight.
  • Such fibres are preferably added at a level of more than 0.5% by weight of the coating, more preferably more than 1% by weight.
  • Surfactant are typically comprised in a detergent composition.
  • 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 sulfates ("AE x
  • 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 in detergent compositions 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 I, 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 4% 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.
  • 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. Preferred synthetic crystalline aluminosilicate ion exchange materials useful herein are available under the designations Zeolite A, Zeolite P (B), Zeolite MAP and Zeolite X.
  • the crystalline aluminosilicate ion exchange material has the formula: Na 12 [(AlO 2 ) 12 (SiO 2 ) 12 ] ⁇ xH 2 O wherein x is from about 20 to about 30, especially about 27.
  • This material is known as Zeolite A.
  • 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.
  • 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.
  • One important category of 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 al, 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. Other suitable polycarboxylates are disclosed in U.S.
  • Fatty acids e.g., C 12 -C 18 monocarboxylic acids
  • Such use of fatty acids will generally result in a diminution of sudsing, which should be taken into account by the formulator.
  • 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 1 ppm to about 500 ppm, of the catalyst species in the laundry liquor.
  • Suitable enzymes for use in the compositions of the present invention include enzymes selected from cellulases, hemicellulases, peroxidases, proteases, gluco-amylases, amylases, xylanases, lipases, phospholipases, esterases, cutinases, pectinases, keratanases, reductases, oxidases, phenoloxidases, lipoxygenases, ligninases, pullulanases, tannases, pentosanases, mannanases, ⁇ -glucanases, arabinosidases, hyaluronidase, chondroitinase, laccase or mixtures thereof.
  • a preferred combination is a cocktail of conventional applicable enzymes like protease, amylase, lipase, cutinase and/or cellulase in conjunction with one or more plant cell wall degrading enzymes.
  • the cellulases usable in the present invention include both bacterial or fungal cellulases. Preferably, they will have a pH optimum of between 5 and 12 and a specific activity above 50 CEVU/mg (Cellulose Viscosity Unit). Suitable cellulases are disclosed in U.S.
  • Patent 4,435,307, Barbesgoard et al, J61078384 and W096/02653 which discloses fungal cellulase produced respectively from Humicola insolens, Trichoderma, Thielavia and Sporotrichum.
  • EP 739 982 describes cellulases isolated from novel Bacillus species. Suitable cellulases are also disclosed in GB-A-2.075.028; GB-A-2.095.275; DE-OS-2.247.832 and W095/26398. Examples of such cellulases are cellulases produced by a strain of Humicola insolens (Humicola grisea var. thermoidea), particularly the Humicola strain DSM 1800.
  • these cellulases originated from Humicola insolens having a molecular weight of about 50KDa, an isoelectric point of 5.5 and containing 415 amino acids; and a ⁇ 43kD endoglucanase derived from Humicola insolens, DSM 1800, exhibiting cellulase activity; a preferred endoglucanase component has the amino acid sequence disclosed in PCT Patent Application No. WO 91/17243.
  • suitable cellulases are the EGIII cellulases from Trichoderma longibrachiatum described in WO94/21801, Genencor, published September 29, 1994. Especially suitable cellulases are the cellulases having color care benefits.
  • cellulases examples include cellulases described in European patent application No. 91202879.2, filed November 6, 1991 (Novo). Carezyme and Celluzyme (Novo Nordisk A/S) are especially useful. See also WO91/17244 and W091/21801. Other suitable cellulases for fabric care and/or cleaning properties are described in W096/34092, WO96/17994 and WO95/24471. Said cellulases are normally incorporated in the detergent composition at levels from 0.0001% to 2% of pure enzyme by weight of the detergent composition.
  • Enzymatic system may be used as bleaching agents : The hydrogen peroxide may also be present by adding an enzymatic system (i.e.
  • Peroxidase enzymes are used in combination with oxygen sources, e.g. percarbonate, perborate, persulfate, hydrogen peroxide, etc and with a phenolic substrate as bleach enhancing molecule. They are used for "solution bleaching", i.e. to prevent transfer of dyes or pigments removed from substrates during wash operations to other substrates in the wash solution.
  • Peroxidase enzymes are known in the art, and include, for example, horseradish peroxidase, ligninase and haloperoxidase such as chloro- and bromoperoxidase.
  • Peroxidase-containing detergent compositions are disclosed, for example, in PCT International Application WO 89/099813, WO89/09813 and in European Patent application EP No. 91202882.6, filed on November 6, 1991 and EP No. 96870013.8, filed February 20, 1996.
  • laccase enzyme are generally comprised at a level of from 0.1% to 5% by weight of total composition.
