US3528921A - Bleaching packets - Google Patents

Bleaching packets Download PDF

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Publication number
US3528921A
US3528921A US632535A US3528921DA US3528921A US 3528921 A US3528921 A US 3528921A US 632535 A US632535 A US 632535A US 3528921D A US3528921D A US 3528921DA US 3528921 A US3528921 A US 3528921A
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Prior art keywords
sodium
packets
film
potassium
weight
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Frederick William Gray
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Colgate Palmolive Co
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Colgate Palmolive Co
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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
    • C11D3/00Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/395Bleaching agents
    • C11D3/3955Organic bleaching agents
    • 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
    • C11D17/0039Coated compositions or coated components in the compositions, (micro)capsules
    • 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
    • C11D3/395Bleaching agents
    • C11D3/3953Inorganic bleaching agents
    • 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
    • C11D3/43Solvents
    • 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
    • C11D9/00Compositions of detergents based essentially on soap
    • C11D9/002Non alkali-metal soaps
    • DTEXTILES; PAPER
    • D06TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06LDRY-CLEANING, WASHING OR BLEACHING FIBRES, FILAMENTS, THREADS, YARNS, FABRICS, FEATHERS OR MADE-UP FIBROUS GOODS; BLEACHING LEATHER OR FURS
    • D06L4/00Bleaching fibres, filaments, threads, yarns, fabrics, feathers or made-up fibrous goods; Bleaching leather or furs
    • D06L4/20Bleaching fibres, filaments, threads, yarns, fabrics, feathers or made-up fibrous goods; Bleaching leather or furs using agents which contain halogen
    • D06L4/27Bleaching fibres, filaments, threads, yarns, fabrics, feathers or made-up fibrous goods; Bleaching leather or furs using agents which contain halogen using organic agents

