EP1072716A1 - Distributeur de détergent en pastilles - Google Patents

Distributeur de détergent en pastilles Download PDF

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Publication number
EP1072716A1
EP1072716A1 EP99202367A EP99202367A EP1072716A1 EP 1072716 A1 EP1072716 A1 EP 1072716A1 EP 99202367 A EP99202367 A EP 99202367A EP 99202367 A EP99202367 A EP 99202367A EP 1072716 A1 EP1072716 A1 EP 1072716A1
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EP
European Patent Office
Prior art keywords
tablet
detergent
acid
tablets
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Withdrawn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
EP99202367A
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German (de)
English (en)
Inventor
Gautier Engisch
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 EP99202367A priority Critical patent/EP1072716A1/fr
Priority to NL1013170A priority patent/NL1013170C1/nl
Priority to DE29917231U priority patent/DE29917231U1/de
Priority to GB9923312A priority patent/GB2345920A/en
Priority to ES009903009U priority patent/ES1044628Y/es
Publication of EP1072716A1 publication Critical patent/EP1072716A1/fr
Withdrawn legal-status Critical Current

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    • 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.
  • Also known is a process of dispersing a detergent tablet in an aqueous medium in a washing machine comprising the first step of providing a detergent tablet and a device being at least partially formed from a flexible water permeable material, 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 flexible water permeable material may let through, prior to use in the wash medium, dry powder which is usually produced by the tablet by friction.
  • the flexible permeable material typically comprises apertures of a size such that the fingers of a user will be in contact with the tablet itself through such apertures once the tablet is inserted into the device and prior to use in the wash medium.
  • the invention seeks to provide a combination and a process of the above mentioned type, which avoids at least some of the above mentioned disadvantages.
  • this object is accomplished in the first and second aspects of the invention in a combination or process of the above mentioned kind characterised in that the device is also partially formed from a flexible water impermeable material.
  • a combination or process in accordance with the invention has a number of advantages. Since the device is also partially formed from a flexible water impermeable material, contact between fingers of a user and the tablet may be prevented by having the user catching the device in its part formed from the water impermeable material. Indeed, such water impermeable material would a fortiori prevent contact between the tablet and the fingers. Further, the part of the device formed from the flexible water permeable material would also prevent any dry powder produced by the tablet by friction to be let through. Due to the flexibility of the water impermeable material, the improvement in dispersion characteristics of the tablet which may result from an increase of mechanical disintegration is maintained.
  • the invention relates to the combination of a detergent tablet and of a device to disperse the tablet in an aqueous medium.
  • a device to disperse a tablet it should be understood a device which is used for dispensing the tablet in an aqueous medium, 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.
  • An aqueous medium is typically formed mainly of water, and typically applies here to the washing medium for laundry.
  • the invention relates to the combination of a detergent tablet and of a device.
  • 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. 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, polyolefin) 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 medium 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 contains the tablet.
  • the device is used as a mean for controlling the dispersion characteristics of the tablet, so that the device defines a first region which is inside the device and contains the tablet, as well as a second region which is outside the device, the characteristics of the device itself allowing to control dispersion of the tablet by means of the characteristics of the separation between the first and the second region.
  • separation is achieved partly by the flexible water permeable material.
  • the characteristics of the separation between the first and the second region depend normally also on the flexible water impermeable material.
  • a material is hereby considered as flexible when it collapses when submitted to its own weight.
  • the device is also 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 an opening and 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.
  • a user will put the empty device onto a supporting surface, the part opposed to the opening being in contact with the supporting surface, and insert a tablet into the device through the opening, whereby the tablet may be inserted together with solid particles which may be separated from the tablet by friction for example, such solid particles being prevented from soiling the supporting surface by means of the impermeable material forming the part opposed to the opening.
  • 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 device comprises at least one wall, but may also comprises more than one wall, in order to be made more resistant, for example.
  • 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 comprises a sleeve.
  • a sleeve is a piece of material in the shape of a tube having two ends.
  • the sleeve has at least one 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.
  • the sleeve has 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.
  • this opening is simply located on one end of the sleeve, the other end of the sleeve being closed as far as a tablet is concerned.
  • the sleeve has two openings for a tablet. Typically, each of these two openings is located on each of both ends of the sleeve.
  • the combination of the length and of the flexibility of the sleeve is such that the egress of a tablet inserted in the sleeve is hindered.
  • the sleeve should have a length and a flexibility allowing to wrap the tablet in the sleeve. More preferably, the length and flexibility of the sleeve allows to wrap the sleeve around the tablet so that the wrapping part of the sleeve goes all around the tablet at least ones.
