EP0388105B1 - Détergent préalablement dosé - Google Patents

Détergent préalablement dosé Download PDF

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Publication number
EP0388105B1
EP0388105B1 EP90302581A EP90302581A EP0388105B1 EP 0388105 B1 EP0388105 B1 EP 0388105B1 EP 90302581 A EP90302581 A EP 90302581A EP 90302581 A EP90302581 A EP 90302581A EP 0388105 B1 EP0388105 B1 EP 0388105B1
Authority
EP
European Patent Office
Prior art keywords
film
detergent
polymer
sheet
unit packaging
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
Application number
EP90302581A
Other languages
German (de)
English (en)
Other versions
EP0388105A3 (fr
EP0388105A2 (fr
Inventor
Takeshi Fujita
Chuzo Isoda
Kazuyo Aketa
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.)
DKS Co Ltd
Original Assignee
Dai Ichi Kogyo Seiyaku Co Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Dai Ichi Kogyo Seiyaku Co Ltd filed Critical Dai Ichi Kogyo Seiyaku Co Ltd
Publication of EP0388105A2 publication Critical patent/EP0388105A2/fr
Publication of EP0388105A3 publication Critical patent/EP0388105A3/fr
Application granted granted Critical
Publication of EP0388105B1 publication Critical patent/EP0388105B1/fr
Anticipated expiration legal-status Critical
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Classifications

    • 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
    • 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
    • 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