Definitions

  • a bleaching packet in which a dry bleach composition containing a hypochlorite generating agent and inorganic builder salt is enclosed in a film of polyvinyl alcohol impregnated with a water-soluble salt of a strong base and a weak acid. Also, a packet in which a water-soluble, polyvinyl alcohol film encloses a dry bleach composition which contains a mixture of dichloroisocyanurate, carbonate, tripolyphosphate and sulfate salts, said salts being either sodium or potassium and being suitably selected to achieve a weight ratio of potassium to sodium of at least 1:1 in the composition.
  • the present invention relates to packets of bleaching powder. More particularly, it relates to water soluble packets which contain a water soluble bleaching powder.
  • a bleaching packet comprises a dry water soluble composition which liberates hypochlorite chlorine on contact with water disposed within an envelope of polyvinyl alcohol film impregnated with a water soluble salt of a strong base and a weak acid, i.e., a water soluble alkaline buffer salt, preferably having the ability to act as a reducing agent.
  • an alkaline buffer salt in the polyvinyl alcohol film of the instant invention is highly beneficial and advantageous in that the instant packets are characterized by improved stability of the bleach content thereof, diminished loss of available chlorine on aging of the packets, diminished formation of insoluble material during storage of the packets, improved maintenance of original color and clarity of the polyvinyl alcohol film during storage and aging the packets, and improved odor characteristics exhibited on use thereof.
  • the instant packets are also characterized by improved maintenance of an original high level of available chlorine and maintenance of original film characteristics on long storage and aging. Minimized film degradation including reduced embrittlement and cracking is a highly desirable characteristic of the packets of the instant invention.
  • the dry composition within the instant packets comprises a dry water soluble compound which, on contact with water, liberates hypochlorite chlorine, said compound preferably constituting about 1 to 90% by weight of the composition, the remainder, i.e., 10 to 99%, being a water soluble diluent therefor such as water soluble inorganic salt.
  • the inorganic salts used suitably are those alkaline buffer salts which do not react deleteriously with the hypochlorite-generating agent, during either stage or use.
  • the instant packets offer the advantage of providing a highly elfective chlorine-type bleaching agent in a dry form. These packets avoid the dustiness of powdered products, and the likelihood or dangers of spillage or splattering characteristic of liquid products. In use, the entire packet is dropped into a washing machine containing water and clothes to be bleached without any need for premeasuring by the housewife.
  • the instant packets also avoid the necessity for handling of bulky containers of glass or fiberboard cartons by the housewife and provide an effective means of making the characteristic and sometimes irritating odor of chlorineliberating bleaches. Moreover, use of the packets of the instant invention eliminates the possibility of contact of the hypochlorite-liberating bleach with the skin of the user, which is especially desirable in cases of those people who are allergic to hypochlorites.
  • the instant packets offer the further outstanding ad vantage that the product container, i.e., the polyvinyl alcohol film in envelope form, contributes considerable soil anti-redeposition properties to the system and thus the instant packets are especially suited for use in conjunction with soap and detergent products in connection with the washing and bleaching of soiled clothes.
  • the use of water soluble polyvinyl alcohol film is also advantageous in that it is thermoplastic and may readily be heat sealed, it offers hi ghresistance to permeability by gases, it has excellent oil and grease resistance, long shelf life, and it can easily be printed with alcohol-type inks.
  • the polyvinyl alcohol film employed in the preparation of the instant packets is water soluble, that is, with mild agitation it dissolves substantially com pletely in water at temperatures of from about to F. within about 30 seconds.
  • Commercial polyvinyl alcohol which is prepared by the hydrolysis of polyvinyl acetate may be employed, however, it has been found highly desirable to avoid the use of water soluble polyvinyl alcohol which has been ethoxylated, i.e., reacted with ethylene oxide, inasmuch as such ethoxylated polyvinyl alcohol appears to be less stable on aging and storage in contact with the instant hypochlorite generating agents than does material which is free from ethoxylation.
  • Polyvinyl alcohol which is devoid of ethoxylation and which contains on the order of from about 12-40 percent by weight of unhydrolized vinyl acetate has been found to be desirably stable towards the hypochlorite liberating agent during storage and use and to possess highly valuable flexibility characteristics and solubility characteristics in both hot (140 F.) and cold (80 F.) water.
  • Hypochlorite generating agents suitable for use in the packets of the present invention are those water soluble dry solid materials which generate hypochlorite ion on contact with, or dissolution in, water.
  • Examples thereof are the dry, particulate heterocyclic N-chloro imides such as trichloroisocyanuric acid, and dichloroisocyanuric acid and salts thereof such as sodium dichloroisocyanurate and potassium dichloroisocyanurate.
  • Other imides may also be used such as N-chlorosuccinimide, N-chloromalonimide, N chlorophthalimide and N chloronaphthalimide.
  • hydantoins such as 1,3 dichloro 5,5 dimethyl hydantoin; N-monochloro- 5,5 dimethylhydantoin; methylene-bis (N-chloro-5,5-dimethylhydantoin); 1,3 dichloro 5 methyl 5 isobutylhydantoin; 1,3 dichloro 5 methyl 5 ethylhydantoin; 1,3 dichloro 5,5 diisobu'tylhydantoin; 1,3 dichloro methyl 5 n amylhydantoin, and the like.
  • hypochlorite-liberating agents are trichloromelamine N,N-dichlorobenzoylene urea, N,N-dichloro-ptoluenesulfonamide and dry, particulate, water-soluble anhydrous inorganic salts such as lithium hypochlorite and calcium hypochlorite.
  • the instant chlorine-liberating agents are employed in a proportion, within the range, indicated above, such as to yield a product which contains from about 1 to about 20% available chlorine on a total weight basis, although other proportions may be employed if desired.
  • the remainder of the bleaching composition is a water soluble diluent therefor, such as a water soluble inorganic salt, the term water soluble being used in the sense of Water soluble or dispersible.
  • the diluent itself normally will constitute a material such as an alkaline inorganic buffer salt, e.g., a detergent builder salt, which does not react deleteriously with a hypochlorite-generating agent either during storage or use.
  • detergents suitable for use in the instant packets include a wide variety of water soluble organic detergents and wetting agents stable in the presence of the hypochlorite generating agent.
  • Such detergents may be an ionic detergent salts having alkyl substituents of 8 to 22 carbon atoms such as the water soluble higher fatty acid alkali metal soaps, e.g., sodium myristate and sodium palmitate; water soluble sulfated and sulfonated anionic alkali metal and alkaline earth metal detergent salts containing a hydrophobic higher alkyl moiety (typically containing from about 8 to 22 carbon atoms) such as salts of higher alkyl mono or polynuclear aryl sulfonates having from about 10 to 16 carbon atoms in the alkyl group (e.g., sodium dodecylbenzenesulfonate, magnesium tridecylbenzenesulfonate, lithium or potassium pentapropylenebenzenesulfon
  • amphoteric, cationic and non-ionic detergents are also contemplated by the present invention. These detergents should, of course, be employed in a compatible proportion and manner, e.g., in encapsulated form, if appropriate.