  • the part of the sleeve used to wrap the tablet is typically the part of the sleeve which comprises the opening, the tablet being normally sitting in the other part opposed to the opening.
  • the tablet would typically sit roughly in the middle of the sleeve, each of the free ends of the sleeve being thereby wrapped around the tablet.
  • the sleeve has a length of at least 10 cm, more preferably of at least 17 cm, even more preferably of at least 22 cm and most preferably of at least 30 cm.
  • the sleeve is of such a flexibility that it is freely pliant or pliable.
  • An opening to insert a tablet may be provided with alternative closing means such as a string, a velcro band or an elastic string or rubber band which allows insertion of the tablet when stretch and prevents egress of a tablet when in normal position.
  • the tablet fits loosely in the device, so that the tablet is not closely constrained by the wall of the sleeve, so that the tablet may move relatively freely within the device. This facilitates insertion of the tablet in the device, and may also favour disintegration of the tablet.
  • 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 invention also relates to a process of dispersing a detergent tablet in an aqueous medium in a washing machine comprising the first step of providing a detergent tablet and a device being at least partially formed from a flexible water permeable material, 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 being characterised in that the device is also partially formed from a flexible water impermeable material.
  • the detergent tablet and the device of the process are preferably according to the first aspect of the invention.
  • 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.
  • the invention also relates to a kit comprising a device and a plurality of detergent tablets according to the first aspect of the invention, 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 medium or 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.
  • 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 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 WO95/26398. 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 WO91/21801. 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.
  • 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. Ltd., Nagoya, Japan, under the trade name Lipase P "Amano,” hereinafter referred to as "Amano-P".
  • 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.
  • 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. Addition 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').
  • One suitable 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.
  • proteases include ALCALASE®, DURAZYM® and SAVINASE® from Novo and MAXATASE®, MAXACAL®, PROPERASE® and MAXAPEM® (protein engineered Maxacal) from Gist-Brocades.
  • Enzymatic detergents comprising protease, one or more other enzymes, and a reversible protease inhibitor are described in WO 92/03529 A to Novo.
  • a protease having decreased adsorption and increased hydrolysis is available as described in WO 95/07791 to Procter & Gamble.
  • a recombinant trypsin-like 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 W095/10591 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,
  • 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.
  • 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. 5,003,257; EP 252,666; WO/91/00353; FR 2,676,456; EP 285,123; EP 525,610; EP 368,341; and British Patent specification no. 1,296,839 (Novo).
  • Other suitable 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.
  • amylases described in EP 277 216, W095/26397 and W096/23873 are also suitable.
  • Examples of commercial ⁇ -amylases products are Purafect Ox Am® from Genencor and Termamyl®, Ban® ,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.
  • variants of the above enzymes 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, August17, 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 WO92/20593, 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 WO92/20593.
  • 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 the second step of the process according to the invention, whereby a detergent tablet having two layers is being inserted in a first embodiment of a device according to the combination of the invention.
  • Figure 2 illustrates the third step of the process according to the invention of inserting the device containing the tablet of figure 1 into a washing machine.
  • Figure 3 illustrates the second step of the process according to the invention, whereby a detergent tablet having two layers is being inserted in a second embodiment of a device according to the combination of the invention.
  • Figure 4 illustrates the third step of the process according to the invention of inserting the device containing the tablet of figure 3 into a washing machine.
  • the device 2 of Figure 1 is partially formed from a flexible water permeable material 3.
  • the flexible water permeable material 3 is a net material.
  • the device 2 also comprises the impermeable flexible material 40, which is located in the part 6 opposed to the opening 5 of the device 2, and has substantially the shape of a cup.
  • the opening 5 of the device 2 is provided with a string 7 linked to the net material 3, whereby such string 7 is used as closing means.
  • the tablet 1 is also illustrated and is ready to be inserted in the device 2 according to the process of the invention to obtain the combination of the invention.
  • Figure 2 illustrates how the device 2 containing the tablet 1 is thereafter inserted in a laundry washing machine.
  • the "cup" shape of the portion of the device 2 made from a water impermeable material 40 allows to avoid particles from the tablet 1 to be deposited onto the supporting surface on which the device 2 is placed. Further, the cup shape comprises a rim or border which has substantially the shape of a band allowing a user to hold the device 2 without direct skin contact with the tablet 1.
  • the device 2 of Figure 3 is similar to the device of Figure 1.
  • the impermeable flexible material 41 is only present in the form of a band, the band circumventing the device 2, so that the device 2 containing the tablet 1 as in Figure 4 may be held by a user avoiding direct contact with the tablet 1, while maximising the proportion of permeable flexible material 3 compared to impermeable flexible material 41 in order to accelerate tablet 1 dispersion.
  • Figure 4 illustrates the insertion of the combination of the invention into a washing machine.