Definitions

  • the present invention relates to a unit packaging detergent and a film suitable for the packaging.
  • unit packaging detergent in the present specification means a detergent packaged in a water soluble polymer film or sheet in such a form that it is suitable for a one time use.
  • detergent powders or granules have usually been sold filled in a box or a water-insoluble bag, for instance a polyethylene bag, and a suitable amount of the detergent powder or granules is measured by a spoon or a measuring cup or poured into a washing machine.
  • a suitable amount of the detergent powder or granules is measured by a spoon or a measuring cup or poured into a washing machine.
  • it is not only inconvenient to use the detergent in a suitable amount for the washing so as not to waste it, but also liable to spill it onto a floor.
  • coin operated laundries have recently been developed, the development of a unit packaging detergent to be used therein has been desired.
  • the present invention provides a unit packaging detergent which comprises a detergent powder or granules packaged with a water soluble film or sheet made of a polymer having the following properties:
  • the present invention also provides a water soluble film or sheet suitable for a packaging substance of a unit packaging detergent, which is made of a polymer having the following properties.
  • the water soluble polymer film or sheet used in the the present invention is prepared from a water soluble polymer having the aforementioned properties.
  • the tear strength is deteremined according to JIS (Japanese Industrial Standard) K 6301-1975.
  • the dissolution time of the polymer in the present specification is defined as the time required for a polymer film having a thickness of 30 »m and an area of 1 cm2 to dissolves completely in water when it is placed on the surface of water at 20°C.
  • the equilibrium moisture content of the polymer is determined as follows: (1) a test film is placed in a Petri dish, and the Petri dish is put in a desiccator in the bottom of which a saturated aqueous solution of ammonium chloride is contained in an amount of about 5 - 10% by volume of the bottom space, whereby the relative humidity in the desiccator is maintained at about 80% at 20°C; (2) the dessicator is held in a thermostatic chamber at 20°C for 10 days; and (3) the film in the dessicator is weighed daily over these 10 days to determine the equilibrium moisture content of the polymer.
  • polymers satisfying the above properties and having film forming properties are polyoxyethylene derivatives, such as polyesters of polyether polyols which contain polyoxyethylene groups, with polycarboxylic acid and the like.
  • Preferred polyether polyols contain polyoxyethylene groups as an essential element, which may contain other polyoxyalkylene groups derived from alkylene oxides such as propylene oxide, butylene oxide, styrene oxide and the like. Such polyether polyols may be obtained by reacting alkylene oxides with a compound having a plurality of active hydrogen atoms in a molecule (referred to as an active hydrogen-containing compound hereinafter).
  • Such an active hydrogen-containing compound may include alkylene glycols such as ethylene glycol, propylene glycol, butylene glycol, hexylene glycol and the like; aliphatic polyols such as glycerin, sorbitan, pentaerythritol, sugar alcohol, polyglycerin, and the like; aromatic polyols such as hydroquinone, phloroglucinol and the like; amines such as ethylamine, hexylenediamine, phenylenediamine, cyclohexylamine, benzylamine, aniline, imidazolidine and the like; amides; mercaptans; and so on.
  • the active hydrogen-containing compound contains hetero atoms such as amines, amides or mercaptans, the compound so-obtained is also included in the term "a polyether polyol" as used in this specification even though it contains hetero atoms.
  • a preferred polyether polyol is a polyether diol, from the viewpoint of solubility in water and polymeric ability.
  • a monoalcohol cannot extend the polymer chain, and a triol or a polyol having more than 3 hydroxyl groups tends to be reticulated and to be insoluble in water.
  • polyether polyols for example, polyethylene glycol and polypropylene glycol; polyethylene glycol and polyoxyethylene/polyoxypropylene copolymer; polyoxyethylene glycerin and polyoxyethylene/polyoxypropylene copolymer; polyoxyethylene triethanolamine and polyoxyethylene/polyoxypropylene copolymer may also be used. These combinations are not restriced to the above.
  • the polyether polyol itself may contain additional groups such as oxyethylene groups or oxypropylene groups, such may be block copolymers or random copolymers.
  • the polyether polyol may be obtained according to conventional methods, for example, by reacting a desired alkylene oxide, or a mixture of two or more thereof, with one or more active hydrogen containing compound(s) in the presence of catalyst, for example, an alkaline catalyst such as potassium hydroxide or sodium carbonate, or acid catalyst such as boron trifluoride, under a suitable pressure such as 0 to 10 atoms (gauge pressure) at a temperature of, for example, from 60 to 160°C.
  • catalyst for example, an alkaline catalyst such as potassium hydroxide or sodium carbonate, or acid catalyst such as boron trifluoride, under a suitable pressure such as 0 to 10 atoms (gauge pressure) at a temperature of, for example, from 60 to 160°C.
  • alkaline catalyst for an addition polymerization of the alkylene oxide is particularly preferred, because the alkaline catalyst can be also be used as the catalyst for a successive esterification without any elimination thereof or use of additional catalyst.
  • the content of the polyoxyethylene moiety in the polyether polyol is preferably more than 50% by weight, more preferably 70 to 100% by weight based on the total weight of the polyether polyol. If the content of the polyoxyethylene moiety is less than 50%, the water-solubility becomes insufficient.
  • the polyether polyol should be water soluble, and preferably has a weight average molecular weight of more than about 1,000, more preferably more than about 2,000, more preferably 3,000 to 50,000 from the viewpoint of its water solubility and tear strength.