  • amphoteric detergents which may be employed include the fatty imidazolines, such as 2-coco-1- hydroxyethyl 1 carboxymethyl 1 hydroxyl imidazoline and similar products made by reacting monocarboxylic fatty acids having chain lengths of 10 to 24 carbon atoms with S-hydroxyethyl ethylene diamine and with monohalo monocarboxylic fatty acids having from 2 to 6 carbon atoms, the fatty beta-alanines such as dodecyl beta-alanine, the inner salt of Z-trimethylamino lauric acid, betaines such as N-dodecyl-N,N-dimethylamino acetic acid, and the like. Mixtures of any two or more of the foregoing may be employed.
  • fatty imidazolines such as 2-coco-1- hydroxyethyl 1 carboxymethyl 1 hydroxyl imidazoline and similar products made by reacting monocarboxylic fatty acids having chain lengths of 10 to 24 carbon atoms with S
  • cationic surface active agents may be employed in the compositions of the present invention, including distearyl dimethyl ammonium chloride, stearyl dimethylbenzyl ammonium chloride, coco dimethylbenzyl ammonium chloride, dicoco dimethyl ammonium chloride, cetylpyridinium chloride, cetyltrimethyl ammonium bromide, the stearyl amine salts that are soluble in water such as stearyl amine acetate and stearyl amine hydrochloride, stearyl-dimethylamine hydrochloride, distearyl amine hydrochloride, octyl phenoxyethoxyethyl dimethylbenzyl ammonium chloride, decyl pyridinium bromide, the pyridinium chloride derivative of the acetylaminoethyl esters of lauric acid, lauryl trimethyl ammonium chloride, decylamine acetate, lauryl dimethylbenzy
  • Nonionic surface active agents which may be employed include the ethylene oxide ethers of alkyl phenols such as nonyl phenol polyoxyethylene ether, the ethylene oxide ethers of fatty alcohols such as tridecyl alcohol polyoxyethylene ether, the ethylene oxide ethers of alkyl mercaptans such as dodecyl mercaptan polyoxyethylene thioether, the ethylene oxide esters of acids such as the lauric ester of polyethylene glycol and the lauric ester of methoxy polyethylene glycol, the ethylene oxide ethers of fatty acid amides, the condensation products of ethylene oxide with partial fatty acid esters of sorbitol such as the lauric ester of sorbitan polyethylene glycol ether, and other similar materials.
  • the proportion of organic surface active agent which is used may vary widely, typically being from about 1 to 30% by weight of the composition contained within the packet.
  • inorganic salts in the instant bleach packets are desirable in that the inorganic salt may serve to adjust pH and also to act as a carrier or dispersion medium for the bleaching agent and if desired, for any other active agents which are employed.
  • Water soluble salts suitable for use in the instant packets include sodium sulfate, sodium chloride, alkaline detergents builder salts having a pH of from 8 to 11 or above such as sodium carbonate, potassium carbonate, borax, and sodium silicate, alkali metal orthophosphates, and polyphosphates such as monosodium phosphate, trisodium phosphate, tetrasodium pyrophosphate, pentasodium tripolyphosphate, pentapotassium tripolyphosphate and acid salts such as sodium bisulphate.
  • sodium carbonate, potassium carbonate, or sodium metasilicate in the instant packets has been found to aid in the retention of the water soluble characteristics of these packets, sodium carbonate or potassium carbonate being especially beneficial in that on dissolution in water, it reacts with any acidic components present (e.g., in the hypochlorite generating agent) to produce bubbles of carbon dioxide gas which contribute a desirable mixing and agitating action.
  • a highly desirable constituent of the composition within the instant packets is a fluorescent brightener or optical dye which is stable in the presence of the hypochlorite generating agent.
  • fluorescent brighteners are of particular assistance in connection with the bleaching of textiles or fabrics in those instances where the chemical bleaching power of the contents of the instant packets may beneficially be supplemented by the action of a blue fluorescing optical bleach.
  • suitable textile substantive optical bleaches which may be present in amounts on the order of about 0.1 to 1 percent by weight of the packets, are triazole compounds such as SOsNa and sulfonated diaminodibenzenethiophene dioxides such S OsNa
  • the packets of the present invention optionally may also contain suitable proportions, i.e., on the order of 0.1 to 1 percent by weight thereof, of hypochlorite-stable, nonsubstantive bluing agent such as ultramarine blue. (It will be appreciated, especially in connection with such bluing agent which is a water insoluble pigment, that for the purposes of this invention, materials which are not truly water soluble may be present as long as they are water dispersible in normal use of the instant packets.)
  • the resistance of the instant packets towards the formation of insoluble material during storage may be improved by sealing these packets within a moisture impermeable container, such as a metal foil or metal foil covered paperboard box and/or within a plastic film characterized by an extremely low moisture vapor transmission rate, e.g., polyethylene; laminates of polyethylene, aluminum foil, and glassine, or wax-coated laminates of metal foil and glassine.
  • a preferred reclosable container which is substantially impermeable to moisture vapor constitutes a bag of polyethylene or like film which is sufiiciently large that the open end may be multiply folded over on it self to provide a substantially moisture vapor tight seal.
  • Such a bag having a folded closure may be placed within a more rigid container or otherwise be provided with means to prevent unravelling of the folded portion of the bag.
  • compositions within the instant packets should be dry i.e., desirably they contain less than 1% and preferably less than 0.5% moisture, in order to prevent decomposition of the hypochlorite liberating agents prior to use of the packets.
  • Various adjuvants may, however, be present including, inter alia, sodium carboxymethyl cellulose, citric acid, resins and polymers such as polyvinyl pyrrolidone, polyacrylates and the like, starch, urea, perfumes, corrosion inhibitors, coloring matter, and the like.
  • the alkaline buffer salts of the present invention are reducing agents, typically salts of strong bases with weak reducing acids, i.e., water soluble inorganic or organic salts which dissolve in water to form dilute (e.g., 0.25%) solutions having a pH greater than about 8.
  • reducing agents typically salts of strong bases with weak reducing acids, i.e., water soluble inorganic or organic salts which dissolve in water to form dilute (e.g., 0.25%) solutions having a pH greater than about 8.
  • reducing agents are sodium sulfite, sodium nitrite, sodium formate, and sodium hypophosphite.
  • Examples of further suitable reducing agents include sodium metabisulfite, sodium hydrosulfite, sodium thiosulfate, sodium dodecylbenzenesulfinate, sodium toluenesulfinate, potassium sulfite, potassium hydrosulfite, lithium sulfite, rubidium sulfite, magnesium sulfite, and the like.
  • alkaline buffer salts include alkali metal salts such as potassium acetate, sodium acetate, and the water soluble inorganic alkali metal detergent builder salts, such as sodium carbonate, sodium bicarbonate, sodium sesquicarbonate, sodium orthosilicate, sodium disilicate, sodium metasilicate, sodium orthophosphate, monohydrogen sodium orthophosphate, dihydrogen sodium orthophosphate, sodium metaphosphate, pentasodium tripolyphosphate, tetrasodium pyrophosphate, disodium dihydrogen pyrophosphate, potassium carbonate, potassium bicarbonate, potassium orthophosphate, monopotassium dihydrogen orthophosphate, dipotassium monohydrogen orthophosphate, dipotassium monohydrogen orthophosphate, tetrapotassium pyrophosphate, potassium metaphosphate, potassium metasilicate, potassium disilicate, potassium hydrogen disilicate, potassium tetrasilicate, lithium carbonate, lithium bicarbonate, lithium orthophosphate, rubidium carbonate, and the like
  • the instant buffers may be present in the film in any amount ranging from a small but suflicient amount NHo oQ-oorn to inhibit attack on the film by the hypochlorite liberating agent up to an amount which adversely affects the physical properties of the film.
