EP1276838B1 - Wash cycle unit dose softener - Google Patents
Wash cycle unit dose softener Download PDFInfo
- Publication number
- EP1276838B1 EP1276838B1 EP01928774A EP01928774A EP1276838B1 EP 1276838 B1 EP1276838 B1 EP 1276838B1 EP 01928774 A EP01928774 A EP 01928774A EP 01928774 A EP01928774 A EP 01928774A EP 1276838 B1 EP1276838 B1 EP 1276838B1
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- EP
- European Patent Office
- Prior art keywords
- unit dose
- softening
- composition
- pentaerythritol
- clay
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
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Classifications
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- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
- C11D1/66—Non-ionic compounds
- C11D1/667—Neutral esters, e.g. sorbitan esters
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- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
- C11D17/0047—Detergents in the form of bars or tablets
- C11D17/0065—Solid detergents containing builders
- C11D17/0073—Tablets
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- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
- C11D17/04—Detergent materials or soaps characterised by their shape or physical properties combined with or containing other objects
- C11D17/041—Compositions releasably affixed on a substrate or incorporated into a dispensing means
- C11D17/042—Water soluble or water disintegrable containers or substrates containing cleaning compositions or additives for cleaning compositions
- C11D17/044—Solid compositions
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- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/0005—Other compounding ingredients characterised by their effect
- C11D3/001—Softening compositions
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- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/02—Inorganic compounds ; Elemental compounds
- C11D3/12—Water-insoluble compounds
- C11D3/124—Silicon containing, e.g. silica, silex, quartz or glass beads
- C11D3/1246—Silicates, e.g. diatomaceous earth
- C11D3/1253—Layer silicates, e.g. talcum, kaolin, clay, bentonite, smectite, montmorillonite, hectorite or attapulgite
- C11D3/126—Layer silicates, e.g. talcum, kaolin, clay, bentonite, smectite, montmorillonite, hectorite or attapulgite in solid compositions
Definitions
- This invention relates to wash cycle unit dose laundry compositions for softening or conditioning fabrics. More particularly, this invention relates to unit dose fabric softening compositions which are compacted granular compositions suitable for use in the wash cycle of an automatic washing machine.
- Detergent compositions manufactured in the form of compacted detergent powder are known in the art.
- U.S. 5,225,100 for example, describes a tablet of compacted powder comprising an anionic detergent compound which will adequately disperse in the wash water.
- detergent compositions in the form of compacted granular tablets of various shapes have received much attention in the patent literature, the use of such tablets to provide a unit dose fabric softener which will soften or condition fabrics in the wash cycle without impairing detergency or otherwise compromise the cleaning benefits provided by the detergent composition is not known.
- a unit dose composition for the rinse cycle must be formulated to readily dispense its contents upon contact with water in a period of time corresponding to the residence time of the unit dose in the dispenser, namely, the period of time during which water enters and flows through the rinse cycle dispenser.
- Laundry detergent compositions which further include a fabric softener to provide softening or conditioning of fabrics in the wash cycle of the laundering operation are well-known in the art and described in the patent literature. See, for example, U.S. Patent 4,605,506 to Wixon; U.S. Patent 4,818,421 to Boris et al. and U.S. Patent 4,569,773 to Ramachandran et al., all assigned to Colgate-Palmolive Co., and U.S. Patent 4,851,138 assigned to Akzo.
- U.S. Patent 5,972,870 to Anderson describes a multi-layered laundry tablet for washing which may include a detergent in the outer layer and a fabric softener, or water softener or fragrance in the inner layer.
- wash cycle active fabric softeners typically in powder form. But, these type products are characterized by the same inconvenience inherent with the use of powered detergents, namely, problems of handling, caking in the container or wash cycle dispenser, and the need for a dosing device to deliver the desired amount of active softener material to the wash water.
- a unit dose wash cycle fabric softening composition in the form of a compacted granular tablet offers numerous advantages, but it is important that such tablets be sufficiently hard and not friable so as to withstand handling and transportation without breaking or fragmenting.
- tablet makers In order to achieve the desired level of hardness, tablet makers generally tend to increase the compacting pressure. But, a high compacting pressure, if favorable to the hardness of the tablet, lowers the disintegration rate of such tablet.
- WO-A-99/40171 discloses laundry detergent tablets containing montmorillonite.
- the unit dose fabric softening compositions which are compacted granular compositions, must be able to disperse in the wash liquor in a short period of time to avoid any residue at the end of the wash cycle.
- the wash cycle time can be as short as 12 minutes and as long as 90 minutes (in typical European washers) depending on the type of washer and the wash conditions. Therefore, to make sure that the compacted unit dose is properly dispersed in the wash liquor before the end of the cycle, disintegrating materials must be added to the granules before compacting.
- This need for disintegrating agents is well-known in the art and the most popular materials used for this purpose are water swelling polymers such as polyvinylpyrrolidone, cellulosic polymers or a blend of citric acid and bicarbonate salt that provide an effervescent matrix.
- the present invention provides a unit dose wash cycle fabric softening composition for softening or conditioning fabrics in the wash cycle of an automatic washing machine, said unit dose comprising (a) a compacted granular fabric softener composition, the amount of (a) being sufficient to form a unit dose capable of providing effective softening or conditioning of fabrics in the wash cycle of said washing machine, and wherein said fabric softener composition comprises a treated montmorillonite-containing clay selected to have initial properties as follows:
- the unit dose fabric softening composition is characterized by being in the form of a tablet and having no discrete outer layer surrounding the fabric softener comprised of an alkaline material such that the pH of the wash water is increased upon dissolution of said outer layer in said wash water.
- granular as used herein in describing the fabric softener is intended to encompass relatively coarser granules varying in size from about 150 to 2,000 microns as well as finer powder having a size as small as 30 to 50 microns.
- fabric softener is used herein for purposes of convenience to refer to materials which provide softening and/or conditioning benefits to fabrics in the wash cycle of a home or automatic laundering machine.
- the compacted granular fabric softener composition of the invention is preferably comprised of a fabric softening clay optionally in combination with an organic fatty softening material.
- a fabric softening clay optionally in combination with an organic fatty softening material.
- Especially preferred fabric softeners comprise a clay mineral softener, such as bentonite, in combination with a pentaerythritol ester compound as further described herein.