  • the most preferred examples of the polymers for the present invention are polyesters of polyether polyols with polycarboxylic acids.
  • Such polymers can be prepared according to Japanese Patent Application KOKAI No. 56-226018.
  • polycarboxylic acids which may be used for the preparation of the polyester are aliphatic polycarboxylic acids such as malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, maleic acid, fumaric acid, mesaconic acid, malic acid, tartaric acid, hexane tricarboxylic acid, and the like; aromatic polycarboxylic acids such as phthalic acid, isophthalic acid, terephthalic acid, trimellitic acid, pyromellitic acid, 1,5-naphthalenedicarboxylic acid, dimmer acid and the like.
  • aliphatic polycarboxylic acids such as malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, maleic acid, fumaric acid, mesaconic acid, malic acid, tartaric acid
  • the polycarboxylic acid may be a partial or complete ester, which can be reacted by an ester interchange reaction, or may be an acid anhydride such as maleic anhydride, phthalic anhydride, pyromellitic dianhydride, and the like.
  • Lower alkyl esters of the polycarboxylic acids are also usable, such as the methyl esters, polymethyl esters, mono or polyethyl esters, and the like.
  • polycarboxylic acids are phthalic acid, terephthalic acid, isophthalic acid, sebacic acid, pyromellitic acid, lower alkyl esters thereof such as dimethyl esters, and the like.
  • a preferred weight average molecular weight of the polymer such as polyesters of the polyether polyols and the polycarboxylic acid is preferably in the range of from 10,000 to 500,000. If the molecular weight is less than 10,000, the water-solubility of the polymer film or sheet so obtained would be sufficient, but the tear strength will be lower than the limit required and the equilibrium moisture content will exceed the upper limit required, whereas with a molecular weight of more than 500,000 the water-solubility will decrease.
  • the ratio of the polyether polyol to the polycarboxylic acid, ester or acid anhydride is not restrictive providing the molecular weight of the polyether polyol is not less than 1,000, and that of the obtained polymer is not less than 10,000 and not more than 500,000.
  • a film or a sheet obtained from the above polymers has an excellent water-solubility, and dissolves rapidly in water, that is, it can be dissolved at a speed of about 2 to 5 times that of a water soluble polyvinyl alcohol film of the same thickness. Accordingly, a unit packaging detergent packaged in the film or sheet made of the above polymers is rapidly and completely dissolved in water, when thrown into a washing machine, and causes no problems such as an insoluble polymer adhering to or depositing on the washed clothes. Further, the film or sheet made from the above polymer has such a high tear strength that it is not torn or broken when used as a packaging film or sheet in an autopackaging machine.
  • the film or sheet obtained from the above polymer has such a low equilibrium moisture content that it can maintain a very high strength under a high humidity, as in the rainy season, in spite of its high water-solubility, which is a specifically desirable property.
  • the aforementioned polymer is chemically stable, and heat sealable, and additionally the water-solubility of the heat sealed part is maintained so that it does not adhere to and remain on washed cloths after washing, in contrast to PVA, it can be used for unit packaging of a detergent for domestic use or for a vending machine.
  • the esterification of the polyether polyol and the polycarboxylic acid, ester, or acid anhydride can be effected in a conventional manner, for example, by heating under reduced pressure in the presence of catalyst such as p-toluene sulfonic acid, boron trifluoride, potassium hydroxide, sodium hydroxide, magnesium hydroxide, alkali methals and the like.
  • catalyst such as p-toluene sulfonic acid, boron trifluoride, potassium hydroxide, sodium hydroxide, magnesium hydroxide, alkali methals and the like.
  • the preferred temperature is 80 to 250°C, and the preferred pressure is 0.133 to 2666,44 Pa (0.001 to 20 Torr).
  • the reaction can be usually completed within 0.5 to 10 hours. Of course, the reaction may be carried out with the removal of generated water or lower alcohol by ventilation with nitrogen gas.
  • the aforementioned esterification is only by way of suitable example, and should not be construed restrictively.
  • the molecular weight of the polymer may be controlled by the ratio of the polyether polyol to the polycarboxylic acid, or by controlling the reduced pressure. The latter is more practical and easier. As the reaction pressure is lowered, a polymer having a larger molecular weight can be obtained.
  • the aformentioned polyesters are the most suitable polymers for providing a film or a sheet for packaging a detergent
  • another water soluble polymer such as methyl cellulose, hydroxyethyl cellulose, hydroxypropyl methyl cellulose, carboxy methyl cellulose, polyvinyl alcohol, polyvinylpyrrolidone, polyacrylate (e.g. sodium, potassium or ammonium salts) and the like may be mixed therewith.
  • the content of another water soluble polymer is preferably less than 10% by weight of the polymer of the present invention.
  • a film or a sheet of the polymer suitable for packaging a detergent can be obtained in a conventional manner such as by solvent casting, melt extrusion, and the like.
  • the film or sheet of the present invention may contain other substances which are usually formulated into detergent compositions, for example, antioxidants, fluorescent agents, defoamers, chelating agents, and the like, or others such as solubility controlling agents, such as a comparatively lower molecular weight polyethylene glycol; plasticizers; mildew-proofing agents; and the like, if desired.
  • solubility controlling agents such as a comparatively lower molecular weight polyethylene glycol; plasticizers; mildew-proofing agents; and the like, if desired.