  • NHo oQ-oorn a small but suflicient amount to inhibit attack on the film by the hypochlorite liberating agent up to an amount which adversely affects the physical properties of the film.
  • suitable proportions typically in the range of from about 1 to 20% thereof may also be employed, the total content of stabilizing element in the film preferably not being greater than about 25% thereof and desirably less than about 15% thereof.
  • EXAMPLE I An aqueous solution of commercially available polyvinyl alcohol resin of the type employed for the preparation of water soluble polyvinyl alcohol films is prepared.
  • the resin is of a grade which contains approximately 88 percent hydrolyzed polyvinyl acetate, and the temperature of the solution is about 30 C.
  • Sodium nitrite is dissolved in the solution in a proportion equal to 7% by weight of the resin therein, the total solids content of the final solution being about 25% by weight.
  • the uniform solution is then cast on the surface of a polished stainless steel band to form a film of uniform thickness.
  • the band is heated to about 275 C. to drive off the water in the film. After drying, the cast film is peeled away from the band.
  • the dried film which is 1.5 mils uniform thickness is then used to prepare packets having measure ments of approximately 2.75 x 1.75 inches and weighing about 0.4 gram.
  • one rectangle of film is placed over a shallow depression in a hollow block.
  • the depression is evacuated, thus drawing the central portion of the film into the depression and forming a pouch or pocket therein.
  • 40 grams of the following compositions are placed in the pouch formed in the film, and the edge portions of the film which protrude from the depression in the block are moistened with water.
  • a second piece of film is then aligned With the first piece and pressed against it to form a closed packet completely enveloping the composition contained therein. Hot air is applied to the surface of the packet to dry the moistened portion thereof, and the completed bleaching packet, after breaking the vacuum, is removed from the block on which it is formed.
  • composition encased within the package is as follows:
  • Perfume and coloring balance to 100.
  • the packets so produced show excellent stability with respect to retention of original chlorine content, water solubility, color, odor, flexibility, and other properties on long storage and on accelerated aging at elevated temperatures, e.g., 130 F.
  • EXAMPLE V Packets containing the same coposition as given in Example I are prepared with the modification that sodium acetate in amounts equal to 5% or 10% by weight of resin solids is used in the film instead of sodium nitrite. Other than for slightly less desirable color and possibly less flexibility, the desirable properties obtained in Example I are achieved.
  • Trisodium isocyanurate 11.5 Potassium carbonate 8.3 Potassium tripolyphosphate 30.0 Potassium sulphate 36.2
  • EXAMPLE VIII Commercial polyvinyl alcohol film-forming resin is dissolved in Water and 10% sodium sulfite is added thereto, the percentage being calculated on the basis of the polyvinyl alcohol resin solids content of the solution.
  • the solution is cast into film about 1.5 mils thick, and packets are formed therefrom in accordance with Example I.
  • the packets are filled with about 40 grams each of the following composition:
  • EXAMPLE XI Packets corresponding to those of Example II are prepared with the modifications (a) that 7% sodium nitrite and 3% disodium monohydrogen phosphate are added to the film in lieu of the inhibitor of that example and (b) that the following bleach compositions are used in these packets.
  • the packets so prepared show excellent stability and retention of original properties.
  • the films employed constitute commercial polyvinyl alcohol film devoid of ethoxylation and containing about 12% of unhydrolyzed acetate.
  • Packets are prepared using films modified with the inhibitors and combinations of inhibitors in the proportion by weight indicated:
  • EXAMPLE XIII 10 (a) 10% sodlum sulfite (Example XVIII) (b) 10% sodium nitrite (Example XIX)
  • Four sets of packets are prepared 1n accordance with (c) 7% Sodium nitrite plus i i hydrogn Example I hereof with the modification that sodium sulphosphate (Example XX) fite is added to the polyvinyl alcohol resin solution in amounts equal to (A) 1 (B) 5, (c) and (D) by as the addit ves 40 g. of the following composition were weight of the resin respectively.
  • Packets are prepared 15 sealed therem: from each of these various films in accordance with Ex- Parts by Welght ample I with the further modification that the comPosi- Potass m drchlorolsocyanurate 16.4- tions packaged therein contain h following; P ntasodlum trlpolyphosphate 40.0 Sodium lauryl sulfate 1.6 Parts Welght Sodium sulfate Potassium dichloroisocyanurate 20 Ultramarine blue 0.3 Sodium sulfate 70 Pentasodium tripolyphosphate 10 Paclzletsgso prepared exh1b1t excellent stability on storage an a mg.
  • the finished packets of each set are stored in polyethylene bags which are hermetically sealed.
  • EXAMPLES XXLXXVI plackets exhibit excellent stability with respect to available
  • the following composition is prepared: c lorine content, formation of insoluble products, discoloration, flexibility and formation of malodors, the T hl oisoc anuric acid Parts by welgfi packets prepared from films having the highest content of m i dro en g 5 u inhibitor exhibiting the best characteristics.
  • composition used in Examples XXI-XXVI is modi- Parts y Weight fied to provide the following compositions: Trichlorlsocyanuric acid 16 Pentasodium tripolyphosphate 20 Potassium carbonate 7 Sodium tridecylbenzenesulfonate 2 Parts by weight Ultramarine 'blue 0.33 A B 0 Sodium sulphate anhydrous, balance to 100.
  • Example XXIX The composition of Example XXIX is modified to contain 20% sodium tripolyphosphate instead of 30% sodium tripolyphosphate. With packets prepared from film containing-- Example:
  • Example 1 the desirable properties described in Example 1 are achieved.
  • a buffer salt of a strong base and aweak acid in combination with a reducing agent is particularly desirable when the bleaching agent is trichlorisocyanuric acid.
  • EXAMPLE XXXIII In any of the modified polyvinyl alcohol film packets described above, the following bleach composition is in serted: 20% sodium dichloroisocyanurate, 40% sodium tripolyphosphate and 40% sodium sulfate.
  • packets having exceptional stability with respect to available chlorine content even under conditions of high humidity by formulating the mixtures enclosed within the polyvinyl alcohol film so that said mixtures contain dichloroisocyanurates and builder salts in such amounts as to include certain proportions of potassium salts and predetermined sodium: potassium ratios.
  • Mixtures characterized by these proportions and ratios may be enclosed in either the preferred polyvinyl alcohol film containing the alkaline buffer salt, as de scribed above, or less desirably, in polyvinyl alcohol film which does not contain the buffer salt.
  • compositions for use in film packets which compositions contain the sodium or potassium salt of dichloroisocyanuric acid (usually in amount such as to supply about 10-15% of available chlorine) and contain builder salts including tripolyphosphates and carbonates
  • the compositions have very good stability with respect to available chlorine content when the weight ratio of potassium to sodium is at least 1:1. It has also been found that while there is a very marked improvement when the weight ratio of potassium to sodium is raised from say 0.1 to 0.25 or even 0.8:1 to the preferred level of at least about 1:1 (e.g.
  • the proportion of available chlorine is in the range of about 11 to 14% (eg., 12 or 13%), the proportion of the dichloroisocyanurate salt being about 20% of the total composition, and there are present relatively large amounts of a tripolyphosphate (the sodium and/or potassium tripolyphosphates constituting for example more than 25% (e.g,. about 25-35%) of the total composition), a smaller amount (e.g., about 1 to 10% of the total composition) of sodium or potassium carbonate, and relatively large amounts of a sulfate, or other neutral salt (the sodium and/or potassium sulfates constituting for example about 4070% of the total composition).