- Useful combinations of such softener may vary from about 80%, to about 90%, by weight, of clay, and from about 10% to about 20%, by weight, of fatty softening material such as a pentaerythritol compound (often abbreviated herein as "PEC").
- PEC pentaerythritol compound
- the present invention is predicated on the use of a treated montmorillonite-containing clay, preferably a treated bentonite, as herein defined, as an active softening ingredient in a unit dose softening composition for the wash cycle.
- a treated montmorillonite-containing clay preferably a treated bentonite, as herein defined
- the resultant unit dose composition has reduced tendency to gel on contact with water so that when used in conjunction with laundry detergent compositions it manifests improved dispersion properties in the wash water without having any adverse effect on its softening properties.
- a process for softening or conditioning laundry which comprises contacting the laundry with an effective amount of the unit dose laundry composition defined above.
- the clays that are useful components of the invented products are those which cooperate with the organic fatty softener materials to provide enhanced softening of laundry.
- Such clays include the montmorillonite-containing clays which have swelling properties (in water) and which are of smectite structure, so that they deposit on fibrous materials, especially cotton and cotton/synthetic blends, such as cotton/polyester, to give such fibers and fabrics made from them a surface lubricity or softness.
- the best of the smectite clays for use in the present invention is bentonite and the best of the bentonites are those which have a substantial swelling capability in water, such as the sodium and potassium bentonites.
- Such swelling bentonites are also known as western or Wyoming bentonites, which are essentially sodium bentonite.
- Other bentonites such as calcium bentonite, are normally non-swelling and usually are, in themselves, unacceptable as fabric softening agents.
- a source of alkali metal or other solubilizing ion such as sodium (which may come from sodium hydroxide, added to the composition, or from sodium salts, such as builders and fillers, which may be functional components of the composition).
- bentonites are those of sodium and potassium, which are normally swelling, and calcium and magnesium, which are normally non-swelling. Of these it is preferred to utilize calcium (with a source of sodium being present) and sodium bentonites.
- the bentonites employed may be produced in the United States of America, such as Wyoming bentonite, but also may be obtained from Europe, including Italy and Spain, as calcium bentonite, which may be converted to sodium bentonite by treatment with sodium carbonate, or may be employed as calcium bentonite.
- other montmorillonite-containing smectite clays of properties like those of the bentonites described may be substituted in whole or in part for the bentonites described herein and similar fabric softening results will be obtained.
- the swellable bentonites and similarly operative clays are of ultimate particle sizes in the micron range, e.g., 0.01 to 20 microns and of actual particle sizes in the range of 38 to 150 microns (No's. 100 to 400 sieves), preferably 45 to 106 microns (140 to 325 sieves, U.S. Sieve Series).
- the bentonite and other such suitable swellable clays may be agglomerated to larger particle sizes too, such as 125 to 250 microns (60 to 120 sieves), but such agglomerates are not preferred unless they include the PEC('s) too (in any particulate products).
- the initial bentonite starting material is selected to have relatively low gelling and swelling properties.
- the starting material bentonite is selected to have the following initial properties: (a) a montmorillonite content of at least 85%; and (b) when the bentonite is activated with sodium ions, dried and ground to particles, the ground particles do not swell more than about 2.5 fold over a period of 24 hours when added to deionized water at room temperature.
- the ground particles of bentonite for purposes of determining swelling herein are particles at least 90% of equal to or less than 75 microns in diameter.
- the chemical composition of the starting material bentonite is preferably comprised by weight of the following: SiO 2 55.0 to 61.0% Al 2 O 3 14.5 to 17.6% Fe 2 O 3 1.45 to 1.7% CaO 2.8 to 7.0% MgO 5.0 to 6.3% K 2 O 0.5 to 0.85% Na 2 O 0.25 to 0.30% Mn 3 O 4 0.04 to 0.25%
- the process of treating the bentonite comprises the following sequential steps:
- a main component of the invented compositions and articles of the present invention, and which is used in combination with the fabric softening clay is an organic fatty softener.
- the organic softener can be anionic, cationic or nonionic fatty chains (C 10 -C 22 preferably C 12- C 18 ).
- Anionic softeners include fatty acids soaps.
- Preferred organic softeners are nonionics such as fatty esters, ethoxylated fatty esters, fatty alcohols and polyols polymers.
- the organic softener is most preferably a higher fatty acid ester of a pentaerythritol compound, which term is used in this specification to describe higher fatty acid esters of pentaerythritol, higher fatty acid esters of pentaerythritol oligomers, higher fatty acid esters of lower alkylene oxide derivatives of pentaerythritol and higher fatty acid esters of lower alkylene oxide derivatives of pentaerythritol oligomers.
- Pentaerythritol compound is often abbreviated as PEC herein, which description and abbreviation may apply to any or all of pentaerythritol, oligomers, thereof and alkoxylated derivatives thereof, as such, or more preferably and more usually, as the esters, as may be indicated by the context.
- the oligomers of pentaerythritol are preferably those of two to five pentaerythritol moieties, more preferably 2 or 3, with such moieties being joined together through etheric bonds.
- the lower alkylene oxide derivatives thereof are preferably of ethylene oxide or propylene oxide monomers, dimers or polymers, which terminate in hydroxyls and are joined to the pentaerythritol or oligomer of pentaerythritol through etheric linkages.
- At least one of the PEC OH groups and preferably at least two, e.g., 1 or 2 to 4 are esterified- by a higher fatty acid or other higher aliphatic acid, which can be of an odd number of carbon atoms.
- the higher fatty acid esters of the pentaerythritol compounds are preferably partial esters. And more preferably there will be at least two free hydroxyls thereon after esterification (on the pentaerythritol, oligomer or alkoxyalkane groups). Frequently, the number of such free hydroxyls is two or about two but sometimes it may by one, as in pentaerythritol tristearate.
- the higher aliphatic or fatty acids that may be employed as esterifying acids are those of carbon atom contents in the range of 8 to 24, preferably 12 to 22 and more preferably 12 to 18, e.g., lauric, myristic, palmitic, oleic, stearic and behenic acids.
- Such may be mixtures of such fatty acids, obtained from natural sources, such as tallow or coconut oil, or from such natural materials that have been hydrogenated. Synthetic acids of odd or even numbers of carbon atoms may also be employed. Of the fatty acids lauric and stearic acids are often preferred, and such preference may depend on the pentaerythritol compound being esterified.
