[go: up one dir, main page]

WO2001083663A1 - Wash cycle unit dose softener - Google Patents

Wash cycle unit dose softener Download PDF

Info

Publication number
WO2001083663A1
WO2001083663A1 PCT/US2001/013079 US0113079W WO0183663A1 WO 2001083663 A1 WO2001083663 A1 WO 2001083663A1 US 0113079 W US0113079 W US 0113079W WO 0183663 A1 WO0183663 A1 WO 0183663A1
Authority
WO
WIPO (PCT)
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.)
Ceased
Application number
PCT/US2001/013079
Other languages
French (fr)
Inventor
Alain Jacques
Juliette Rousselet
Hoai-Chau Cao
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.)
Colgate Palmolive Co
Original Assignee
Colgate Palmolive 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
Priority claimed from US09/558,822 external-priority patent/US6258767B1/en
Priority claimed from US09/685,756 external-priority patent/US6291421B1/en
Priority to JP2001580273A priority Critical patent/JP2003531969A/en
Priority to MXPA02010286A priority patent/MXPA02010286A/en
Application filed by Colgate Palmolive Co filed Critical Colgate Palmolive Co
Priority to BR0110349-0A priority patent/BR0110349A/en
Priority to EP01928774A priority patent/EP1276838B1/en
Priority to AU2001255595A priority patent/AU2001255595B2/en
Priority to DK01928774T priority patent/DK1276838T3/en
Priority to HK03105255.6A priority patent/HK1053143B/en
Priority to DE60123414T priority patent/DE60123414T2/en
Priority to CA002405727A priority patent/CA2405727A1/en
Priority to AU5559501A priority patent/AU5559501A/en
Publication of WO2001083663A1 publication Critical patent/WO2001083663A1/en
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

Links

Classifications

    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/66Non-ionic compounds
    • C11D1/667Neutral esters, e.g. sorbitan esters
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D17/00Detergent materials or soaps characterised by their shape or physical properties
    • C11D17/0047Detergents in the form of bars or tablets
    • C11D17/0065Solid detergents containing builders
    • C11D17/0073Tablets
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D17/00Detergent materials or soaps characterised by their shape or physical properties
    • C11D17/04Detergent materials or soaps characterised by their shape or physical properties combined with or containing other objects
    • C11D17/041Compositions releasably affixed on a substrate or incorporated into a dispensing means
    • C11D17/042Water soluble or water disintegrable containers or substrates containing cleaning compositions or additives for cleaning compositions
    • C11D17/044Solid compositions
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/0005Other compounding ingredients characterised by their effect
    • C11D3/001Softening compositions
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/02Inorganic compounds ; Elemental compounds
    • C11D3/12Water-insoluble compounds
    • C11D3/124Silicon containing, e.g. silica, silex, quartz or glass beads
    • C11D3/1246Silicates, e.g. diatomaceous earth
    • C11D3/1253Layer silicates, e.g. talcum, kaolin, clay, bentonite, smectite, montmorillonite, hectorite or attapulgite
    • C11D3/126Layer silicates, e.g. talcum, kaolin, clay, bentonite, smectite, montmorillonite, hectorite or attapulgite in solid compositions

Definitions

  • 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.
  • 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.
  • 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.
  • 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.
  • 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 No's. 100 to 400 sieves, preferably 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 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 about 75 microns in diameter.
  • the chemical composition of the starting material bentonite is preferably comprised by weight of the following:
  • 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;
  • 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 (C1 0 -C22 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 ! CH 3 - (CH 2 ) 16 -COO-
  • R 2 CH 3 - (CH 2 ) 16 -COO-
  • R 3 CH 3 - (CH 2 )i 6 -COO-
  • R 4 OH
  • R 3 CH 3 -(CH 2 ) 16 -CO
  • R 4 CH 3 - (CH 2 )i 6 -CO
  • 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 about 50% to about 95% bentonite and about 5% to about 50% fatty softening material, and most preferably from about 80% to 90% bentonite and from about 10% to about 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 PNP 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 Horn, 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:
  • Rj represents an oleyl alkyl carbon chain
  • R 2 represents H or (EO) x with x varying from 0 to 6 (the degree of ethoxylation).
  • 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.
  • compositions were prepared from the following ingredients:
  • 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. 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.
  • 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.
  • 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.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Wood Science & Technology (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Inorganic Chemistry (AREA)
  • Detergent Compositions (AREA)
  • Treatment Of Water By Ion Exchange (AREA)
  • Chemical Or Physical Treatment Of Fibers (AREA)
  • Infusion, Injection, And Reservoir Apparatuses (AREA)
  • External Artificial Organs (AREA)
  • Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
  • Developing Agents For Electrophotography (AREA)

Abstract

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 about 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 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.