  • a tripolyphosphate the sodium and/or potassium tripolyphosphates constituting for example more than 25% (e.g,. about 25-35%) of the total composition
  • a smaller amount e.g., about 1 to 10% of the total composition
  • sodium or potassium carbonate e.g., sodium or potassium carbonate
  • the total amount of sodium and potassium (calculated in terms of the amount of the element, which is, however, present in the form of its salt, of course) is preferably above 20% and more preferably above 25%, e.g., about 30-40%, of the total composition, and the total amount of potassium is preferably correspondingly above 10%, more preferably above 15% (e.g., about 17%) of the total composition.
  • the amount of available chlorine, in a composition where all the chlorine is present as the dichloroisocyanurate, is equal to twice the actual chlorine percentage; this is the conventional way of expressing the available chlorine which is an indication of bleaching power.
  • the presence of the carbonate in the composition is particularly important since it decreases the tendency for the film to become insolubilized. Also, the carbonate has a beneficial effect in promoting the disintegration of the composition on contact with the wash water.
  • Example II An all-potassium formulation is illustrated in Example II above.
  • Still another formulation which shows a chlorine retention (measured as indicated above) at least as good as the composition of Example II is identical with Example II except that 20 parts of sodium dichloroisocyanurate are used in place of the 20 parts of potassium dichloroisocyanurate and 5 parts of sodium carbonate are used in place of the 5 parts of potassium carbonate.
  • each of these formulations may be enclosed in the buffercontaining polyvinyl alcohol film described in the above examples or, as previously indicated, it may be enclosed, less desirably, in an otherwise identical film from which the buffer has been omitted. While in each of the foregoing specific embodiments any given anion is attached to a single cation, it will be understood that this is by no means an essential condition and that compositions may be used in which there are mixtures of two salts of the anion, e.g., a mixture containing both potassium sulfate and sodium sulfates, or both potassium carbonate and sodium carbonate, both potassium dichloroisocyanurate and sodium dichloroisocyanurate or any combination of these.
  • the other auxiliary ingredients previously mentioned in this application may be present, such as the detergent shown in Example XII and the coloring materials, brighteners, etc.
  • compositions corresponding to this aspect of the invention are disclosed in Examples VI, VII, VIII, XIV, to XVII, XXI to XXVI, XXV III to XXXII.
  • the preferred compositions also contain pentasodium tripolyphosphate and sodium sulfate, each in proportion of at least 35%.
  • the potassium carbonate inhibits the formation of obnoxious odors on storage of dry bleach compositions containing trichlorocyanuric acid, and, when the weight ratio of potassium carbonate to trichlorocyanuric acid is within the range described above, the compositions have good stability with respect to chlorine retention.
  • the weight ratio of potassium carbonate to trichlorocyanuric acid is above about 0.5 :1, the stability with respect to chlorine retention is adversely affected.
  • the available chlorine contents of the compositions used in the packets preferably be within the range of about 5-20%, more preferably in the range of about 745%, and still more preferably above
  • the percentage of available chlorine is, according to the conventional practice in the art of bleaching compositions, twice the actual percentage of active chlorine; thus a typical commercial grade of trichlorocyanuric acid has an available chlorine content of 90.2%.
  • Example X)Q(III the dry bleach composition, which contains sodium dichloroisocyanaurate and is free of carbonate, has good chlorine solubility and disperses readily in the wash water.
  • the presence of the buffer in the polyvinyl alcohol film protects the film against the insolubilizing effects of the composition of that example.
  • hypochlorite chlorine refers to chlorine present as hypochlorous ion (OCl-), as is conventional in the art.
  • a bleaching packet which consists essentially of a dry, water-soluble, bleaching composiiton; 190% by weight of said bleaching composition being a bleaching agent which generates hypochlorite ion on contact with water selected from the group consisting of heterocyclic N-chloro imides, trichloromelamine, N,N-dichlorobenzoylene urea, N,N dichloro p toluene sulfonamide, lithium hypochlorite and calcium hypochlorite, 10 to 99% by Weight thereof being water-soluble, alkali metal, inorganic builder salt, and less than 1% by weight thereof being moisture; said bleaching composition being disposed within an envelope of water-soluble, non-ethoxylated, polyvinyl alcohol film containing about 12 to 40% by weight of unhydrolyzed vinyl acetate, said film being impregnated with a water-soluble salt of a strong base and a weak acid selected from the group consisting of organic and inorganic salts
  • a bleaching packet consisting essentially of a dry, water-soluble composition; l-90% by weight of said bleaching composition being a hypochlorite liberating agent selected from the grou consisting of trichlorocyanuric acid, dichlorocyanuric acid, potassium, dichloroisocyanurate, sodium dichloroisocyanurate and mixtures thereof, 10 to 99% by weight thereof being water-soluble, alkali metal, inorganic builder salt, and less than 1% by weight thereof being moisture, said bleaching packet being disposed within an envelope of Water-soluble, non-ethoxylated, polyvinyl alcohol film containing about 12 0t 40% by Weight of unhydrolyzed vinyl acetate, said film being impregnated with sodium hypophosphite, the amount of hypophosphite being selected from the range of 0.5 to 25% by Weight, based on the total weight of the film, and being effective to inhibit insolubilization of the film.
  • hypochlorite liberating agent selected from the
  • a bleaching packet which consists essentially of a dry, water-soluble bleaching composition; 190% by weight of said bleaching composition being a dry, solid heterocyclic N-chloro-imide bleach which generates hypochlorite ion on contact with water, 10 to 99% by Weight thereof being water-soluble, alkali metal, inorganic builder salt, and less than 1% by weight thereof being moisture, said bleaching packet being disposed within an envelope of water-soluble non-ethoxylated, polyvinyl alcohol film containing about 12 to 40% by weight of unhydrolyzed vinyl acetate, said film being impregnated with a watersoluble salt of a strong base and a weak acid selected from the group consisting of organic and inorganic salts having a pH greater than about 8 at a 0.25% salt concentration in water, the amount of impregnating salt being selected from the range of 0.5 to 25 by Weight, based on the total weight of the film, and being effective to inhibit insolubilization of the film.
  • a bleaching packet as set forth in claim 7 is sodium nitrite.
  • a bleaching packet which consists essentially of (A) a dry, water-soluble, bleaching composition consisting essentially of (1) a hypochlorite generating agent selected from the group consisting of potassium dichloroisocyanurate, sodium dichloroisocyanurate, and mixtures thereof in an amount sufiicient to provide 5 to 20% by weight of available chlorine; (2) l to 10% by weight of sodium or potassium carbonate; (3) less than 1% by weight of moisture; and (4) the balance being substantially a mixture of water-soluble, inorganic, sodium or potassium tripolyphosphate and soidum or potassium sulfate; the total amount of potassium calculated in terms of the element being above 10% by weight of the composition and the Weight ratio of potassium to sodium being at least 1:1; disposed within (B) an envelope of wateralcohol is partially hydrolyzed polyvinyl acetate, the hy- 1O drolysis being about 88% complete.
  • a hypochlorite generating agent selected from the group consisting of potassium dichloro

