US3186869A - Coated film for laundry package - Google Patents

Coated film for laundry package Download PDF

Info

Publication number
US3186869A
US3186869A US16931662A US3186869A US 3186869 A US3186869 A US 3186869A US 16931662 A US16931662 A US 16931662A US 3186869 A US3186869 A US 3186869A
Authority
US
United States
Prior art keywords
film
barrier coating
water
package
agents
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
Inventor
Friedman Jack
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.)
Individual
Original Assignee
Individual
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 Individual filed Critical Individual
Priority to US16931662 priority Critical patent/US3186869A/en
Priority to US378285A priority patent/US3322674A/en
Application granted granted Critical
Publication of US3186869A publication Critical patent/US3186869A/en
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

Links

Images

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
    • 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
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B65CONVEYING; PACKING; STORING; HANDLING THIN OR FILAMENTARY MATERIAL
    • B65DCONTAINERS FOR STORAGE OR TRANSPORT OF ARTICLES OR MATERIALS, e.g. BAGS, BARRELS, BOTTLES, BOXES, CANS, CARTONS, CRATES, DRUMS, JARS, TANKS, HOPPERS, FORWARDING CONTAINERS; ACCESSORIES, CLOSURES, OR FITTINGS THEREFOR; PACKAGING ELEMENTS; PACKAGES
    • B65D75/00Packages comprising articles or materials partially or wholly enclosed in strips, sheets, blanks, tubes, or webs of flexible sheet material, e.g. in folded wrappers
    • B65D75/26Articles or materials wholly enclosed in laminated sheets or wrapper blanks
    • 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
    • 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
    • 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
    • C11D3/395Bleaching agents
    • C11D3/3955Organic bleaching agents
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10STECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S220/00Receptacles
    • Y10S220/30Biodegradable
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10TTECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00Stock material or miscellaneous articles
    • Y10T428/26Web or sheet containing structurally defined element or component, the element or component having a specified physical dimension
    • Y10T428/263Coating layer not in excess of 5 mils thick or equivalent
    • Y10T428/264Up to 3 mils
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10TTECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00Stock material or miscellaneous articles
    • Y10T428/31504Composite [nonstructural laminate]
    • Y10T428/31801Of wax or waxy material
    • Y10T428/31804Next to cellulosic
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10TTECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00Stock material or miscellaneous articles
    • Y10T428/31504Composite [nonstructural laminate]
    • Y10T428/31971Of carbohydrate