  • Preferred enhancers are substitued phenthiazine and phenoxasine 10-Phenothiazinepropionicacid (PPT), 10-ethylphenothiazine-4-carboxylic acid (EPC), 10-phenoxazinepropionic acid (POP) and 10-methylphenoxazine (described in WO 94/12621) and substitued syringates (C3-C5 substitued alkyl syringates) and phenols.
  • Sodium percarbonate or perborate are preferred sources of hydrogen peroxide.
  • Said peroxidases are normally incorporated in the detergent composition at levels from 0.0001% to 2% of pure enzyme by weight of the detergent composition.
  • Other preferred enzymes that can be included in the detergent compositions of the present invention include lipases.
  • 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.
  • Suitable lipases include those which show a positive immunological cross-reaction with the antibody of the lipase, produced by the microorganism Pseudomonas fluorescent IAM 1057. This lipase is available from Amano Pharmaceutical Co.
  • Lipase P Lipase P
  • Other suitable commercial lipases include Amano-CES, lipases ex Chromobacter viscosum, e.g. Chromobacter viscosum var. lipolyticum NRRLB 3673 from Toyo Jozo Co., Tagata, Japan; Chromobacter viscosum lipases from U.S. Biochemical Corp., U.S.A. and Disoynth Co., The Netherlands, and lipases ex Pseudomonas gladioli.
  • Chromobacter viscosum e.g. Chromobacter viscosum var. lipolyticum NRRLB 3673 from Toyo Jozo Co., Tagata, Japan
  • Chromobacter viscosum lipases from U.S. Biochemical Corp., U.S.A. and Disoynth Co., The Netherlands
  • lipases ex Pseudomonas gladioli.
  • lipases such as M1 Lipase R and Lipomax R (Gist-Brocades) and Lipolase R and Lipolase Ultra R (Novo) which have found to be very effective when used in combination with the compositions of the present invention.
  • lipolytic enzymes described in EP 258 068, WO 92/05249 and WO 95/22615 by Novo Nordisk and in WO 94/03578, WO 95/35381 and WO 96/00292 by Unilever.
  • cutinases [EC 3.1.1.50] which can be considered as a special kind of lipase, namely lipases which do not require interfacial activation.
  • cutinases additive of cutinases to detergent compositions have been described in e.g. WO-A-88/09367 (Genencor); WO 90/09446 (Plant Genetic System) and WO 94/14963 and WO 94/14964 (Unilever).
  • the lipases and/or cutinases are normally incorporated in the detergent composition at levels from 0.0001% to 2% of pure enzyme by weight of the detergent composition.
  • Suitable proteases are the subtilisins which are obtained from particular strains of B. subtilis and B. licheniformis (subtilisin BPN and BPN').
  • protease is obtained from a strain of Bacillus, having maximum activity throughout the pH range of 8-12, developed and sold as ESPERASE® by Novo Industries A/S of Denmark, hereinafter "Novo". The preparation of this enzyme and analogous enzymes is described in GB 1,243,784 to Novo.
  • suitable proteases include ALCALASE®, DURAZYM® and SAVINASE® from Novo and MAXATASE®, MAXACAL®, PROPERASE® and MAXAPEM® (protein engineered Maxacal) from Gist-Brocades.
  • proteases described in patent applications EP 251 446 and WO 91/06637, protease BLAP® described in WO91/02792 and their variants described in WO 95/23221. See also a high pH protease from Bacillus sp. NCIMB 40338 described in WO 93/18140 A to Novo. Enzymatic detergents comprising protease, one or more other enzymes, and a reversible protease inhibitor are described in WO 92/03529 A to Novo. When desired, a protease having decreased adsorption and increased hydrolysis is available as described in WO 95/07791 to Procter & Gamble.
  • protease for detergents suitable herein is described in WO 94/25583 to Novo.
  • Other suitable proteases are described in EP 516 200 by Unilever.
  • Proteolytic enzymes also encompass modified bacterial serine proteases, such as those described in European Patent Application Serial Number 87 303761.8, filed April 28, 1987 (particularly pages 17, 24 and 98), and which is called herein "Protease B", and in European Patent Application 199,404, Venegas, published October 29, 1986, which refers to a modified bacterial serine protealytic enzyme which is called "Protease A" herein.
  • Protease C is a variant of an alkaline serine protease from Bacillus in which lysine replaced arginine at position 27, tyrosine replaced valine at position 104, serine replaced asparagine at position 123, and alanine replaced threonine at position 274.
  • Protease C is described in EP 90915958:4, corresponding to WO 91/06637, Published May 16, 1991. Genetically modified variants, particularly of Protease C, are also included herein.
  • a preferred protease referred to as "Protease D” is a carbonyl hydrolase variant having an amino acid sequence not found in nature, which is derived from a precursor carbonyl hydrolase by substituting a different amino acid for a plurality of amino acid residues at a position in said carbonyl hydrolase equivalent to position +76, preferably also in combination with one or more amino acid residue positions equivalent to those selected from the group consisting of +99, +101, +103, +104, +107, +123, +27, +105, +109, +126, +128, +135, +156, +166, +195, +197, +204, +206, +210, +216, +217, +218, +222, +260, +265, and/or +274 according to the numbering of Bacillus amyloliquefaciens subtilisin, as described in WO95/10591 and in the patent application of C.