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Wood Science & Technology (AREA)
  • Organic Chemistry (AREA)
  • Textile Engineering (AREA)
  • Detergent Compositions (AREA)
  • Chemical Or Physical Treatment Of Fibers (AREA)
  • Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
US632535A 1966-07-08 1967-04-21 Bleaching packets Expired - Lifetime US3528921A (en)

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US56367566A 1966-07-08 1966-07-08
US63253567A 1967-04-21 1967-04-21
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US656998A Expired - Lifetime US3528922A (en) 1966-07-08 1967-07-27 Novel surfactant combination in a solvent degreasing self-emulsifying cleaning composition

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AT (2) AT286223B (no)
BE (1) BE700853A (no)
CA (1) CA813298A (no)
CH (1) CH539162A (no)
DE (2) DE1586551A1 (no)
ES (1) ES342705A1 (no)
FR (1) FR1536449A (no)
GB (3) GB1197983A (no)
NL (1) NL6709475A (no)
NO (1) NO125106B (no)
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Cited By (47)

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US3645390A (en) * 1969-08-07 1972-02-29 Robert F Ryan Diazo copying machine roll cleaner package
US3892905A (en) * 1970-08-12 1975-07-01 Du Pont Cold water soluble plastic films
US4099912A (en) * 1974-05-15 1978-07-11 Colgate-Palmolive Company Detergent compositions and washing methods including and utilizing separate tablets of components
US4129415A (en) * 1976-10-15 1978-12-12 American Cyanamid Company Method for removing permanent dyes from hair and other keratinaceous materials
US4234442A (en) * 1978-07-14 1980-11-18 Akzo N.V. Feed unit of a detergent composition based on alkali carbonate
US4279764A (en) * 1980-06-30 1981-07-21 Fmc Corporation Encapsulated bleaches and methods of preparing them
US4334610A (en) * 1979-01-23 1982-06-15 Nissan Chemical Industries, Ltd. Method of storing a solid chlorinating agent and an article for storing same
US4506783A (en) * 1974-06-21 1985-03-26 Shila Morganroth Hair bleaching art
US4522738A (en) * 1983-04-26 1985-06-11 Magid David J Toilet bowl cleaner
US4544693A (en) * 1984-01-03 1985-10-01 Monsanto Company Water-soluble film
US4608187A (en) * 1984-04-02 1986-08-26 The Clorox Company Rubber toughened polyvinyl alcohol film compositions
US4622037A (en) * 1984-05-16 1986-11-11 Basf Aktiengesellschaft Bleaching cotton-containing fabrics with hypochlorite at elevated temperatures
US4626372A (en) * 1981-11-10 1986-12-02 The Clorox Company Borate solution soluble polyvinyl alcohol films
US4765916A (en) * 1987-03-24 1988-08-23 The Clorox Company Polymer film composition for rinse release of wash additives
US4797221A (en) * 1985-09-12 1989-01-10 S. C. Johnson & Son, Inc. Polymer sheet for delivering laundry care additive and laundry care product formed from same
US4801636A (en) * 1987-03-24 1989-01-31 The Clorox Company Rinse soluble polymer film composition for wash additives
US4972017A (en) * 1987-03-24 1990-11-20 The Clorox Company Rinse soluble polymer film composition for wash additives
US5078301A (en) * 1987-10-02 1992-01-07 Ecolab Inc. Article comprising a water soluble bag containing a multiple use amount of a pelletized functional material and methods of its use
US5222595A (en) * 1990-07-18 1993-06-29 Rhone-Poulenc Ag Company Bag in a bag for containerization of toxic or hazardous material
US5224601A (en) * 1990-07-18 1993-07-06 Rhone-Poulenc Ag Company Water soluble package
US5234615A (en) * 1987-10-02 1993-08-10 Ecolab Inc. Article comprising a water soluble bag containing a multiple use amount of a pelletized functional material and methods of its use
US5234140A (en) * 1992-07-28 1993-08-10 S. C. Johnson & Son, Inc. Re-useable aerosol container
AU648865B2 (en) * 1987-10-02 1994-05-05 Ecolab Inc. Article comprising a water soluble bag containing a multiple use amount of a pelletized functional material and methods of its use
US5362413A (en) * 1984-03-23 1994-11-08 The Clorox Company Low-temperature-effective detergent compositions and delivery systems therefor
US5627150A (en) * 1995-10-16 1997-05-06 Ecolab Inc. Paperboard container for solid block detergents
GB2319521A (en) * 1996-11-21 1998-05-27 Derek Acca Water-soluble sanitizing package
US6037319A (en) * 1997-04-01 2000-03-14 Dickler Chemical Laboratories, Inc. Water-soluble packets containing liquid cleaning concentrates
US6136776A (en) * 1997-04-01 2000-10-24 Dickler Chemical Laboratories, Inc. Germicidal detergent packet
US20020137648A1 (en) * 2000-11-27 2002-09-26 Sanjeev Sharma Dishwashing method
US20020142931A1 (en) * 2000-07-19 2002-10-03 The Procter & Gamble Company Gel form automatic dishwashing compositions, methods of preparation and use thereof
US20030092596A1 (en) * 2001-07-24 2003-05-15 Unilever Home & Personal Care Usa, Division Of Conopco, Inc. Polymer products
GB2383320A (en) * 2000-08-25 2003-06-25 Reckitt Benckiser Inflated water-soluble container
US6624130B2 (en) 2000-12-28 2003-09-23 Unilever Home & Personal Care Usa Division Of Conopco, Inc. Laundry product
US6670314B2 (en) 2000-11-27 2003-12-30 The Procter & Gamble Company Dishwashing method
US20050061703A1 (en) * 2000-11-27 2005-03-24 Catlin Tanguy Marie Louis Alexandre Detergent products, methods and manufacture
US20060105992A1 (en) * 2004-11-08 2006-05-18 Buchanan Charles M Pharmaceutical formulations of cyclodextrins and selective estrogen receptor modulator compounds
US20060105045A1 (en) * 2004-11-08 2006-05-18 Buchanan Charles M Cyclodextrin solubilizers for liquid and semi-solid formulations
WO2006078804A1 (en) * 2005-01-22 2006-07-27 The Procter & Gamble Company Methods of making water-soluble film with resistance to solubility prior to being immersed in water
US20060165625A1 (en) * 2005-01-22 2006-07-27 Verrall Andrew P Water-soluble film article having salt layer, and method of making the same
WO2006078897A1 (en) * 2005-01-22 2006-07-27 The Procter & Gamble Company Water-soluble film with resistance to solubility prior to being immersed in water
US20060260973A1 (en) * 2003-06-20 2006-11-23 Plantic Technologies Ltd. Easy open water soluble blister package
WO2007073702A2 (es) 2005-12-29 2007-07-05 Osmotica Corp. Comprimido multicapa con combinaciĆ³n de triple liberaciĆ³n
US20090054295A1 (en) * 2007-08-24 2009-02-26 Celanese International Corporation Chemical Delivery Product And Process For Making The Same
US20090291282A1 (en) * 2005-06-16 2009-11-26 The Nippon Synthetic Chemical Industry Co., Ltd. Water-soluble film
US8283300B2 (en) 2000-11-27 2012-10-09 The Procter & Gamble Company Detergent products, methods and manufacture
US8940676B2 (en) 2000-11-27 2015-01-27 The Procter & Gamble Company Detergent products, methods and manufacture
GB2520604A (en) * 2013-09-26 2015-05-27 Bcuk Aquatics Ltd Water treatment