Description

Wash Cycle Unit Dose Softener
Field of the Invention 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.
Background of the Invention
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.
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.
Summary of the Invention
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 about 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 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.
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.
Detailed Description of the Invention
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 No's. 100 to 400 sieves, preferably 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 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 about 75 microns in diameter.
The chemical composition of the starting material bentonite is preferably comprised by weight of the following:
Si02 55.0 to 61.0%
A1203 14.5 to 17.6%
Fe203 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%
Mn304 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 filed in the name of Colin Stewart Minchem, Ltd., the disclosure of which is incorporated herein by reference.
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:
Monopentaerythritol Esters
CH2-R2
I P - CH2 — C— CH2— R3
I
Figure imgf000008_0001
Monopentaerythritol Dilaurate
Rι=CH3 - (CH2)ιo -COO- R2=CH3 - (CH2)ιo -COO- R3=OH R4=OH
Monopentaerythritol Monostearate
Figure imgf000009_0001
R2=OH R3=OH
R4=OH
Monopentaerythritol Distearate
R!=CH3 - (CH2)16 -COO-
Figure imgf000009_0002
R3=OH R4=OH
Monopentaerythritol Tristearate
Figure imgf000009_0003
R2=CH3 - (CH2)16 -COO- R3=CH3 - (CH2)i6 -COO- R4=OH
Monopentaerythritol Monobehenate
R!=CH3 - (CH2)20 -COO-
R2=OH
R3=OH
R4=OH
Monopentaerythritol Dibehenate
Ri=CH3 - (CH2)20 -COO- R2=CH3 - (CH2)20 -COO-
R3=OH R4=OH Dipentaervthritol Esters
CH2OR! CH2OR2 I I
HO CH2— C— CH2- O— CH2-C— CH2OH
CH2OR3 CH2OR4
Dipentaerythritol Tetralaurate
Figure imgf000010_0001
R2=CH3 - (CH2)10 -CO R3=CH3-(CH2)10-CO R4=CH3-(CH2)10-CO
Dipentaerythritol Tetrastearate
Figure imgf000010_0002
R3=CH3-(CH2)16-CO R4=CH3 - (CH2)i6 -CO
Pentaerythritol 10 Ethylene Oxide Ester
CH2~ O— (CH2~ CH2O)nH
I Ri— CH2 — C — CH2— R2
CH-O- (CH2-CH20)n.H with n + n' = 10
Monopentaerythritol 10 Ethylene Oxide Distearate
Figure imgf000010_0003
Pentaerythritol 4 Propylene Oxide Esters
CH2 — O — (CH2 - CH - CH20)2H
Figure imgf000010_0004
CH2 — O — (CH2 - CH - CH2O)2H Monopentaerythritol 4 Propylene Oxide Monostearate
R!=CH3 - (CH2)16 -COO- R2=OH
Monopentaerythritol 4 Propylene Oxide Distearate
Figure imgf000011_0001
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 about 50% to about 95% bentonite and about 5% to about 50% fatty softening material, and most preferably from about 80% to 90% bentonite and from about 10% to about 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 PNP 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 Horn, 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:
O O ii II
Rj — C— N— CH2— CH2— NR2— CH2— N — C— ^
wherein Rj represents an oleyl alkyl carbon chain; and R2 represents H or (EO)x with x varying from 0 to 6 (the degree of ethoxylation).
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.
Example 1
Compacted granular unit dose compositions (A and B) were prepared from the following ingredients:
Figure imgf000013_0001
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:
(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

Claims What is claimed is:
1. 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 about 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 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.
2. 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.
3. 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 about 75 microns in diameter.
4. A unit dose softening composition as in claim 1 wherein the montmorillonite- containing clay is a bentonite.
5. 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.
6. A unit softening composition as in claim 4 wherein the bentonite starting material has the following composition by weight:
Si02 from 55.0 to 61.0%; A1203 from 14.5 to 17.6%; Fe203 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%; and Mn304 from 0.04 to 0.25%
7. 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.
8. 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.
9. 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.
10. 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.
11. 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.
12. A unit dose softening composition as in claim 8 wherein the combination of bentonite and said PEC comprises, by weight, from about 50% to about 95% of bentonite and from about 5% to about 50%) of said PEC.
13. A unit dose softening composition as in claim 12 which comprises from about 80 to about 90% of bentonite and from about 10% to about 20% of said PEC.
14. A unit dose softening composition as in claim 1 wherein said fabric softener comprises a liquid fatty ester.
15. A unit dose softening composition as in claim 14 wherein said fatty ester is sunflower oil.
16. A unit dose softening composition as in claim 1 wherein said fabric softener composition comprises a liquid silicone.
17. A unit dose softening composition as in claim 1 wherein said fabric softener composition comprises a liquid oleyl alcohol.
18. 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.
19. A process according to claim 18 wherein the fabric softener composition comprises a treated bentonite clay in combination with an organic fatty softening material.
20. 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.
21. A process according to claim 18 wherein the fabric softener composition comprises a liquid fatty ester.
22. A process according to claim 21 wherein said fatty ester is sunflower oil.
PCT/US2001/013079 2000-04-26 2001-04-23 Wash cycle unit dose softener Ceased WO2001083663A1 (en)