  • a carbonyl hydrolase variant of the protease described in WO95/10591 having an amino acid sequence derived by replacement of a plurality of amino acid residues replaced in the precursor enzyme corresponding to position +210 in combination with one or more of the following residues : +33, +62, +67, +76, +100, +101, +103, +104, +107, +128, +129, +130, +132, +135, +156, +158, +164, +166, +167, +170, +209, +215, +217, +218, and +222, where the numbered position corresponds to naturally-occurring subtilisin from Bacillus amyloliquefaciens or to equivalent amino acid residues in other carbonyl hydrolases or subtilisins, such as Bacillus lentus subtilisin (
  • proteases are multiply-substituted protease variants. These protease variants comprise a substitution of an amino acid residue with another naturally occuring amino acid residue at an amino acid residue position corresponding to position 103 of Bacillus amyloliquefaciens subtilisin in combination with a substitution of an amino acid residue positions corresponding to positions 1, 3, 4, 8, 9, 10, 12, 13, 16, 17, 18, 19, 20, 21, 22, 24, 27, 33, 37, 38, 42, 43, 48, 55, 57, 58, 61, 62, 68, 72, 75, 76, 77, 78, 79, 86, 87, 89, 97, 98, 99, 101, 102, 104, 106, 107, 109, 111, 114, 116, 117, 119, 121, 123, 126, 128, 130, 131, 133, 134, 137, 140, 141, 142, 146, 147, 158, 159,
  • the proteolytic enzymes are incorporated in the detergent compositions of the present invention a level of from 0.0001% to 2%, preferably from 0.001% to 0.2%, more preferably from 0.005% to 0.1% pure enzyme by weight of the composition.
  • Amylases ( ⁇ and/or ⁇ ) can be included for removal of carbohydrate-based stains. W094/02597, Novo Nordisk A/S published February 03, 1994, describes cleaning compositions which incorporate mutant amylases. See also WO95/10603, Novo Nordisk A/S, published April 20, 1995.
  • Other amylases known for use in cleaning compositions include both ⁇ - and ⁇ -amylases.
  • ⁇ -Amylases are known in the art and include those disclosed in US Pat. no.
  • amylases are stability-enhanced amylases described in WO94/18314, published August 18, 1994 and W096/05295, Genencor, published February 22, 1996 and amylase variants having additional modification in the immediate parent available from Novo Nordisk A/S, disclosed in WO 95/10603, published April 95. Also suitable are amylases described in EP 277 216, W095/26397 and W096/23873 (all by Novo Nordisk).
  • ⁇ -amylases examples are Purafect Ox Am® from Genencor and Termamyl®, Band®, Fungamyl® and Duramyl®, all available from Novo Nordisk A/S Denmark.
  • W095/26397 describes other suitable amylases : ⁇ -amylases characterised by having a specific activity at least 25% higher than the specific activity of Termamyl® at a temperature range of 25°C to 55°C and at a pH value in the range of 8 to 10, measured by the Phadebas® ⁇ -amylase activity assay.
  • the variants are those demonstrating improved thermal stability, more preferably those wherein at least one amino acid residue equivalent to F180, R181, G182, T183, G184, or K185 has been deleted from the parent ⁇ -amylase.
  • Particularly preferred are those variants having improved thermal stability which comprise the amino acid deletions R181* + G182* or T183* + G184*.
  • Other amylolytic enzymes with improved properties with respect to the activity level and the combination of thermal stability and a higher activity level are described in W095/35382.
  • the amylolytic enzymes are incorporated in the detergent compositions of the present invention a level of from 0.0001% to 2%, preferably from 0.00018% to 0.06%, more preferably from 0.00024% to 0.048% pure enzyme by weight of the composition.
  • the above-mentioned enzymes may be of any suitable origin, such as vegetable, animal, bacterial, fungal and yeast origin. Origin can further be mesophilic or extremophilic (psychrophilic, psychrotrophic, thermophilic, barophilic, alkalophilic, acidophilic, halophilic, etc.). Purified or non-purified forms of these enzymes may be used. Also included by definition, are mutants of native enzymes. Mutants can be obtained e.g.
  • enzymes are normally incorporated in the detergent composition at levels from 0.0001% to 2% of pure enzyme by weight of the detergent composition.
  • the enzymes can be added as separate single ingredients (prills, granulates, stabilized liquids, etc. containing one enzyme ) or as mixtures of two or more enzymes ( e.g. cogranulates ).
  • Other suitable detergent ingredients that can be added are enzyme oxidation scavengers which are described in Copending European Patent application 92870018.6 filed on January 31, 1992.
  • enzyme oxidation scavengers are ethoxylated tetraethylene polyamines.
  • a range of enzyme materials and means for their incorporation into synthetic detergent compositions is also disclosed in WO 9307263 A and WO 9307260 A to Genencor International, WO 8908694 A to Novo, and U.S. 3,553,139, January 5, 1971 to McCarty et al.