- R 1 CH 3 -(CH 2 ) 10 -COO-
- R 2 CH 3 -(CH 2 ) 10 -COO-
- R 3 OH
- R 4 OH
- R 1 CH 3 -(CH 2 ) 16 -COO-
- R 2 CH 3 -(CH 2 ) 16 -COO-
- R 3 OH
- R 4 OH
- R 1 CH 3 -(CH 2 ) 16 -COO-
- R 2 CH 3 -(CH 2 ) 16 -COO-
- R 3 CH 3 -(CH 2 ) 16 -COO-
- R 4 OH
- R 1 CH 3 -(CH 2 ) 20 -COO-
- R 2 CH 3 -(CH 2 ) 20 -COO-
- R 3 OH
- R 4 OH
- R 1 CH 3 -(CH 2 ) 10 -CO
- R 2 CH 3 -(CH 2 ) 10 -CO
- R 3 CH 3 -(CH 2 ) 10 -CO
- R 4 CH 3 -(CH 2 ) 10 -CO
- R 1 CH 3 -(CH 2 ) 16 -CO
- R 2 CH 3 -(CH 2 ) 16 -CO
- R 3 CH 3 -(CH 2 ) 16 -CO
- R 4 CH 3 -(CH 2 ) 16 -CO
- R 1 CH 3 -(CH 2 ) 16 -COO-
- R 2 CH 3 -(CH 2 ) 16 -COO-
- R 1 CH 3 -(CH 2 ) 16 -COO-
- R 2 OH
- R 1 CH 3 -(CH 2 ) 16 -COO-
- R 2 CH 3 -(CH 2 ) 16 -COO-
- pentaerythritol compounds that are useful in the practice of this invention are illustrated it will be understood that various other such pentaerythritol compounds within the description thereof may also be employed herein, including such as pentaerythritol dihydrogenated tallowate, pentaerythritol ditallowate, pentaerythritol dipalmitate, and dipentaerythritol tetratallowate.
- cationic softeners such as conventional quaternary ammonium softening compounds may optionally be added in minor amounts.
- the combination of bentonite and organic fatty softening material is generally from about 10% to about 100% bentonite and from about 1% to about 100% fatty softening material, preferably from 50% to 95% bentonite and 5% to 50% fatty softening material, and most preferably from 80% to 90% bentonite and from 10% to 20% fatty softening material.
- compositions of the invention include disintegration materials to enhance the disintegration of the unit dose in the wash water.
- materials include an effervescent matrix such as citric acid combined with baking soda, or materials such as PVP polymer and cellulose.
- Granulating agents may be used such as polyethylene glycol; bactericides, perfumes, dyes and materials to protect against color fading, dye transfer, anti-pilling and anti-shrinkage.
- cosmetic ingredients such as dyes, micas and waxes may be used as coating ingredients to improve the appearance and feel of the unit dose.
- the encapsulation provided for the liquid or granular softening or conditioning materials is preferably a gelatin shell which is readily soluble in the wash water and compatible with detergents used in the wash cycle.
- the manufacture of such gelatin capsules utilizes technology well known in the art and is described, for example, in the following publications which are incorporated herein by reference: "Softgels: Manufacturing Considerations", Paul Wilkinson and Foo Song Hom, Drugs Pharmaceutical Science (1990), pps. 409-449, Mediventure Inc., Ann Arbor, MI, USA; and “Coating of Gelatin Capsules", Ann Mari Hannula and Peter Jardinr, Acta Pharmaceutical Technology (1988), pps. 234-236.
- Preferred liquid softeners of the invention include fatty alcohols, such as oleyl alcohol, fatty acids, such as oleyl carboxylic acid; fatty esters, such as oleyl esters or vegetable fatty esters such as sunflower oil ; silicones, such as polydimethylsiloxanes, linear or crosslinked, ethoxylated or without ethoxylation and optionally including an amide functionality; polyethylene waxes, having a molecular weight of from 8,000 to 60,000; and fatty amides, such as dioleyl amide formed by the reaction of diethylene triamine with oleic acid having predominantly the following structure: wherein R 1 represents an oleyl alkyl carbon chain; and R 2 represents H or (EO) x with x varying from 0 to 6 (the degree of ethoxylation).
- fatty alcohols such as oleyl alcohol, fatty acids, such as oleyl carboxylic acid
- fatty esters such as oleyl esters or vegetable
- oleyl carbon chain length is most preferred for purposes of providing softening efficacy and dispersion in the wash water, other higher alkyl chain lengths may also be used for the invention.
- Typical unit dose compositions for use herein may vary from about 5 to about 10 ml corresponding on a weight basis to about 5 to about 10 grams (which includes the weight of the capsule), and the number of doses per wash is two.
- the corresponding volume and weight is from about 10 to about 20 ml and from about 10 to about 20 grams (including the capsule weight), respectively.
- Compacted granular unit dose compositions were prepared from the following ingredients: Weight Percent A B Clay/Pentaerythritol ditallowate (PDT) in a ratio of 83% : 17% 80.0% 78.7% Effervescent matrix of baking soda and citric acid 17 ---- Polyvinylpyrrolidone 1 ---- Perfume 2 2.9 Treated bentonite ---- 18.4
- Composition A was a comparative composition and Composition B was a composition in accordance with the invention containing treated bentonite clay.
- the method of manufacture consisted of mixing all the ingredients with the exception of perfume in a Loedige-type mixer. The resulting blend was dried in an oven and perfume was then added to the dried powder. The powder was then compacted using an alternative or rotative press mounted with appropriate dyes. The weight of the spherical unit dose was 60g and such unit dose dispersed in water within 20 minutes when introduced in the wash load at the beginning of the wash in a European Miele W832 front loading washing machine set a Program White Colors at 40°C.
- compositions A and B were essentially equivalent.
- compositions A and B provided equivalent softness after one wash cycle with regard to cotton tee-shirts and cotton kitchen towels.
- Composition Friability (1) Hardness (2) Dispersion time in water (3) A 57% 75 gr 50 min. B 12% 100 gr 9 min. (1) Friability : Measurement of the residues in the bottom receptacle after sieving during 15 minutes (amplitude 4) on a vibrating 4 mm meshes sieve; the lower, the less friable. (2) Hardness : Resistance to breakage when various weights are falling onto the sphere; the higher, the more resistant. (3) Dispersion in beaker : Dispersion time of 1 sphere in 1 cold water beaker under moderate agitation; the shorter, the better.