Definitions

  • the present invention is a continuation-in-part of application Serial No. 90,959, filed February 23, 1961, entitled Laundry Package, now abandoned, and relates to a water soluble package adapted to contain corrosive or volatile compounds. More particularly, the present invention is useful as a water soluble package containing a bleach and, if desired, a detergent or soap, for laundry use.
  • packages have been used for laundry purposes which comprise a water soluble bag containing detergents and a weak bleaching agent. Such bags have particular appeal for home use where a measured amount of bleach and detergent may be thrown into a laundry machine without waste or mess. Such packages are intended to provide the required amount of bleach and in most cases detergent required for a single filling of the machine. Unfortunately, such packages are inefiicient because Weak bleaching agents, such as oxygen containing compounds must be used.
  • Chlorine bleaches will react with every known water soluble film useful for such packaging including, for example, polyvinyl alcohol, methyl cellulose, carboxymethyl cellulose and film derivatives of polyethylene glycol. When a chlorine bleach reacts with this film forming material, it becomes insoluble and loses its disintegrating or dissolving properties. Consequently, if the package is allowed to stand long enough, it will not satisfactorily dissolve when thrown into the laundry water.
  • the present invention overcomes such difiiculties, and provides a package containing a strong bleaching compound, preferably a chlorine containing bleach, which has an indefinite shelf-life, and in which the packages does not react with the bleach.
  • a strong bleaching compound preferably a chlorine containing bleach
  • the present invention also provides a water soluble laundry package adapted to contain detergents and/ or a chlorine bleach, in which the package will readily dissolve in water and in which the package material will not react with the bleach and thereby become insoluble.
  • a further object of the present invention is to provide a coated film material which is particularly useful for containing highly reactive oxidizing agents, such as chlorine containing bleaches without the likelihood of the coated film material reacting with the bleach.
  • FIG. 1 is a plan view of a laundry package embodying the invention.
  • FIG. 2 is a cross sectional view taken along the line 22 of FIG. 1.
  • the laundry package of the present invention may be formed of a thin Walled flexible bag having flexible walls 3 of water soluble film forming material, whose inner surfaces are provided with a Water dispersible barrier coating 2, which is non-rective with the bleach and/ or detergent material 1 contained within the package.
  • the flexible Walls 3 may be heatsealed together about their peripheral margins 4.
  • the wall 3 formed by the film forming material is of bag thickness, preferably from about .001 to approximately .003 of an inch in thickness.
  • a typical bag may have overall dimensions of 2 1" by about 4 /2", with a heatsealed margin i of approximately /3". These figures are examplary and may be varied depending upon the particular use desired.
  • the barrier coating 2 is contiguous with the wall 3 and forms a complete covering for its inner surface. The thickness of the barrier coating 2 is preferably in the range of about .001 to .003 of an inch, but this may be varied depending on the particular use and content of the bag. 7
  • the film forming material may comprise any of a number of water soluble film forming materials which are generally used to package laundry material in water soluble packages.
  • Such film forming materials includes, for example, polyvinyl alcohol, preferably plasticized: methyl cellulose; 21 carboxymethyl cellulose such as sodium carboxymethyl cellulose; sodium carboxymethylhydroxyethyl cellulose; or, a film derivative of polyethylene glycol.
  • Other film forming materials such as set forth in Canadian Patent 510,555, issued March 1, 1955, or comprising high molecular Weight polymeric materials containing water solubilizing groups or hydrophilic groups, such as hydroxyl groups or carboxylic groups may be useful even though they are reactive with strong bleaches and in particular with chlorine, providing they are coated with a barrier as described herein.
  • the barrier coating 2 is preferably formed of a Wax or oleaginous substance, for example, a wax selected from the group consisting of hydrocarbon, microcrystalline, animal and vegetable Waxes, saponified fatty acids, saponified fatty acid esters, condensation products of ethylene oxide, esters and mixtures of these and similar substances.
  • the material forming the barrier coating should melt between room temperature of approximately 68 F. and the boiling point of water, 212 F. and preferably should melt in hot water in a melting temperature range preferably of about F. to about F., but this depends upon the specific nature of the coating material.
  • This barrier coating material should be water dispersible. it functions to seal the inner surface of the walls 3 from contact with the bleach material.
  • the barrier material which preferably comprises paraffin is itself not water soluble, it should preferably have incorporated or homogeneously dispersed throughout, a dispersing agent which will, upon wetting of the bag, cause the barrier material to disperse in colloidal form. Since the barrier material does not have structural strength, it Will readily break up when the film forming material dissolves in water. The barrier material will thereupon disperse in the water in colloidal form, releasing the contents of the package into the Water.
  • This Wax or oleaginous substance comprises the major portion of the barrier coating and preferably constitutes up to approximately 85 by weight of the coating.
  • an emulsifier Preferably mixed with the wax or oleaginous substance is an emulsifier, a film forming material, and/ or a softener.
  • the function of the emulsifier is to assure a suitable colloidal dispersion of the barrier coating when the bag is immersed in water so that the barrier coating material will not interfere with the washing process.
  • a film forming material is incorporated into the barrier coating. This film forming material is intended to assure a uniform and consistent barrier coating which is not likely to break or crack during application or stor-- age. It is also useful to incorporate a softener into the barrier coating, for purposes of assuring flexibility of the barrier coating so that it will not crack or otherwise become defective during handling or storage of the laundry package. Certain materials may have a dual function as such an emulsifier, film forming material or softener.