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)
  • Detail Structures Of Washing Machines And Dryers (AREA)
EP99202367A 1999-07-19 1999-07-19 Distributeur de détergent en pastilles Withdrawn EP1072716A1 (fr)

Priority Applications (5)

Application Number Priority Date Filing Date Title
EP99202367A EP1072716A1 (fr) 1999-07-19 1999-07-19 Distributeur de détergent en pastilles
NL1013170A NL1013170C1 (nl) 1999-07-19 1999-09-29 Afgifte-inrichting voor een wasmiddeltablet.
DE29917231U DE29917231U1 (de) 1999-07-19 1999-09-30 Dispensiervorrichtung für eine Waschmitteltablette
GB9923312A GB2345920A (en) 1999-07-19 1999-10-01 A dispensing device for a detergent tablet
ES009903009U ES1044628Y (es) 1999-07-19 1999-11-26 Dispensador de detergente en pastilla.

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
EP99202367A EP1072716A1 (fr) 1999-07-19 1999-07-19 Distributeur de détergent en pastilles

Publications (1)

Publication Number Publication Date
EP1072716A1 true EP1072716A1 (fr) 2001-01-31

Family

ID=8240471

Family Applications (1)

Application Number Title Priority Date Filing Date
EP99202367A Withdrawn EP1072716A1 (fr) 1999-07-19 1999-07-19 Distributeur de détergent en pastilles

Country Status (5)

Country Link
EP (1) EP1072716A1 (fr)
DE (1) DE29917231U1 (fr)
ES (1) ES1044628Y (fr)
GB (1) GB2345920A (fr)
NL (1) NL1013170C1 (fr)

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2006061065A1 (fr) * 2004-12-08 2006-06-15 Unilever Plc Dispositif de distribution
WO2006061086A1 (fr) * 2004-12-08 2006-06-15 Unilever Plc Diffuseur
WO2006105863A1 (fr) * 2005-04-05 2006-10-12 Unilever Plc Dispositif de distribution
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

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB0119710D0 (en) * 2001-08-13 2001-10-03 Unilever Plc Cleaning and rinsing of textile fabrics
ES2671176T3 (es) * 2007-09-19 2018-06-05 Zobele Holding Spa Dispositivo dosificador de liberación gradual de sustancias en aparatos de uso doméstico en presencia de agua

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0345409A1 (fr) * 1988-02-15 1989-12-13 Henkel Kommanditgesellschaft auf Aktien Dispositif doseur pour retenir et distribuer un produit de traitement pour le linge
EP0576234A1 (fr) * 1992-06-22 1993-12-29 Unilever Plc Dispositif diffuseur
WO1995011330A1 (fr) * 1993-10-18 1995-04-27 The Procter & Gamble Company Ensemble emballage pour produits granulaires
GB2327093A (en) * 1997-07-08 1999-01-13 Unilever Plc Detergent packaging and detergent dispensing combination

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE3211470A1 (de) * 1982-03-29 1983-10-06 Henkel Kgaa Mittel zur pflege von textilien
DE3833536A1 (de) * 1988-10-01 1990-04-05 Henkel Kgaa Dosierelement
DE19806113A1 (de) 1998-02-14 1999-08-19 Henkel Ecolab Gmbh & Co Ohg Verfahren zur Dosierung von Waschmitteln und dazu geeignete Vorrichtung

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0345409A1 (fr) * 1988-02-15 1989-12-13 Henkel Kommanditgesellschaft auf Aktien Dispositif doseur pour retenir et distribuer un produit de traitement pour le linge
EP0576234A1 (fr) * 1992-06-22 1993-12-29 Unilever Plc Dispositif diffuseur
WO1995011330A1 (fr) * 1993-10-18 1995-04-27 The Procter & Gamble Company Ensemble emballage pour produits granulaires
GB2327093A (en) * 1997-07-08 1999-01-13 Unilever Plc Detergent packaging and detergent dispensing combination

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2006061065A1 (fr) * 2004-12-08 2006-06-15 Unilever Plc Dispositif de distribution
WO2006061086A1 (fr) * 2004-12-08 2006-06-15 Unilever Plc Diffuseur
WO2006105863A1 (fr) * 2005-04-05 2006-10-12 Unilever Plc Dispositif de distribution
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

Also Published As

Publication number Publication date
ES1044628Y (es) 2001-05-01
DE29917231U1 (de) 1999-12-16
NL1013170C1 (nl) 1999-12-27
GB9923312D0 (en) 1999-12-08
GB2345920A (en) 2000-07-26
ES1044628U (es) 2000-05-16

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