  • Enzymes are further disclosed in U.S. 4,101,457, Place et al, July 18, 1978, and in U.S. 4,507,219, Hughes, March 26, 1985.
  • Enzyme materials useful for liquid detergent formulations, and their incorporation into such formulations are disclosed in U.S. 4,261,868, Hora et al, April 14, 1981.
  • Enzymes for use in detergents can be stabilised by various techniques. Enzyme stabilisation techniques are disclosed and exemplified in U.S. 3,600,319, August 17, 1971, Gedge et al, EP 199,405 and EP 200,586, October 29, 1986, Venegas. Enzyme stabilisation systems are also described, for example, in U.S. 3,519,570. A useful Bacillus, sp. AC13 giving proteases, xylanases and cellulases, is described in WO 9401532 A to Novo.
  • detergent compositions include chelating agents, soil release agents, soil antiredeposition agents, dispersing agents, suds suppressors, fabric softeners, dye transfer inhibition agents and perfumes.
  • a packaging system may be formed from a sheet of flexible material.
  • Materials suitable for use as a flexible sheet include mono-layer, co-extruded or laminated films.
  • Such films may comprise various components, such as poly-ethylene, poly-propylene, poly-styrene, poly-ethylene-terephtalate.
  • the packaging system is composed of a poly-ethylene and bi-oriented-polypropylene co-extruded film with an MVTR of less than 5 g/day/m 2 .
  • the MVTR of the packaging system is preferably of less than 10 g/day/m 2 , more preferably of less than 5 g/day/m 2 .
  • the film (2) may have various thicknesses.
  • the thickness should typically be between 10 and 150 ⁇ m, preferably between 15 and 120 ⁇ m, more preferably between 20 and 100 ⁇ m, even more preferably between 25 and 80 ⁇ m and most preferably between 30 and 40 ⁇ m.
  • a packaging material preferably comprises a barrier layer typically found with packaging materials having a low oxygen transmission rate, typically of less than 300 cm 3 /m 2 /day, preferably of less than 150 cm 3 /m 2 /day, more preferably of less than 100 cm 3 /m 2 /day, even more preferably of less than 50 cm 3 /m 2 /day and most preferably of less than 10 cm 3 /m 2 /day.
  • Typical materials having such barrier properties include bi oriented polypropylene, poly ethylene terephthalate, Nylon, poly(ethylene vinyl alcohol) , or laminated materials comprising one of these, as well as SiOx (Silicium oxydes), or metallic foils such as aluminium foils for example.
  • Such packaging material may have a beneficial influence on the stability of the product during storage for example.
  • the packing method used are typically the wrapping methods disclosed in W092/20593, including flow wrapping or over wrapping.
  • a longitudinal seal is provided, which may be a fin seal or an overlapping seal, after which a first end of the packaging system is closed with a first end seal, followed by closure of the second end with a second end seal.
  • the packaging system may comprise re-closing means as described in W092/20593.
  • a cold seal or an adhesive is particularly suited.
  • a band of cold seal or a band of adhesive may be applied to the surface of the packaging system at a position adjacent to the second end of the packaging system, so that this band may provide both the initial seal and re-closure of the packaging system.
  • the adhesive or cold seal band may correspond to a region having a cohesive surface, i.e. a surface which will adhere only to another cohesive surface.
  • Such re-closing means may also comprise spacers which will prevent unwanted adhesion. Such spacers are described in WO 95/13225, published on the 18 th of May 1995.
  • a cold seal may be used, and in particular a grid of cold seal, whereby the cold seal is adapted so as to facilitate opening of the packaging system.
  • Figure 1 illustrates a device according to the invention, whereby the flap of the device is partially lifted.
  • Figure 2 illustrates the device of Figure 1, whereby a tablet is being inserted in the device.
  • Figure 3 illustrates the device of Figure 2, the device containing the tablet being inserted in a washing machine.
  • the device 1 of Figure 1 is entirely made from a net material 4 and comprises one wall only.
  • the flap 2 is an extension of the wall of the device which covers another part of the wall of the device, the opening 3 to insert the tablet being located under the flap 2.
  • the flap 2 is retained pleated over the opening 3 in that a lateral side 20 of the flap is threaded to the wall.
  • both lateral sides 20 and 21 of the flap may be threaded, so that a tablet 5 may still be inserted under the flap 2 and through the opening 3 of the device 1 by means of the flexibility of the net material 4.
  • the device comprises a top 11, a bottom 12 and left 13 and right 14 sides. However, a simpler version may be formed only from top 11 and bottom 12 sides, the internal volume for the tablet 5 being formed by the flexibility of the net material 4.
  • the tablet 5 is being inserted into the device 1 by lifting the flap 2 and passing the tablet through the opening 3. Once this is done, the device containing the tablet 10 as illustrated in Figure 3 may be inserted in the washing machine for a normal wash to be carried out.