- Composition B provided a significantly smoother feel and texture to the touch as evaluated by a panel of judges as compared to Composition A.
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Abstract
Description
- This invention relates to wash cycle unit dose laundry compositions for softening or conditioning fabrics. More particularly, this invention relates to unit dose fabric softening compositions which are compacted granular compositions suitable for use in the wash cycle of an automatic washing machine.
- Detergent compositions manufactured in the form of compacted detergent powder are known in the art. U.S. 5,225,100, for example, describes a tablet of compacted powder comprising an anionic detergent compound which will adequately disperse in the wash water.
- Although detergent compositions in the form of compacted granular tablets of various shapes have received much attention in the patent literature, the use of such tablets to provide a unit dose fabric softener which will soften or condition fabrics in the wash cycle without impairing detergency or otherwise compromise the cleaning benefits provided by the detergent composition is not known.
- Another possible option for providing a unit dose softener apart from the wash cycle is to introduce the softening ingredients directly into the rinse cycle. But, for this type of product to be effective several practical requirements must be met. To begin with, the size and shape of the unit dose container must be readily compatible with the geometry of a wide variety of rinse cycle dispensers designed for home washing machines in order to insure its easy introduction into the dispenser. Moreover, in common with the general use of rinse cycle softeners, it is necessary to clean the rinse dispenser on a regular basis to avoid residue from accumulating within the dispenser or even, at times, prevent bacterial growth from occurring.
- Still further, a unit dose composition for the rinse cycle must be formulated to readily dispense its contents upon contact with water in a period of time corresponding to the residence time of the unit dose in the dispenser, namely, the period of time during which water enters and flows through the rinse cycle dispenser. The aforementioned practical requirements have to date not been successfully met with any commercially available product and hence there remains a need in the art for a unit dose softener capable of activation in the rinse cycle.
- Laundry detergent compositions which further include a fabric softener to provide softening or conditioning of fabrics in the wash cycle of the laundering operation are well-known in the art and described in the patent literature. See, for example, U.S. Patent 4,605,506 to Wixon; U.S. Patent 4,818,421 to Boris et al. and U.S. Patent 4,569,773 to Ramachandran et al., all assigned to Colgate-Palmolive Co., and U.S. Patent 4,851,138 assigned to Akzo. U.S. Patent 5,972,870 to Anderson describes a multi-layered laundry tablet for washing which may include a detergent in the outer layer and a fabric softener, or water softener or fragrance in the inner layer. But, these type of multi-benefit products suffer from a common drawback, namely, there is an inherent compromise which the user necessarily makes between the cleaning and softening benefits provided by such products as compared to using a separate detergent composition solely for cleaning in the wash cycle and a separate softening composition solely for softening in the rinse cycle. In essence, the user of such detergent softener compositions does not have the ability to independently adjust the amount of detergent and softener added to the wash cycle of a machine in response to the cleaning and softening requirements of the particular wash load.
- Some attempts have been made in the art to develop wash cycle active fabric softeners, typically in powder form. But, these type products are characterized by the same inconvenience inherent with the use of powered detergents, namely, problems of handling, caking in the container or wash cycle dispenser, and the need for a dosing device to deliver the desired amount of active softener material to the wash water.
- The use of a unit dose wash cycle fabric softening composition in the form of a compacted granular tablet offers numerous advantages, but it is important that such tablets be sufficiently hard and not friable so as to withstand handling and transportation without breaking or fragmenting. In order to achieve the desired level of hardness, tablet makers generally tend to increase the compacting pressure. But, a high compacting pressure, if favorable to the hardness of the tablet, lowers the disintegration rate of such tablet.
- WO-A-99/40171 discloses laundry detergent tablets containing montmorillonite.
- To be effective, the unit dose fabric softening compositions, which are compacted granular compositions, must be able to disperse in the wash liquor in a short period of time to avoid any residue at the end of the wash cycle.
- Typically, the wash cycle time can be as short as 12 minutes and as long as 90 minutes (in typical European washers) depending on the type of washer and the wash conditions. Therefore, to make sure that the compacted unit dose is properly dispersed in the wash liquor before the end of the cycle, disintegrating materials must be added to the granules before compacting. This need for disintegrating agents is well-known in the art and the most popular materials used for this purpose are water swelling polymers such as polyvinylpyrrolidone, cellulosic polymers or a blend of citric acid and bicarbonate salt that provide an effervescent matrix.
- The problem with these disintegrating materials and swelling polymers is that they constitute a significant weight and cost of the overall composition and they serve only he single purpose of dispersion of the tablet. Also the use of a typical effervescent matrix results in a typical feel of the tablet surface that can be described as dry and "stony", which is generally not favored by consumers.
- It has now been found that a particular grade of clay (described in WO 00/03959) can replace the usual disintegrating agents while contributing to the softness of the clothes. The use of such clay enhances the disintegration rate of the unit dose while allowing the use of higher compacting pressure and reducing the friability of the dose. Moreover, it provides the finished tablet with a very smooth feel.
- The present invention provides a unit dose wash cycle fabric softening composition for softening or conditioning fabrics in the wash cycle of an automatic washing machine, said unit dose comprising (a) a compacted granular fabric softener composition, the amount of (a) being sufficient to form a unit dose capable of providing effective softening or conditioning of fabrics in the wash cycle of said washing machine, and wherein said fabric softener composition comprises a treated montmorillonite-containing clay selected to have initial properties as follows:
- (i) a montmorillonite content of at least 85%; and
- (ii) when said clay is activated with sodium ions, dried and ground to particles, said ground particles do not swell more than 2.5 fold over a period of 24 hours when added to deionized water at room temperature; and wherein said montmorillonite-containing clay is treated by the process comprising the following sequential steps:
- (a) drying said clay to a moisture content of from 25 to 35%, by weight;
- (b) extruding the dried material through a die to form a paste;
- (c) drying said paste to a moisture content of from 10% to 14% by weight; and
- (d) calcining at a temperature of 120°C to 250°C.