Priority Applications (10)

Application Number Priority Date Filing Date Title
CA002405727A CA2405727A1 (en) 2000-04-26 2001-04-23 Wash cycle unit dose softener
AU5559501A AU5559501A (en) 2000-04-26 2001-04-23 Wash cycle unit dose softener
HK03105255.6A HK1053143B (en) 2000-04-26 2001-04-23 Wash cycle unit dose softener
JP2001580273A JP2003531969A (en) 2000-04-26 2001-04-23 Washing cycle unit softener
BR0110349-0A BR0110349A (en) 2000-04-26 2001-04-23 Washing cycle unit dose fabric softener composition, and process for softening or conditioning laundry
EP01928774A EP1276838B1 (en) 2000-04-26 2001-04-23 Wash cycle unit dose softener
AU2001255595A AU2001255595B2 (en) 2000-04-26 2001-04-23 Wash cycle unit dose softener
DK01928774T DK1276838T3 (en) 2000-04-26 2001-04-23 Washing softening agent containing dosage unit for use in a washing process
MXPA02010286A MXPA02010286A (en) 2000-04-26 2001-04-23 Wash cycle unit dose softener.
DE60123414T DE60123414T2 (en) 2000-04-26 2001-04-23 WASH-SOFT DISPOSABLE DOSING UNIT FOR USE IN A WASHING PROCESS

Applications Claiming Priority (6)

Application Number Priority Date Filing Date Title
US09/558,822 2000-04-26
US09/558,822 US6258767B1 (en) 2000-04-26 2000-04-26 Spherical compacted unit dose softener
US09/620,515 2000-07-20
US09/620,515 US6294516B1 (en) 2000-04-26 2000-07-20 Wash cycle unit dose softener
US09/685,756 2000-10-09
US09/685,756 US6291421B1 (en) 2000-04-26 2000-10-09 Wash cycle unit dose softener

Publications (1)

Publication Number Publication Date
WO2001083663A1 true WO2001083663A1 (en) 2001-11-08

Family

ID=27415782

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/US2001/013079 Ceased WO2001083663A1 (en) 2000-04-26 2001-04-23 Wash cycle unit dose softener

Country Status (12)

Country Link
EP (1) EP1276838B1 (en)
JP (1) JP2003531969A (en)
CN (1) CN1439047A (en)
AT (1) ATE340843T1 (en)
AU (2) AU2001255595B2 (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)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US12215302B1 (en) 2024-06-28 2025-02-04 Bala Nathan Smectite clay-based fabric softener compositions with etheramine stabilizers

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
AU2006276563B2 (en) 2005-08-01 2011-10-06 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 (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0048163A2 (en) * 1980-09-17 1982-03-24 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
EP0530958A2 (en) * 1991-09-06 1993-03-10 Colgate-Palmolive Company Fabric softening products based on a combination of pentaerythritol compound and bentonite
JPH0987696A (en) * 1995-09-27 1997-03-31 Lion Corp Tablet type nonionic detergent composition
WO1999040171A1 (en) * 1998-02-04 1999-08-12 Unilever Plc Detergent compositions
US5972870A (en) * 1997-08-21 1999-10-26 Vision International Production, Inc. Multi-layered laundry tablet
WO2000003959A1 (en) * 1998-07-17 2000-01-27 Colin Stewart Minchem Ltd. Process for treating bentonite and products thereof

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE3708132A1 (en) * 1987-03-13 1988-09-22 Henkel Kgaa AQUEOUS SOFTENER FOR TEXTILE TREATMENT
US5332513A (en) * 1990-01-09 1994-07-26 Colgate-Palmolive Co. Particulate fabric softening and detergent compositions
US5656585A (en) * 1994-12-21 1997-08-12 Colgate-Palmolive Company Clear, concentrated liquid fabric softener compositions