  • the thickness of the film or sheet should be controlled in respect of the strength or durability to the packaging process, potential use in a vending machine, storage, commercial transporation and the like; water-solubility in use in order to make the detergent dissolve rapidly and to prevent an insoluble substance from redepositing on washed clothes; moisture permeability in order to prevent the detergent from caking, wetting or deteriorating; and the economics thereof.
  • a usual thickness of the film for the packaging of a detergent is from 10 to 100 »m, more preferably 20 to 60 »m. It would also be preferable to use a film or a sheet having such a thickness in the present invention, because a film or a sheet within this range of thickness is applicable to packaging machines generally used.
  • the polymers to be used for the film or sheet of the present invention should have (1) a tear strength, (2) a dissolution time and (3) an equilibrium moisture content as aforementioned.
  • the detergent to be packaged in the water soluble polymer film or sheet of the present invention is not restricted, and may be any usual detergent.
  • the detergent may typically contain surface active agents such as alkylbenzene sulfonate, alkyl sulfonate, soap, polyoxyalkylene alkyl ether, polyoxyalkylene alkylphenyl ether, fatty acid alkyolamide and the like; builders, such as polyphosphates, zeolite, carbonates, silicate, organic builders including chelating agents and the like; fluorescent whitening agents; redeposition preventing agents such as sodium silicate, carboxymethylcellulose, hydroxypropyl methyl cellulose, hydroxybuthyl methyl cellulose and the like; enzymes such as protease, lipase, amylase and the like; softening agents such as dimethyldialkyl quaternary ammonium salts, imidazolinium compounds and the like; bleaching agents such as sodium percarbonate, sodium perborate and the like; perfumes;
  • the weight of one package (unit) of the unit packaging detergent of the present invention may preferably contain from 3 g to 100 g, more preferably 5 g to 50 g of a detergent.
  • unit packaging means a pack in which the detergent is packaged in such an amount that it is used in a standard one time wash, but it does not mean the exclusion of two or more packs of detergent used in a one time wash, because the amount of the detergent to be used depends on the dirtiness of washing, amount of washing, volume of washing machine, hardness of water, temperature of water, kind of detergent and the like.
  • a detergent package which is intentionally prepared so that two or more units are used in a one time wash is also included in the term "unit packaging"
  • Ethylene oxide 4,500 parts were introduced dropwise into an deaerated autoclave (5 liter) containing propylene glycol 15 parts over about 11 hs. in the presence of potassium hydroxide 2.2 parts as a catalyst as maintaining the reaction temperature at about 90 ⁇ 130 °C and the pressure at about 1 to 2 atmos (gauge pressure) to give a polyether polyol having a weight average molecular weight of 15,000, into which then diethyl isophthalate 68 parts were added and heated at about 180 to 190 °C for 1 h. remaining the same catalyst as removing produced ethyl alcohol under a reduced pressure of about 13,332 Pa (0.1 Torr) to give a polyester having an average molecular weight of about 150,000.
  • the obtained polyester was dissolved in water to give a 20 % aqueous solution (viscosity: about 10,000 cps at 25 °C), the aqueous solution was cast by a coater, and dried at 80 °C for 0.5 hs. to give an even film of 30 »m after cooling.
  • a tear strength is determined according to JIS (Japanese Industrial Standard) K 6301-1975.
  • a dissolution time of the polymer in the present specification is defined as the time required for a polymer film having an area of 1 cm2 to completely dissolve in water when it is placed on the surface of water at 20°C.
  • An equilibrium moisture content of the polymer is determined by (1) a test film is placed in a Petri dish, and the Petri dish is put in a desiccator in the bottom of which a saturated aqueous solution of ammonium chloride is contained in an amount of about 5 ⁇ 10 % by volume of the bottom space, whereby the relative humidity in the desiccator is maintained at about 80% at 20°C for 10 days, and is held in a thermostatic chamber at 20 °C for 10 days, and the film in the desiccator is weighed daily over these 10 days to determine the equilibrium moisture content of the polymer.
  • a powder detergent containing sodium salt of a linear alkylbenzene sulfonic acid as a main surfactant was packaged in the film obtained in the process (2) as containing the detergent of 20 g in one package to yield a unit packaging detergent.
  • the unit packaging detergent was packed in a cardboard case as occupying about 80 % volume (remaining about 20 % space), and subjected to a practical test (packing, carrying, storing and the like in a commercial route). Neither broken nor wetting package was observed.
  • Film of 50 »m thick was prepared from the polyester obtained in the process (1) of the Example 2 using a calender roll.
  • the film has following properties: tear strength: 150 kg/cm, dissolution time (20°C): 15 seconds at 50 »m thick, 8 seconds at 30 »m thick and equilibrium moisture content (at 20 °C and at a relative humidity of 80 %) : 7 %
  • Example 1 According the same manner as in the Example 1 except that the polyester film of the Example 2 was used instead of that of the Example 1 a unit packaging detergent was prepared and evaluated. The same results as in the Example 1 were obtained.
  • the powder detergent (New Beads) was packaged using a film of 30 »m thick made of polyvinyl alcohol soluble in cold water according to the same manner as in the Example 1.
  • the film has following physical properties: tear strength: 180 kg/cm, and equilibrium moisture content (at 20 °C and at a relative humidity of 80 %) : 13 % but the dissolution time (at 20°C) is 35 seconds.
  • Example 2 According to a similar manner to the Example 1 three kinds of water soluble film were obtained, and the physical properties were determined.
  • the kinds of polyether polyol and polycarboxylic acid used, and the properties are shown in Table 1.