- In a preferred embodiment the unit dose fabric softening composition is characterized by being in the form of a tablet and having no discrete outer layer surrounding the fabric softener comprised of an alkaline material such that the pH of the wash water is increased upon dissolution of said outer layer in said wash water.
- The term "granular" as used herein in describing the fabric softener is intended to encompass relatively coarser granules varying in size from about 150 to 2,000 microns as well as finer powder having a size as small as 30 to 50 microns.
- The term "fabric softener" is used herein for purposes of convenience to refer to materials which provide softening and/or conditioning benefits to fabrics in the wash cycle of a home or automatic laundering machine.
- The compacted granular fabric softener composition of the invention is preferably comprised of a fabric softening clay optionally in combination with an organic fatty softening material. Especially preferred fabric softeners comprise a clay mineral softener, such as bentonite, in combination with a pentaerythritol ester compound as further described herein. Useful combinations of such softener may vary from about 80%, to about 90%, by weight, of clay, and from about 10% to about 20%, by weight, of fatty softening material such as a pentaerythritol compound (often abbreviated herein as "PEC").
- The present invention is predicated on the use of a treated montmorillonite-containing clay, preferably a treated bentonite, as herein defined, as an active softening ingredient in a unit dose softening composition for the wash cycle. The resultant unit dose composition has reduced tendency to gel on contact with water so that when used in conjunction with laundry detergent compositions it manifests improved dispersion properties in the wash water without having any adverse effect on its softening properties.
- In accordance with the process aspect of the invention there is provided a process for softening or conditioning laundry which comprises contacting the laundry with an effective amount of the unit dose laundry composition defined above.
- The clays that are useful components of the invented products are those which cooperate with the organic fatty softener materials to provide enhanced softening of laundry. Such clays include the montmorillonite-containing clays which have swelling properties (in water) and which are of smectite structure, so that they deposit on fibrous materials, especially cotton and cotton/synthetic blends, such as cotton/polyester, to give such fibers and fabrics made from them a surface lubricity or softness. The best of the smectite clays for use in the present invention is bentonite and the best of the bentonites are those which have a substantial swelling capability in water, such as the sodium and potassium bentonites. Such swelling bentonites are also known as western or Wyoming bentonites, which are essentially sodium bentonite. Other bentonites, such as calcium bentonite, are normally non-swelling and usually are, in themselves, unacceptable as fabric softening agents. However, it has been found that such non-swelling bentonites exhibit even better fabric softening in combination with PEC's than do the swelling bentonites, provided that there is present in the softening composition, a source of alkali metal or other solubilizing ion, such as sodium (which may come from sodium hydroxide, added to the composition, or from sodium salts, such as builders and fillers, which may be functional components of the composition). Among the preferred bentonites are those of sodium and potassium, which are normally swelling, and calcium and magnesium, which are normally non-swelling. Of these it is preferred to utilize calcium (with a source of sodium being present) and sodium bentonites. The bentonites employed may be produced in the United States of America, such as Wyoming bentonite, but also may be obtained from Europe, including Italy and Spain, as calcium bentonite, which may be converted to sodium bentonite by treatment with sodium carbonate, or may be employed as calcium bentonite. Also, other montmorillonite-containing smectite clays of properties like those of the bentonites described may be substituted in whole or in part for the bentonites described herein and similar fabric softening results will be obtained.
- The swellable bentonites and similarly operative clays are of ultimate particle sizes in the micron range, e.g., 0.01 to 20 microns and of actual particle sizes in the range of 38 to 150 microns (No's. 100 to 400 sieves), preferably 45 to 106 microns (140 to 325 sieves, U.S. Sieve Series). The bentonite and other such suitable swellable clays may be agglomerated to larger particle sizes too, such as 125 to 250 microns (60 to 120 sieves), but such agglomerates are not preferred unless they include the PEC('s) too (in any particulate products).
For purposes of providing a treated bentonite in accordance with the invention, the initial bentonite starting material is selected to have relatively low gelling and swelling properties. Specifically, the starting material bentonite is selected to have the following initial properties: (a) a montmorillonite content of at least 85%; and (b) when the bentonite is activated with sodium ions, dried and ground to particles, the ground particles do not swell more than about 2.5 fold over a period of 24 hours when added to deionized water at room temperature. The ground particles of bentonite for purposes of determining swelling herein are particles at least 90% of equal to or less than 75 microns in diameter. - The chemical composition of the starting material bentonite is preferably comprised by weight of the following:
SiO2 55.0 to 61.0% Al2O3 14.5 to 17.6% Fe2O3 1.45 to 1.7% CaO 2.8 to 7.0% MgO 5.0 to 6.3% K2O 0.5 to 0.85% Na2O 0.25 to 0.30% Mn3O4 0.04 to 0.25% - The process of treating the bentonite comprises the following sequential steps:
- (a) drying said clay to a moisture content of from about 25 to about 35%, by weight;
- (b) extruding the dried material through a die to form a paste;
- (c) drying said paste to a moisture content of from about 10% to about 14% by weight; and
- (d) calcining at a temperature of about 120°C to about 250°C.
- A detailed description of the process for treating bentonite in accordance with the present invention is disclosed in WO 00/03959.
- A main component of the invented compositions and articles of the present invention, and which is used in combination with the fabric softening clay is an organic fatty softener. The organic softener can be anionic, cationic or nonionic fatty chains (C10-C22 preferably C12-C18). Anionic softeners include fatty acids soaps. Preferred organic softeners are nonionics such as fatty esters, ethoxylated fatty esters, fatty alcohols and polyols polymers. The organic softener is most preferably a higher fatty acid ester of a pentaerythritol compound, which term is used in this specification to describe higher fatty acid esters of pentaerythritol, higher fatty acid esters of pentaerythritol oligomers, higher fatty acid esters of lower alkylene oxide derivatives of pentaerythritol and higher fatty acid esters of lower alkylene oxide derivatives of pentaerythritol oligomers. Pentaerythritol compound is often abbreviated as PEC herein, which description and abbreviation may apply to any or all of pentaerythritol, oligomers, thereof and alkoxylated derivatives thereof, as such, or more preferably and more usually, as the esters, as may be indicated by the context.