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0048163A2 (en) * 1980-09-17 1982-03-24 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
EP0530958A2 (en) * 1991-09-06 1993-03-10 Colgate-Palmolive Company Fabric softening products based on a combination of pentaerythritol compound and bentonite
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
WO1999040171A1 (en) * 1998-02-04 1999-08-12 Unilever Plc Detergent compositions
WO2000003959A1 (en) * 1998-07-17 2000-01-27 Colin Stewart Minchem Ltd. Process for treating bentonite and products thereof

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
DATABASE WPI Section Ch Week 198703, Derwent World Patents Index; Class D25, AN 1987-018526, XP002174417 *
PATENT ABSTRACTS OF JAPAN vol. 1997, no. 07 31 July 1997 (1997-07-31) *

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US12215302B1 (en) 2024-06-28 2025-02-04 Bala Nathan Smectite clay-based fabric softener compositions with etheramine stabilizers

Also Published As

Publication number Publication date
AU5559501A (en) 2001-11-12
CA2405727A1 (en) 2001-11-08
ATE340843T1 (en) 2006-10-15
EP1276838A1 (en) 2003-01-22
DK1276838T3 (en) 2007-02-05
EP1276838B1 (en) 2006-09-27
JP2003531969A (en) 2003-10-28
BR0110349A (en) 2004-06-22
MXPA02010286A (en) 2003-04-25
AU2001255595B2 (en) 2005-06-30
DE60123414D1 (en) 2006-11-09
HK1053143A1 (en) 2003-10-10
DE60123414T2 (en) 2007-08-23
HK1053143B (en) 2007-04-27
CN1439047A (en) 2003-08-27

Similar Documents

Publication Publication Date Title
US6291421B1 (en) Wash cycle unit dose softener
US6294516B1 (en) Wash cycle unit dose softener
EP1525294B1 (en) Improved wash cycle unit dose softener containing a disintegrating agent
AU2001255577A1 (en) Wash cycle unit dose softener
JP2003531312A (en) Spherical compression unit dose softener
EP1276838B1 (en) Wash cycle unit dose softener
AU2001253770A1 (en) Spherical compacted unit dose softener
AU2001255595A1 (en) Wash cycle unit dose softener
EP1468071A1 (en) Spherical compacted unit dose softener
EP1534810B1 (en) Improved wash cycle unit dose softener containing a controlled amount of moisture
HK1078606A (en) Wash cycle unit dose softener
US6664222B1 (en) Wash cycle unit dose softener
AU2003209273A1 (en) Spherical compacted unit dose softener
HK1069842B (en) Spherical compacted unit dose softener

Legal Events

Date Code Title Description
AK Designated states

Kind code of ref document: A1

Designated state(s): AE AG AL AM AT AU AZ BA BB BG BR BY BZ CA CH CN CO CR CU CZ DE DK DM DZ EE ES FI GB GD GE GH GM HR HU ID IL IN IS JP KE KG KP KR KZ LC LK LR LS LT LU LV MA MD MG MK MN MW MX MZ NO NZ PL PT RO RU SD SE SG SI SK SL TJ TM TR TT TZ UA UG UZ VN YU ZA ZW

AL Designated countries for regional patents

Kind code of ref document: A1

Designated state(s): GH GM KE LS MW MZ SD SL SZ TZ UG ZW AM AZ BY KG KZ MD RU TJ TM AT BE CH CY DE DK ES FI FR GB GR IE IT LU MC NL PT SE TR BF BJ CF CG CI CM GA GN GW ML MR NE SN TD TG

121 Ep: the epo has been informed by wipo that ep was designated in this application
DFPE Request for preliminary examination filed prior to expiration of 19th month from priority date (pct application filed before 20040101)
WWE Wipo information: entry into national phase

Ref document number: 2405727

Country of ref document: CA

WWE Wipo information: entry into national phase

Ref document number: PA/a/2002/010286

Country of ref document: MX

WWE Wipo information: entry into national phase

Ref document number: 2001928774

Country of ref document: EP

ENP Entry into the national phase

Ref country code: JP

Ref document number: 2001 580273

Kind code of ref document: A

Format of ref document f/p: F

WWE Wipo information: entry into national phase

Ref document number: 2001255595

Country of ref document: AU

WWE Wipo information: entry into national phase

Ref document number: 018117015

Country of ref document: CN

WWP Wipo information: published in national office

Ref document number: 2001928774

Country of ref document: EP

WWG Wipo information: grant in national office

Ref document number: 2001255595

Country of ref document: AU

WWG Wipo information: grant in national office

Ref document number: 2001928774

Country of ref document: EP