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GB1430610A (en) * 1973-09-04 1976-03-31 Procter & Gamble Ltd Liquid detergent compositions
US3933674A (en) * 1975-02-07 1976-01-20 Farnsworth Albert M Cleaning composition
US4060496A (en) * 1976-04-29 1977-11-29 Burnishine Products Inc. Stainless steel cleaner
US4416791A (en) 1981-11-11 1983-11-22 Lever Brothers Company Packaging film and packaging of detergent compositions therewith
GB8410826D0 (en) * 1984-04-27 1984-06-06 Unilever Plc Bleach products
US4774015A (en) * 1986-02-28 1988-09-27 Cherokee Chemical Co., Inc. Carburetor cleaner

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US3108077A (en) * 1958-04-14 1963-10-22 Colgate Palmolive Co Oxidizing scouring cleanser and process of preparing same
US3150132A (en) * 1960-06-21 1964-09-22 Monsanto Co Novel chlorocyanurate compounds
US3186869A (en) * 1961-02-23 1965-06-01 Friedman Jack Coated film for laundry package

Cited By (79)

* Cited by examiner, ā€  Cited by third party
Publication number Priority date Publication date Assignee Title
US3645390A (en) * 1969-08-07 1972-02-29 Robert F Ryan Diazo copying machine roll cleaner package
US3892905A (en) * 1970-08-12 1975-07-01 Du Pont Cold water soluble plastic films
US4099912A (en) * 1974-05-15 1978-07-11 Colgate-Palmolive Company Detergent compositions and washing methods including and utilizing separate tablets of components
US4506783A (en) * 1974-06-21 1985-03-26 Shila Morganroth Hair bleaching art
US4129415A (en) * 1976-10-15 1978-12-12 American Cyanamid Company Method for removing permanent dyes from hair and other keratinaceous materials
US4234442A (en) * 1978-07-14 1980-11-18 Akzo N.V. Feed unit of a detergent composition based on alkali carbonate
US4334610A (en) * 1979-01-23 1982-06-15 Nissan Chemical Industries, Ltd. Method of storing a solid chlorinating agent and an article for storing same
US4279764A (en) * 1980-06-30 1981-07-21 Fmc Corporation Encapsulated bleaches and methods of preparing them
US4626372A (en) * 1981-11-10 1986-12-02 The Clorox Company Borate solution soluble polyvinyl alcohol films
US4522738A (en) * 1983-04-26 1985-06-11 Magid David J Toilet bowl cleaner
US4544693A (en) * 1984-01-03 1985-10-01 Monsanto Company Water-soluble film
US5362413A (en) * 1984-03-23 1994-11-08 The Clorox Company Low-temperature-effective detergent compositions and delivery systems therefor
US4608187A (en) * 1984-04-02 1986-08-26 The Clorox Company Rubber toughened polyvinyl alcohol film compositions
US4622037A (en) * 1984-05-16 1986-11-11 Basf Aktiengesellschaft Bleaching cotton-containing fabrics with hypochlorite at elevated temperatures
US4797221A (en) * 1985-09-12 1989-01-10 S. C. Johnson & Son, Inc. Polymer sheet for delivering laundry care additive and laundry care product formed from same
US4972017A (en) * 1987-03-24 1990-11-20 The Clorox Company Rinse soluble polymer film composition for wash additives
US4765916A (en) * 1987-03-24 1988-08-23 The Clorox Company Polymer film composition for rinse release of wash additives
US4801636A (en) * 1987-03-24 1989-01-31 The Clorox Company Rinse soluble polymer film composition for wash additives
US5078301A (en) * 1987-10-02 1992-01-07 Ecolab Inc. Article comprising a water soluble bag containing a multiple use amount of a pelletized functional material and methods of its use
US5234615A (en) * 1987-10-02 1993-08-10 Ecolab Inc. Article comprising a water soluble bag containing a multiple use amount of a pelletized functional material and methods of its use
AU648865B2 (en) * 1987-10-02 1994-05-05 Ecolab Inc. Article comprising a water soluble bag containing a multiple use amount of a pelletized functional material and methods of its use
US5222595A (en) * 1990-07-18 1993-06-29 Rhone-Poulenc Ag Company Bag in a bag for containerization of toxic or hazardous material
US5224601A (en) * 1990-07-18 1993-07-06 Rhone-Poulenc Ag Company Water soluble package
US5234140A (en) * 1992-07-28 1993-08-10 S. C. Johnson & Son, Inc. Re-useable aerosol container
US5627150A (en) * 1995-10-16 1997-05-06 Ecolab Inc. Paperboard container for solid block detergents
GB2319521A (en) * 1996-11-21 1998-05-27 Derek Acca Water-soluble sanitizing package
GB2319521B (en) * 1996-11-21 2000-11-22 Derek Acca Water sanitising
US6037319A (en) * 1997-04-01 2000-03-14 Dickler Chemical Laboratories, Inc. Water-soluble packets containing liquid cleaning concentrates
US6136776A (en) * 1997-04-01 2000-10-24 Dickler Chemical Laboratories, Inc. Germicidal detergent packet
US20020142931A1 (en) * 2000-07-19 2002-10-03 The Procter & Gamble Company Gel form automatic dishwashing compositions, methods of preparation and use thereof
GB2383320A (en) * 2000-08-25 2003-06-25 Reckitt Benckiser Inflated water-soluble container
GB2383320B (en) * 2000-08-25 2004-05-19 Reckitt Benckiser Water-soluble containers
US20060090779A1 (en) * 2000-11-27 2006-05-04 The Procter & Gamble Company Dishwashing method
US8435935B2 (en) 2000-11-27 2013-05-07 The Procter & Gamble Company Detergent products, methods and manufacture