- The oligomers of pentaerythritol are preferably those of two to five pentaerythritol moieties, more preferably 2 or 3, with such moieties being joined together through etheric bonds. The lower alkylene oxide derivatives thereof are preferably of ethylene oxide or propylene oxide monomers, dimers or polymers, which terminate in hydroxyls and are joined to the pentaerythritol or oligomer of pentaerythritol through etheric linkages. Preferably there will be one to ten alkylene oxide moieties in each such alkylene oxide chain, more preferably 2 to 6, and there will be one to ten such groups on a PEC, depending on the oligomer. At least one of the PEC OH groups and preferably at least two, e.g., 1 or 2 to 4, are esterified- by a higher fatty acid or other higher aliphatic acid, which can be of an odd number of carbon atoms.
- The higher fatty acid esters of the pentaerythritol compounds are preferably partial esters. And more preferably there will be at least two free hydroxyls thereon after esterification (on the pentaerythritol, oligomer or alkoxyalkane groups). Frequently, the number of such free hydroxyls is two or about two but sometimes it may by one, as in pentaerythritol tristearate. The higher aliphatic or fatty acids that may be employed as esterifying acids are those of carbon atom contents in the range of 8 to 24, preferably 12 to 22 and more preferably 12 to 18, e.g., lauric, myristic, palmitic, oleic, stearic and behenic acids. Such may be mixtures of such fatty acids, obtained from natural sources, such as tallow or coconut oil, or from such natural materials that have been hydrogenated. Synthetic acids of odd or even numbers of carbon atoms may also be employed. Of the fatty acids lauric and stearic acids are often preferred, and such preference may depend on the pentaerythritol compound being esterified.
- Examples of some esters (PEC's) within the present invention follow:
-
-
R1=CH3-(CH2)10-COO-
R2=CH3-(CH2)10-COO-
R3=OH
R4=OH
-
R1=CH3-(CH2)16-COO-
R2=OH
R3=OH
R4=OH
-
R1=CH3-(CH2)16-COO-
R2=CH3-(CH2)16-COO-
R3=OH
R4=OH
-
R1=CH3-(CH2)16-COO-
R2=CH3-(CH2)16-COO-
R3=CH3-(CH2)16-COO-
R4=OH
-
R1=CH3-(CH2)20-COO-
R2=OH
R3=OH
R4=OH
-
R1=CH3-(CH2)20-COO-
R2=CH3-(CH2)20-COO-
R3=OH
R4=OH
-
-
R1=CH3-(CH2)10-CO
R2=CH3-(CH2)10-CO
R3=CH3-(CH2)10-CO
R4=CH3-(CH2)10-CO
-
R1=CH3-(CH2)16-CO
R2=CH3-(CH2)16-CO
R3=CH3-(CH2)16-CO
R4=CH3-(CH2)16-CO
-
-
R1=CH3-(CH2)16-COO-
R2=CH3-(CH2)16-COO-
-
-
R1=CH3-(CH2)16-COO-
R2=OH
-
R1=CH3-(CH2)16-COO-
R2=CH3-(CH2)16-COO-
- Although in the formulas given herein some preferred pentaerythritol compounds that are useful in the practice of this invention are illustrated it will be understood that various other such pentaerythritol compounds within the description thereof may also be employed herein, including such as pentaerythritol dihydrogenated tallowate, pentaerythritol ditallowate, pentaerythritol dipalmitate, and dipentaerythritol tetratallowate.
- To enhance the softening efficacy of the unit dose compositions described herein cationic softeners such as conventional quaternary ammonium softening compounds may optionally be added in minor amounts.
- The combination of bentonite and organic fatty softening material is generally from about 10% to about 100% bentonite and from about 1% to about 100% fatty softening material, preferably from 50% to 95% bentonite and 5% to 50% fatty softening material, and most preferably from 80% to 90% bentonite and from 10% to 20% fatty softening material.
- Other useful ingredients for the unit dose compacted granular compositions of the invention include disintegration materials to enhance the disintegration of the unit dose in the wash water. Such materials include an effervescent matrix such as citric acid combined with baking soda, or materials such as PVP polymer and cellulose. Granulating agents may be used such as polyethylene glycol; bactericides, perfumes, dyes and materials to protect against color fading, dye transfer, anti-pilling and anti-shrinkage. For purposes of enhancing the aesthetic properties of the final composition, cosmetic ingredients such as dyes, micas and waxes may be used as coating ingredients to improve the appearance and feel of the unit dose.
- The encapsulation provided for the liquid or granular softening or conditioning materials is preferably a gelatin shell which is readily soluble in the wash water and compatible with detergents used in the wash cycle. The manufacture of such gelatin capsules utilizes technology well known in the art and is described, for example, in the following publications which are incorporated herein by reference: "Softgels: Manufacturing Considerations", Paul Wilkinson and Foo Song Hom, Drugs Pharmaceutical Science (1990), pps. 409-449, Mediventure Inc., Ann Arbor, MI, USA; and "Coating of Gelatin Capsules", Ann Mari Hannula and Peter Speiser, Acta Pharmaceutical Technology (1988), pps. 234-236.
- Preferred liquid softeners of the invention include fatty alcohols, such as oleyl alcohol, fatty acids, such as oleyl carboxylic acid; fatty esters, such as oleyl esters or vegetable fatty esters such as sunflower oil ; silicones, such as polydimethylsiloxanes, linear or crosslinked, ethoxylated or without ethoxylation and optionally including an amide functionality; polyethylene waxes, having a molecular weight of from 8,000 to 60,000; and fatty amides, such as dioleyl amide formed by the reaction of diethylene triamine with oleic acid having predominantly the following structure:
- While the oleyl carbon chain length is most preferred for purposes of providing softening efficacy and dispersion in the wash water, other higher alkyl chain lengths may also be used for the invention.
- Typical unit dose compositions for use herein may vary from about 5 to about 10 ml corresponding on a weight basis to about 5 to about 10 grams (which includes the weight of the capsule), and the number of doses per wash is two. Alternatively, when using 1 unit dose/wash, the corresponding volume and weight is from about 10 to about 20 ml and from about 10 to about 20 grams (including the capsule weight), respectively.
- Compacted granular unit dose compositions (A and B) were prepared from the following ingredients:
Weight Percent A B Clay/Pentaerythritol ditallowate (PDT) in a ratio of 83% : 17% 80.0% 78.7% Effervescent matrix of baking soda and citric acid 17 ---- Polyvinylpyrrolidone 1 ---- Perfume 2 2.9 Treated bentonite ---- 18.4 - Composition A was a comparative composition and Composition B was a composition in accordance with the invention containing treated bentonite clay.