  • Suitable emulsifiers comprise, for example, various nonionic surface active agents such as, glycerol monostearate.
  • Other synthetic emulsifiers include salts of fatty acids, as for example, salts of oleic or stearic acids.
  • Triethanclamine has also been found to be a suitable emulsifier. These compounds may also be used in various combinations with one another for specific desired effects.
  • the emulsifier may preferably comprise up to approximately 20% by weight of the barrier coating.
  • Glycerol monostearate has also been found suitable as a film forming material and may preferably constitute up to approximately 20% of the total weight of the barrier coating.
  • nonionic emulsifiers or surface active agents may be used and substituted as emulsifiers.
  • materials include materials referred to on page 970 of Merck Index, 7th Edition, copyright 1960 under the definition of Span and Tween.
  • Ionic surface active agents as for example, salt of fatty acids, such as the reaction product of oleic and/ or stearic acid with triethanolamine and/or morpholine may be used.
  • Such substitutes may be used in the same range as glycerol monostearate.
  • Suitable softening agents include for example, lanolin and petroleum jelly.
  • Other softening agents may be used in place of petroleum jelly or lanolin, provided they are chemically inert with respect to the chlorine or other bleaches and detergents contained within the package, and provided they are chemically compatible with the paraffin.
  • Such a softener may comprise up to approximately 25% by weight of the barrier coating.
  • the materials referred to above may perform multiple functions.
  • glycerol monostearate may function both as an emulsifier and a film forming material
  • lanolin may function both as an emulsifier and as a softener.
  • This multiple utility permits a wide range of compositions in the barrier coating.
  • any of the materials used in the barrier coating must be chemically inert with respect to the material contained within the package, and other materials normally encountered in washing.
  • the materials of the barrier coating must be emulsifiable on dissolution of the supporting film and must be flexible or capable of being made flexible in film form.
  • composition comprising the barrier coating may comprise merely the wax or oleaginous material.
  • this composition is not as satisfactory as a composition containing the emulsifier, fllm forming material, and/ or the softener for reasons set forth above.
  • the barrier coating material should comprise a homogeneous mixture of the materials referred to and may be applied to the flexible walls 3 at a temperature just above melting point of the barrier coating material.
  • the coating operation may be performed in any suitable manner, as for example, by roller coating, or spraying.
  • the thickness of the barrier coating will depend upon the method and temperature used.' A preferred coating temperature is within the range of 130 F. to approximately 160 F. This again will depend upon the specific composition of the barrier coating material.
  • the contents ofthe package preferably comprise in combination, a synthetic detergent and a chlorine containing bleaching agent.
  • a synthetic detergent and a chlorine containing bleaching agent preferably comprise in combination, a synthetic detergent and a chlorine containing bleaching agent.
  • an alkaline source preferably a washing aid, a stabilizing water softener sequestering agent, a soil suspending agent and an optical bleach.
  • the synthetic detergent and chlorine conatining bleaching agent are com,-
  • Suitable detergents include for example, alkali metal salts, ammonium salts and ethanolamine salts of 7 will of course, function only as a bleaching agent.
  • the contents which includes the detergents and chlorine con- 7 in dry form and packaged within the packaging material.
  • sulfonated higher alkyl mononuclear aryl hydrocarbons having from 9 to 18 carbon atoms, for example, sodium dodecylbenzene sulfonate, alkali metal salts of fatty acids such as sodium oleate and sodium palmitate.
  • Other synthetic detergents commercially available may also be used.
  • Thebleach should be a strong oxidizing agent and preferably comprises a chlorine containing bleaching chemical.
  • This bleach must be solid at room temperature and must decompose water to release the bleaching agent, preferably chlorine.
  • Suitable chlorine donor materials may comprise, for example, dichloroisocyanuric acid and tricmoroisocyanuric acid. Other chlorine releasing agents,
  • lithium hypochlorite and calcium hypochlorite such as lithium hypochlorite and calcium hypochlorite
  • a source of alkalinity may be provided from a compound selected from a group consisting of anhydrous sodiurn metasilicate, anhydrous potassium metasilicate, various metal phosphates or polyphosphates, such as sodium or potassium phosphates, or trisodium phosphate anhydrous may be useful.
  • sodium carbonate may also be used as an alkaline source.
  • the alkaline source is optional and is useful primarily as an aid in the washing process. It has been found that soaps or detergents, ionize better in alkaline media. This alkaline source also functions to aid in stabilizing a chlorine containing material in the combination.
  • a suitable washing aid such as anhydrous tripolyphosphate may also if desired, be included in the composition. This washing aid functions to keep complex heavy metal ions from precipitating when the package is dissolved in water.
  • a similar function is performed by the stabilizing water softener sequestering agent.
  • Such agents may include for example, sodium tetraethylenediamine tetra-- acetic acid.
  • a soil suspending agent as for example, carboxymethyl cellulose may also be incorporated into the composition, together with an optical bleach such as products marketed under the names Calcofluor and Tinopal.
  • the soil suspending agent and the optical bleach are conventional in washing compounds and their use is not critical. If desired various inert fillers such as sodium sulphate may also be used.
  • the detergent preferably comprises from about 10% to about 20% by weight of the total mixture