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  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Wood Science & Technology (AREA)
  • Organic Chemistry (AREA)
  • Detergent Compositions (AREA)
  • Wrappers (AREA)

Claims (12)

  1. Détergent conditionné en paquets unitaires, qui comprend un détergent en poudre ou granulés empaqueté avec une pellicule ou feuille hydrosoluble constituée d'un polymère ayant les propriétés suivantes :
    (1) une résistance à la déchirure supérieure à 50 kg/cm,
    (2) un temps de dissolution inférieur à 20 secondes à 20°C, et
    (3) une teneur en humidité à l'équilibre inférieure à 20 % à 20°C et à une humidité relative de 80 %.
  2. Détergent conditionné en paquets unitaires tel que revendiqué dans la revendication 1, dans lequel la pellicule hydrosoluble a une épaisseur comprise dans l'intervalle de 10 à 100 micromètres.
  3. Détergent conditionné en paquets unitaires tel que revendiqué dans la revendication 1 ou la revendication 2, dans lequel le polymère comprend un polyester d'un polyéther-polyol.
  4. Détergent conditionné en paquets unitaires tel que revendiqué dans la revendication 3, dans lequel le polyester a un poids moléculaire moyen en poids compris dans l'intervalle de 10 000 à 500 000.
  5. Détergent conditionné en paquets unitaires tel que revendiqué dans la revendication 3, dans lequel le polyester contient des groupes polyéther-polyol ayant un poids moléculaire moyen en poids supérieur à 1000 environ.
  6. Détergent conditionné en paquets unitaires tel que revendiqué dans l'une quelconque des revendications 3 à 5, dans lequel le polymère comprend de plus un polymère hydrosoluble autre que le polyester.
  7. Pellicule ou feuille hydrosoluble convenant comme matière d'empaquetage pour un détergent conditionné en paquets unitaires, qui est constituée d'un polymère ayant les propriétés suivantes :
    (1) une résistance à la déchirure supérieure à 50 kg/cm,
    (2) un temps de dissolution inférieur à 20 secondes à 20°C, et
    (3) une teneur en humidité à l'équilibre inférieure à 20 % à 20°C et à une humidité relative de 80 %.
  8. Pellicule ou feuille telle que revendiquée dans la revendication 7, qui a une épaisseur comprise dans l'intervalle de 10 à 100 micromètres.
  9. Pellicule ou feuille telle que revendiquée dans la revendication 7, dans laquelle le polymère comprend un polyester d'un polyéther-polyol.
  10. Pellicule ou feuille telle que revendiquée dans la revendication 9, dans laquelle le polyester a un poids moléculaire moyen en poids compris dans l'intervalle de 10 000 à 500 000.
  11. Pellicule ou feuille telle que revendiquée dans la revendication 9 ou la revendication 10, dans laquelle le polyester contient des groupes polyéther-polyol ayant un poids moléculaire moyen en poids supérieur à 1000 environ.
  12. Pellicule ou feuille telle que revendiquée dans l'une quelconque des revendications 9 à 11, dans laquelle le polymère comprend de plus un polymère hydrosoluble autre que le polyester.
EP90302581A 1989-03-13 1990-03-12 Détergent préalablement dosé Expired - Lifetime EP0388105B1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP60280/89 1989-03-13
JP1060280A JP2603535B2 (ja) 1989-03-13 1989-03-13 単位包装洗剤