- The method of manufacture consisted of mixing all the ingredients with the exception of perfume in a Loedige-type mixer. The resulting blend was dried in an oven and perfume was then added to the dried powder. The powder was then compacted using an alternative or rotative press mounted with appropriate dyes. The weight of the spherical unit dose was 60g and such unit dose dispersed in water within 20 minutes when introduced in the wash load at the beginning of the wash in a European Miele W832 front loading washing machine set a Program White Colors at 40°C.
- The softness provided by the unit dose compositions of A and B on terry towels, cotton tee-shirts and cotton kitchen towels was evaluated after cumulative washes and compared with a commercial liquid fabric softener. A 3Kg laundry ballast was used in the machine. Softness was evaluated by a panel of six judges using 9 replicates. The results were as follows:
- The softness performance of Compositions A and B were essentially equivalent.
- As compared to a commercial liquid fabric softener, Compositions A and B provided equivalent softness after one wash cycle with regard to cotton tee-shirts and cotton kitchen towels.
- A comparison of Compositions A and B with regard to physical properties and dispersion in water is shown below:
Composition Friability (1) Hardness (2) Dispersion time in water (3) A 57% 75 gr 50 min. B 12% 100 gr 9 min. (1) Friability: Measurement of the residues in the bottom receptacle after sieving during 15 minutes (amplitude 4) on a vibrating 4 mm meshes sieve; the lower, the less friable.
(2) Hardness: Resistance to breakage when various weights are falling onto the sphere; the higher, the more resistant.
(3) Dispersion in beaker: Dispersion time of 1 sphere in 1 cold water beaker under moderate agitation; the shorter, the better. - Composition B provided a significantly smoother feel and texture to the touch as evaluated by a panel of judges as compared to Composition A.
Claims (22)
- A unit dose wash cycle fabric softening composition for softening or conditioning fabrics in the wash cycle of an automatic washing machine, said unit dose comprising (a) a compacted granular fabric softener composition, the amount of (a) being sufficient to form a unit dose capable of providing effective softening or conditioning of fabrics in the wash cycle of said washing machine, and wherein said fabric softener composition comprises a treated montmorillonite-containing clay selected to have initial properties as follows:(i) a montmorillonite content of at least 85%; and(ii) when said clay is activated with sodium ions, dried and ground to particles, said ground particles do not swell more than 2.5 fold over a period of 24 hours when added to deionized water at room temperature; and wherein said montmorillonite-containing clay is treated by the process comprising the following sequential steps:(a) drying said clay to a moisture content of from 25 to 35%, by weight;(b) extruding the dried material through a die to form a paste;(c) drying said paste to a moisture content of from 10% to 14% by weight; and(d) calcining at a temperature of 120°C to 250°C.
- A unit dose softening composition as in claim 1 characterized by being in the form of a tablet and having no discrete outer layer surrounding the fabric softener comprised of an alkaline material such that the pH of the wash water is increased upon the dissolution of said outer layer in said wash water.
- A unit dose softening composition as in claim 1 wherein the defined initial swelling property of said montmorillonite-containing clay is measured with ground particles of clay at least 90% of which are not greater than 75 µm (microns) in diameter.
- A unit dose softening composition as in claim 1 wherein the montmorillonite-containing clay is a bentonite.
- A unit dose softening composition as in claim 4 wherein the bentonite has a further initial property of containing at least 4.0% by weight of MgO.
- A unit softening composition as in claim 4 wherein the bentonite starting material has the following composition by weight:SiO2 from 55.0 to 61.0%;Al2O3 from 14.5 to 17.6%;Fe2O3 from 1.45 to 1.7%;CaO from 2.8 to 7.0%;MgO from 5.0 to 6.3%;K2O from 0.5 to 0.85%;Na2O from 0.25 to 0.30%; andMn3O4 from 0.04 to 0.25%
- A unit dose softening composition as in claim 1 wherein said fabric softener composition comprises a montmorillonite-containing clay in combination with an organic fatty softening material.
- A unit dose softening composition as in claim 7 wherein said montmorillonite-containing clay is a bentonite and said organic fatty softening material is a pentaerythritol compound ("PEC") selected from the group consisting of a higher aliphatic acid ester of pentaerythritol, an oligomer of pentaerythritol, a lower alkylene oxide derivative of an oligomer of pentaerythritol, and a mixture thereof.
- A unit dose softening composition as in claim 7 wherein said montmorillonite-containing clay is a bentonite and said organic fatty softening material is a fatty alcohol.
- A unit dose softening composition as in claim 7 wherein said clay is at least partially coated with said organic fatty softening material and serves as a carrier for such fatty softening material.
- A unit dose softening composition as in claim 8 wherein said PEC is a higher aliphatic ester of pentaerythritol or of an oligomer of pentaerythritol.
- A unit dose softening composition as in claim 8 wherein the combination of bentonite and said PEC comprises, by weight, from 50% to 95% of bentonite and from 5% to 50% of said PEC.
- A unit dose softening composition as in claim 12 which comprises from 80 to 90% of bentonite and from 10% to 20% of said PEC.
- A unit dose softening composition as in claim 1 wherein said fabric softener comprises a liquid fatty ester.
- A unit dose softening composition as in claim 14 wherein said fatty ester is sunflower oil.
- A unit dose softening composition as in claim 1 wherein said fabric softener composition comprises a liquid silicone.
- A unit dose softening composition as in claim 1 wherein said fabric softener composition comprises a liquid oleyl alcohol.
- A process for softening or conditioning laundry which comprises contacting the laundry with an effective amount of the unit dose softening composition of claim 1.
- A process according to claim 18 wherein the fabric softener composition comprises a treated bentonite clay in combination with an organic fatty softening material.
- A process according to claim 19 wherein said organic softening material comprises a fatty alcohol or pentaerythritol compound (PEC) selected from the group consisting of a higher aliphatic acid ester of pentaerythritol, an oligomer of pentaerythritol, a lower alkylene oxide derivative of an oligomer of pentaerythritol, and a mixture thereof.
- A process according to claim 18 wherein the fabric softener composition comprises a liquid fatty ester.
- A process according to claim 21 wherein said fatty ester is sunflower oil.