  • the alkalinity imparting compound preferably comprises up to about 25 to 35% by weight of the total mixture; the chlorine donor material comprises by weight at least 5% of the total mixture; the washing aid is employed in amounts up to about 25% to about 35% by weight of the total mixture; the stabilizing sequestering agent is used in amounts up to about .10% to about 2.5% by Weight of the total mixture; the soil suspending agent may be used in amounts up to about .5% to 1%, and the optical bleach maybe used in amounts of up to about .2% to .5 Each of these amounts are weights of the total composition.
  • the package may consist in one embodiment, of the packaging material and a chlorine containing bleaching chemical alone.
  • This composition taining chemical in the preferred embodiment are mixed
  • the constituents are weighed out, dried, and put through a sieve in a mixer, for example a Day-Type.
  • the ingredients are thus mixed together thoroughly, forming a uniform dry powder.
  • T his procedure is carried out in a dry room having for example, less than 50% humidity at room temperature. The exact temperature and humidity is not critical.
  • the mixed composition is then fed to a hopper in the packaging machine which makes the packages and then fills and seals them in a conventional manner.
  • packages which are formed of the coated film material previously described, are water soluble and consequently dissolve readily when the package is placed in Water. When the package disintegrates there is no deposit left on the wash.
  • Example 1 The supporting film is formed Of polyvinyl alcohol having a thickness of two mils.
  • ing film composition is a mixture of glycerol monostearate, oleic acid and triethanolamine.
  • the preferred concentration of the glycerol monostearate is 85%, the oleic acid 5% and the triethanolamine
  • the permissible range of glycerol monostearate may vary from about to about 85%, the oleic acid, 3% to 10% and the triethanolamine from 1% to 10% by weight of the total composition.
  • the glycerol monostearate presumably functions in this example primarily as a film forming material.
  • the oleic acid and the triethanolamine in combination form an emulsifier (oleic acid triethyl ammonium salt).
  • Other surface active agents, nonionic or ionic may be substituted for the oleic acid and triethanolamine.
  • the composition may include lanolin or petroleum jelly or other softeners to give greater flexibility to the film. If included, such softeners should not exceed about of the total composition by weight.
  • the composition is mixed preferably at -a temperature of 130 F., but a range of 130 F. to 140 F. is satisfactory.
  • the coating material was applied to the supporting film by passing the film over rollers running in a bath of melt at a temperature of about 140 F., with a range of 150 F. to 180 F. being permissible, so that a film having a thickness of approximately .002" is applied to the supporting film.
  • the barrier coating solidifies almost immediately.
  • Supporting film carrying the barrier coating may be led to a package forming and filling machine, and packages are made continuously having dimensions of approximately 2%" in width and about 4 /2" in length, with a heat sealed margin of about
  • the washing compound which fills the bags may contain a combination of a detergent in the range of 10% to 20%, an alkaline source in the range of 25 to a chlorine donating chemical of at least 5%, a washing aid in the range of 25% to 35% and a stabilizing water softener sequestering agent in the range of .l% to .25 all by weight. These materials forming the washing compound are selected from one of the aforementioned compounds.
  • Example 2.-A package made in accordance with Example 1 was thrown into a washing machine containing water at a temperature of 130 F.
  • the supporting and barrier films of the bag dissolved quickly and released the contents into the wash water.
  • Example 3 A preferred coating material is made up from the following constituents, the percentages being the weight of the total composition.
  • coating made in accordance with the present invention also effectively prevent deterioration of bags containing detergents or other Washing compounds alone, which in the absence of the coating described, would deteriorate the bag over a period of time.
  • a film comprising a continuous base film of a watersoluble synthetic organic film-forming material normally reactive with chemical bleaching and washing agents provided with a thin continuous barrier coating capable of being emulsified and having a water-dispersible waxy maerial containing an emulsifier, said waxy material being non-reactive with such agents,
  • said barrier coating adapted to prevent the reaction of the agents with the substance of the supporting film, said emulsifier being present in sufiicient quantity to act as a dispersing agent for said waxy material,
  • the composite film being adapted to disperse in water at a temperature in the range of from 68 F. to 212 F.
  • said water soluble film-forming material is selected from the group consisting of polyvinyl alcohol, methyl cellulose, carboxymethyl cellulose and a water soluble film forming derivative of polyethylene glycol.
  • barrier coating comprises in approximate percentages by weight:
  • a film in accordance with the film of claim 1 wherein said barrier coating comprises in percentage by weight from about 20 to 85% glycerol monostearate, about 3- 10% oleic acid and about 110% triethanolamine.
  • barrier coating contains a film forming material and a softener for said barrier coating.
  • said waxy material is selected from the group consisting of hydrocarbon Waxes, microcrystalline waxes, animal waxes, vegetable waxes, saponified fatty acids, saponified fatty acid esters and condensation products of ethylene oxide.
  • a composite film comprising a continuous base supporting film of a water-soluble synthetic organic filmforming material normally reactive with chemical bleaching and washing agents provided with a thin continuous barrier coating capable of being emulsified and having a water dispersible waxy material containing an emulsifier,
  • waxy material being non-reactive with such agents
  • said barrier coating adapted to prevent the reaction of the agents with the substance of the supporting film
  • said emulsifier being present in sufiicient quantity to act as a dispersing agent for said waxy material
  • said barrier coating having a thickness of from between approximately 1 to 3 mils
  • the composite film being adapted to disperse in Water at a temperature in the range of from 68 F. to 212 F.