Landscapes

  • Engineering & Computer Science (AREA)
  • Textile Engineering (AREA)
  • Detergent Compositions (AREA)
  • Measurement Of The Respiration, Hearing Ability, Form, And Blood Characteristics Of Living Organisms (AREA)
EP99202368A 1999-07-19 1999-07-19 Abgabevorrichtung für Waschmitteltabletten Withdrawn EP1072717A1 (de)

Priority Applications (5)

Application Number Priority Date Filing Date Title
EP99202368A EP1072717A1 (de) 1999-07-19 1999-07-19 Abgabevorrichtung für Waschmitteltabletten
NL1013169A NL1013169C1 (nl) 1999-07-19 1999-09-29 Afgifte-inrichting voor een wasmiddeltablet.
DE29917230U DE29917230U1 (de) 1999-07-19 1999-09-30 Dispensiervorrichtung für eine Waschmitteltablette
GB9923310A GB2339579A (en) 1999-07-19 1999-10-01 A dispensing device for a detergent tablet
ES009903010U ES1044629U (es) 1999-07-19 1999-11-26 Dispensador de detergente en pastilla

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
EP99202368A EP1072717A1 (de) 1999-07-19 1999-07-19 Abgabevorrichtung für Waschmitteltabletten

Publications (1)

Publication Number Publication Date
EP1072717A1 true EP1072717A1 (de) 2001-01-31

Family

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Family Applications (1)

Application Number Title Priority Date Filing Date
EP99202368A Withdrawn EP1072717A1 (de) 1999-07-19 1999-07-19 Abgabevorrichtung für Waschmitteltabletten

Country Status (5)

Country Link
EP (1) EP1072717A1 (de)
DE (1) DE29917230U1 (de)
ES (1) ES1044629U (de)
GB (1) GB2339579A (de)
NL (1) NL1013169C1 (de)

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2003053212A2 (de) * 2001-12-21 2003-07-03 Henkel Kommanditgesellschaft Auf Aktien Vorrichtung zur verbesserung des klarspüleffektes in geschirrspülmaschinen
WO2006105863A1 (en) * 2005-04-05 2006-10-12 Unilever Plc Dispensing device
WO2012127257A1 (en) * 2011-03-19 2012-09-27 Dental Care Innovation Gmbh System for dissolution of a tablet or granulate in a stream of water
US10371834B2 (en) 2012-05-31 2019-08-06 Minnesota Imaging And Engineering Llc Detector systems for integrated radiation imaging
US10509136B2 (en) 2012-05-31 2019-12-17 Minnesota Imaging And Engineering Llc Detector systems for radiation imaging
US11073625B2 (en) 2016-09-09 2021-07-27 Minnesota Imaging And Engineering Llc Structured detectors and detector systems for radiation imaging
USD947366S1 (en) 2016-12-15 2022-03-29 Water Pik, Inc. Oral irrigator handle