US6670314B2 (en) 2000-11-27 2003-12-30 The Procter & Gamble Company Dishwashing method
US10889786B2 (en) 2000-11-27 2021-01-12 The Procter & Gamble Company Detergent products, methods and manufacture
US20040235697A1 (en) * 2000-11-27 2004-11-25 The Procter & Gamble Company Dishwashing method
US20050061703A1 (en) * 2000-11-27 2005-03-24 Catlin Tanguy Marie Louis Alexandre Detergent products, methods and manufacture
US20020137648A1 (en) * 2000-11-27 2002-09-26 Sanjeev Sharma Dishwashing method
US20060097424A1 (en) * 2000-11-27 2006-05-11 The Procter & Gamble Company Dishwashing method
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US9434916B2 (en) 2000-11-27 2016-09-06 The Procter & Gamble Company Detergent products, methods and manufacture
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US8658585B2 (en) 2000-11-27 2014-02-25 Tanguy Marie Louise Alexandre Catlin Detergent products, methods and manufacture
US8518866B2 (en) 2000-11-27 2013-08-27 The Procter & Gamble Company Detergent products, methods and manufacture
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US20080041020A1 (en) * 2000-11-27 2008-02-21 Alexandre Catlin Tanguy M L Detergent products, methods and manufacture
US20080076693A1 (en) * 2000-11-27 2008-03-27 The Procter & Gamble Company Dishwashing method
US7386971B2 (en) 2000-11-27 2008-06-17 The Procter & Gamble Company Detergent products, methods and manufacture
US7648951B2 (en) 2000-11-27 2010-01-19 The Procter & Gamble Company Dishwashing method
US7521411B2 (en) 2000-11-27 2009-04-21 The Procter & Gamble Company Dishwashing method
US7550421B2 (en) 2000-11-27 2009-06-23 The Procter & Gamble Company Dishwashing method
US6624130B2 (en) 2000-12-28 2003-09-23 Unilever Home & Personal Care Usa Division Of Conopco, Inc. Laundry product
US20030092596A1 (en) * 2001-07-24 2003-05-15 Unilever Home & Personal Care Usa, Division Of Conopco, Inc. Polymer products
US20060260973A1 (en) * 2003-06-20 2006-11-23 Plantic Technologies Ltd. Easy open water soluble blister package
US20060105992A1 (en) * 2004-11-08 2006-05-18 Buchanan Charles M Pharmaceutical formulations of cyclodextrins and selective estrogen receptor modulator compounds
US20060105045A1 (en) * 2004-11-08 2006-05-18 Buchanan Charles M Cyclodextrin solubilizers for liquid and semi-solid formulations
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US8728449B2 (en) 2005-01-22 2014-05-20 Monosol Llc Water-soluble film article having salt layer, and method of making the same
US20080020220A1 (en) * 2005-01-22 2008-01-24 Maurer Joshua A Water-soluble film with resistance to solubility prior to being immersed in water
US20060216424A1 (en) * 2005-01-22 2006-09-28 Maurer Joshua A Methods of making water-soluble film with resistance to solubility prior to being immersed in water
WO2006078804A1 (en) * 2005-01-22 2006-07-27 The Procter & Gamble Company Methods of making water-soluble film with resistance to solubility prior to being immersed in water
AU2006206456B2 (en) * 2005-01-22 2009-06-18 Monosol, Llc Water-soluble film article having salt layer, and method of making the same
US8563105B2 (en) 2005-01-22 2013-10-22 The Procter & Gamble Company Water-soluble film with resistance to solubility prior to being immersed in water
US8642129B2 (en) 2005-01-22 2014-02-04 The Procter & Gamble Company Methods of making water-soluble film with resistance to solubility prior to being immersed in water
WO2006078844A1 (en) * 2005-01-22 2006-07-27 Monosol, Llc Water-soluble film article having salt layer, and method of making the same
US20060165625A1 (en) * 2005-01-22 2006-07-27 Verrall Andrew P Water-soluble film article having salt layer, and method of making the same
US7754318B2 (en) 2005-06-16 2010-07-13 The Nippon Synthetic Chemical Industry Co., Ltd. Water-soluble film
US20090291282A1 (en) * 2005-06-16 2009-11-26 The Nippon Synthetic Chemical Industry Co., Ltd. Water-soluble film
WO2007073702A2 (es) 2005-12-29 2007-07-05 Osmotica Corp. Comprimido multicapa con combinaciĆ³n de triple liberaciĆ³n
US8772220B2 (en) 2007-08-24 2014-07-08 Sekisui Specialty Chemicals America, Llc Chemical delivery product and process for making the same
US20090054295A1 (en) * 2007-08-24 2009-02-26 Celanese International Corporation Chemical Delivery Product And Process For Making The Same
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GB2520604A (en) * 2013-09-26 2015-05-27 Bcuk Aquatics Ltd Water treatment

Also Published As

Publication number Publication date
CH539162A (de) 1973-08-31
FR1536449A (fr) 1968-08-16
GB1197981A (en) 1970-07-08
AT286223B (de) 1970-11-25
DE1769980A1 (de) 1971-11-18
BE700853A (no) 1967-12-18
AT297651B (de) 1972-04-10
NL6709475A (no) 1968-01-09
SE325014B (no) 1970-06-22
GB1197982A (en) 1970-07-08
SE325014C (sv) 1977-10-17
DE1586551A1 (de) 1969-12-18
GB1197983A (en) 1970-07-08
CA813298A (en) 1969-05-20
NO125106B (no) 1972-07-17
US3528922A (en) 1970-09-15
ES342705A1 (es) 1968-08-01

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