Applications Claiming Priority (7)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US558822 | 2000-04-26 | ||
US09/558,822 US6258767B1 (en) | 2000-04-26 | 2000-04-26 | Spherical compacted unit dose softener |
US09/620,515 US6294516B1 (en) | 2000-04-26 | 2000-07-20 | Wash cycle unit dose softener |
US620515 | 2000-07-20 | ||
US685756 | 2000-10-09 | ||
US09/685,756 US6291421B1 (en) | 2000-04-26 | 2000-10-09 | Wash cycle unit dose softener |
PCT/US2001/013079 WO2001083663A1 (en) | 2000-04-26 | 2001-04-23 | Wash cycle unit dose softener |
Publications (2)
Publication Number | Publication Date |
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EP1276838A1 EP1276838A1 (en) | 2003-01-22 |
EP1276838B1 true EP1276838B1 (en) | 2006-09-27 |
Family
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Application Number | Title | Priority Date | Filing Date |
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EP01928774A Expired - Lifetime EP1276838B1 (en) | 2000-04-26 | 2001-04-23 | Wash cycle unit dose softener |
Country Status (12)
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EP (1) | EP1276838B1 (en) |
JP (1) | JP2003531969A (en) |
CN (1) | CN1439047A (en) |
AT (1) | ATE340843T1 (en) |
AU (2) | AU5559501A (en) |
BR (1) | BR0110349A (en) |
CA (1) | CA2405727A1 (en) |
DE (1) | DE60123414T2 (en) |
DK (1) | DK1276838T3 (en) |
HK (1) | HK1053143B (en) |
MX (1) | MXPA02010286A (en) |
WO (1) | WO2001083663A1 (en) |
Families Citing this family (2)
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US8034760B2 (en) | 2005-08-01 | 2011-10-11 | Kao Corporation | Softening detergent composition |
CN101581037B (en) * | 2009-06-09 | 2011-10-12 | 深圳市成为生物科技有限公司 | Particles capable of softening clothes and preparation method thereof |
Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4832856A (en) * | 1987-03-13 | 1989-05-23 | Henkel Kommanditgesellschaft Auf Aktien | Aqueous fabric softener for the treatment of fabrics: containing alkylamine, hydroxyalkylamine or quaternary ammonium derivative and a carboxylic acid |
EP0570237A2 (en) * | 1992-05-15 | 1993-11-18 | Colgate-Palmolive Company | Particulate fabric softening and detergent compositions |
US5656585A (en) * | 1994-12-21 | 1997-08-12 | Colgate-Palmolive Company | Clear, concentrated liquid fabric softener compositions |
Family Cites Families (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4328110A (en) * | 1980-09-17 | 1982-05-04 | Beecham Inc. | Fabric conditioning articles and methods of use |
JPS61276896A (en) * | 1985-06-03 | 1986-12-06 | 花王株式会社 | Softener tablet for washing bath |
FI921148A (en) * | 1991-09-06 | 1993-03-07 | Colgate Palmolive Co | TYGMJUKGOERANDE PRODUKTER BASERADE PAO EN KOMBINATION AV EN PENTAERYTRITOLFOERINING OCH BENTONIT |
JPH0987696A (en) * | 1995-09-27 | 1997-03-31 | Lion Corp | Tablet type nonionic detergent composition |
US5972870A (en) * | 1997-08-21 | 1999-10-26 | Vision International Production, Inc. | Multi-layered laundry tablet |
GB9802390D0 (en) * | 1998-02-04 | 1998-04-01 | Unilever Plc | Detergent compositions |
GB9815450D0 (en) * | 1998-07-17 | 1998-09-16 | Colin Stewart Minchem Ltd | Process for treating bentonite and products thereof |
-
2001
- 2001-04-23 DK DK01928774T patent/DK1276838T3/en active
- 2001-04-23 DE DE60123414T patent/DE60123414T2/en not_active Expired - Fee Related
- 2001-04-23 AT AT01928774T patent/ATE340843T1/en not_active IP Right Cessation
- 2001-04-23 WO PCT/US2001/013079 patent/WO2001083663A1/en active IP Right Grant
- 2001-04-23 AU AU5559501A patent/AU5559501A/en active Pending
- 2001-04-23 BR BR0110349-0A patent/BR0110349A/en not_active Application Discontinuation
- 2001-04-23 MX MXPA02010286A patent/MXPA02010286A/en active IP Right Grant
- 2001-04-23 CA CA002405727A patent/CA2405727A1/en not_active Abandoned
- 2001-04-23 CN CN01811701A patent/CN1439047A/en active Pending
- 2001-04-23 JP JP2001580273A patent/JP2003531969A/en active Pending
- 2001-04-23 AU AU2001255595A patent/AU2001255595B2/en not_active Ceased
- 2001-04-23 EP EP01928774A patent/EP1276838B1/en not_active Expired - Lifetime
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Patent Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4832856A (en) * | 1987-03-13 | 1989-05-23 | Henkel Kommanditgesellschaft Auf Aktien | Aqueous fabric softener for the treatment of fabrics: containing alkylamine, hydroxyalkylamine or quaternary ammonium derivative and a carboxylic acid |
EP0570237A2 (en) * | 1992-05-15 | 1993-11-18 | Colgate-Palmolive Company | Particulate fabric softening and detergent compositions |
US5656585A (en) * | 1994-12-21 | 1997-08-12 | Colgate-Palmolive Company | Clear, concentrated liquid fabric softener compositions |
Also Published As
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HK1053143A1 (en) | 2003-10-10 |
AU2001255595B2 (en) | 2005-06-30 |
MXPA02010286A (en) | 2003-04-25 |
CA2405727A1 (en) | 2001-11-08 |
WO2001083663A1 (en) | 2001-11-08 |
ATE340843T1 (en) | 2006-10-15 |
CN1439047A (en) | 2003-08-27 |
JP2003531969A (en) | 2003-10-28 |
DK1276838T3 (en) | 2007-02-05 |
EP1276838A1 (en) | 2003-01-22 |
BR0110349A (en) | 2004-06-22 |
DE60123414D1 (en) | 2006-11-09 |
HK1053143B (en) | 2007-04-27 |
DE60123414T2 (en) | 2007-08-23 |
AU5559501A (en) | 2001-11-12 |
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