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE10053416A1 (de) 2000-10-27 2002-05-08 Bsh Bosch Siemens Hausgeraete Verfahren zum maschinellen Reinigen von Textilien oder festen Gegenständen

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DE9016224U1 (de) * 1990-04-02 1991-02-14 Henkel KGaA, 40589 Düsseldorf Gefalteter Beuteldosierer
EP0576234A1 (de) * 1992-06-22 1993-12-29 Unilever Plc Verteilungsvorrichtung
WO1995011330A1 (en) * 1993-10-18 1995-04-27 The Procter & Gamble Company Package assembly for granular product
GB2327093A (en) * 1997-07-08 1999-01-13 Unilever Plc Detergent packaging and detergent dispensing combination

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GB8811794D0 (en) * 1988-05-18 1988-06-22 Procter & Gamble Single-dose fabric-treatment articles
GB8909778D0 (en) * 1989-04-28 1989-06-14 Procter & Gamble Fabric-treatment sachets with handling device
DE4010525A1 (de) * 1990-04-02 1991-10-10 Henkel Kgaa Gefalteter beuteldosierer

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Publication number Priority date Publication date Assignee Title
DE9016224U1 (de) * 1990-04-02 1991-02-14 Henkel KGaA, 40589 Düsseldorf Gefalteter Beuteldosierer
EP0576234A1 (de) * 1992-06-22 1993-12-29 Unilever Plc Verteilungsvorrichtung
WO1995011330A1 (en) * 1993-10-18 1995-04-27 The Procter & Gamble Company Package assembly for granular product
GB2327093A (en) * 1997-07-08 1999-01-13 Unilever Plc Detergent packaging and detergent dispensing combination

Cited By (14)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2003053212A2 (de) * 2001-12-21 2003-07-03 Henkel Kommanditgesellschaft Auf Aktien Vorrichtung zur verbesserung des klarspüleffektes in geschirrspülmaschinen
WO2003053212A3 (de) * 2001-12-21 2003-10-02 Henkel Kgaa Vorrichtung zur verbesserung des klarspüleffektes in geschirrspülmaschinen
WO2006105863A1 (en) * 2005-04-05 2006-10-12 Unilever Plc Dispensing device
CN103476548B (zh) * 2011-03-19 2017-11-14 牙科保健创新公司 用于片剂或颗粒在水流中溶解的系统
CN103476548A (zh) * 2011-03-19 2013-12-25 牙科保健创新公司 用于片剂或颗粒在水流中溶解的系统
US9492361B2 (en) 2011-03-19 2016-11-15 Dental Care Innovation Gmbh System for dissolution of a tablet or granulate in a stream of water
WO2012127257A1 (en) * 2011-03-19 2012-09-27 Dental Care Innovation Gmbh System for dissolution of a tablet or granulate in a stream of water
US10371834B2 (en) 2012-05-31 2019-08-06 Minnesota Imaging And Engineering Llc Detector systems for integrated radiation imaging
US10509136B2 (en) 2012-05-31 2019-12-17 Minnesota Imaging And Engineering Llc Detector systems for radiation imaging
US10663606B2 (en) 2012-05-31 2020-05-26 Minnesota Imaging And Engineering Llc Detector systems for integrated radiation imaging
US10955569B2 (en) 2012-05-31 2021-03-23 Minnesota Imaging And Engineering Llc Detector systems for integrated radiation imaging
US11073625B2 (en) 2016-09-09 2021-07-27 Minnesota Imaging And Engineering Llc Structured detectors and detector systems for radiation imaging
US12019194B2 (en) 2016-09-09 2024-06-25 Minnesota Imaging And Engineering Llc Structured detectors and detector systems for radiation imaging
USD947366S1 (en) 2016-12-15 2022-03-29 Water Pik, Inc. Oral irrigator handle

Also Published As

Publication number Publication date
DE29917230U1 (de) 1999-12-16
GB2339579A (en) 2000-02-02
GB9923310D0 (en) 1999-12-08
ES1044629U (es) 2000-05-16
NL1013169C1 (nl) 1999-12-27

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