Publications (3)

Publication Number Publication Date
EP0388105A2 EP0388105A2 (fr) 1990-09-19
EP0388105A3 EP0388105A3 (fr) 1991-11-06
EP0388105B1 true EP0388105B1 (fr) 1994-06-15

Family

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Family Applications (1)

Application Number Title Priority Date Filing Date
EP90302581A Expired - Lifetime EP0388105B1 (fr) 1989-03-13 1990-03-12 Détergent préalablement dosé

Country Status (4)

Country Link
EP (1) EP0388105B1 (fr)
JP (1) JP2603535B2 (fr)
KR (1) KR950006296B1 (fr)
DE (1) DE69009808T2 (fr)

Families Citing this family (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0634485B1 (fr) * 1993-07-14 2001-09-05 The Procter & Gamble Company Combinaison détergent-conditionnement
ATE203053T1 (de) * 1994-09-12 2001-07-15 Procter & Gamble Portionsverpacktes waschmittel
GB2305931A (en) * 1995-10-02 1997-04-23 Burman Mueller Frances Honor Dissolvable container
CH695688A5 (de) * 1999-07-06 2006-07-31 Mifa Ag Frenkendorf Flüssiges portionierbares wasserfreies Waschmittelkonzentrat.
GB2367557A (en) * 2000-10-05 2002-04-10 Procter & Gamble Compositions packaged in pouches
DE10100339A1 (de) * 2001-01-05 2002-07-18 Henkel Kgaa Tensidhaltige Waschmittel-, Spülmittel- oder Reinigungsmittel-Portion
US6492312B1 (en) 2001-03-16 2002-12-10 Unilever Home & Personal Care Usa, Division Of Conopco, Inc. Water soluble sachet with a dishwashing enhancing particle
US20030060387A1 (en) * 2001-09-20 2003-03-27 Unilever Home And Personal Care, Usa, Division Of Conopco, Inc. Water-soluble package with fluorescent dye in the film

Family Cites Families (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3277009A (en) * 1961-10-03 1966-10-04 Gen Aniline & Film Corp Water-soluble package and method for making and using same
US3413229A (en) * 1964-03-03 1968-11-26 Mono Sol Division Baldwin Mont Polyvinyl alcohol compositions
US3892905A (en) * 1970-08-12 1975-07-01 Du Pont Cold water soluble plastic films
CA1112534A (fr) * 1976-11-03 1981-11-17 John Pardo Detergent pour lave-vaisselle automatique
CA1279749C (fr) * 1985-09-12 1991-01-29 Johnson (S. C.) & Son, Inc. Feuille de polymere debitrice d'additif pour le traitement de la lessive, et agent de traitement derive de ladite feuille
JPS638497A (ja) * 1986-06-27 1988-01-14 ライオン株式会社 水溶性フイルム入り高嵩密度洗剤

Also Published As

Publication number Publication date
JP2603535B2 (ja) 1997-04-23
EP0388105A3 (fr) 1991-11-06
DE69009808D1 (de) 1994-07-21
EP0388105A2 (fr) 1990-09-19
DE69009808T2 (de) 1994-10-06
KR950006296B1 (ko) 1995-06-13
JPH02238100A (ja) 1990-09-20
KR900014474A (ko) 1990-10-24

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