Description

June 1, 1965 J. FRIEDMAN COATED FILM FOR LAUNDRY PACKAGE Filed Jan. 29, 1962 FIG.2
INVENT OR.
ATTORN ES 3,186,869 CQATED FETJM FQR LAUNDRY PACKAGE lack Friedman, 250 Kensington Ave, iontreal, Quebec, Canada Filed ran. 29, 1962, S61. No. 169,316 19 Claims. (Cl. 117--138.8)
The present invention is a continuation-in-part of application Serial No. 90,959, filed February 23, 1961, entitled Laundry Package, now abandoned, and relates to a water soluble package adapted to contain corrosive or volatile compounds. More particularly, the present invention is useful as a water soluble package containing a bleach and, if desired, a detergent or soap, for laundry use.
Heretofore, packages have been used for laundry purposes which comprise a water soluble bag containing detergents and a weak bleaching agent. Such bags have particular appeal for home use where a measured amount of bleach and detergent may be thrown into a laundry machine without waste or mess. Such packages are intended to provide the required amount of bleach and in most cases detergent required for a single filling of the machine. Unfortunately, such packages are inefiicient because Weak bleaching agents, such as oxygen containing compounds must be used.
Some attempts have been made to improve these laundry packages by using stronger bleaches, and in particular by using chlorine bleaches. However, these stronger bleaches and in particular chlorine bleaches, react with the material which has heretofore been used to form the walls of the package. Chlorine bleaches will react with every known water soluble film useful for such packaging including, for example, polyvinyl alcohol, methyl cellulose, carboxymethyl cellulose and film derivatives of polyethylene glycol. When a chlorine bleach reacts with this film forming material, it becomes insoluble and loses its disintegrating or dissolving properties. Consequently, if the package is allowed to stand long enough, it will not satisfactorily dissolve when thrown into the laundry water.
The present invention overcomes such difiiculties, and provides a package containing a strong bleaching compound, preferably a chlorine containing bleach, which has an indefinite shelf-life, and in which the packages does not react with the bleach. The present invention also provides a water soluble laundry package adapted to contain detergents and/ or a chlorine bleach, in which the package will readily dissolve in water and in which the package material will not react with the bleach and thereby become insoluble.
A further object of the present invention is to provide a coated film material which is particularly useful for containing highly reactive oxidizing agents, such as chlorine containing bleaches without the likelihood of the coated film material reacting with the bleach.
These and other objects and advantages of the present invention will be more clearly understood when considered in conjunction with the accompanying drawings, in which:
FIG. 1 is a plan view of a laundry package embodying the invention, and
FIG. 2 is a cross sectional view taken along the line 22 of FIG. 1.
As illustrated in the drawing, the laundry package of the present invention may be formed of a thin Walled flexible bag having flexible walls 3 of water soluble film forming material, whose inner surfaces are provided with a Water dispersible barrier coating 2, which is non-rective with the bleach and/ or detergent material 1 contained Within the package. The flexible Walls 3 may be heatsealed together about their peripheral margins 4.
3,l8fi,8fi0 Patented June 1, 1965 The wall 3 formed by the film forming material is of bag thickness, preferably from about .001 to approximately .003 of an inch in thickness. A typical bag may have overall dimensions of 2 1" by about 4 /2", with a heatsealed margin i of approximately /3". These figures are examplary and may be varied depending upon the particular use desired. The barrier coating 2 is contiguous with the wall 3 and forms a complete covering for its inner surface. The thickness of the barrier coating 2 is preferably in the range of about .001 to .003 of an inch, but this may be varied depending on the particular use and content of the bag. 7
The film forming material may comprise any of a number of water soluble film forming materials which are generally used to package laundry material in water soluble packages. Such film forming materials includes, for example, polyvinyl alcohol, preferably plasticized: methyl cellulose; 21 carboxymethyl cellulose such as sodium carboxymethyl cellulose; sodium carboxymethylhydroxyethyl cellulose; or, a film derivative of polyethylene glycol. Other film forming materials such as set forth in Canadian Patent 510,555, issued March 1, 1955, or comprising high molecular Weight polymeric materials containing water solubilizing groups or hydrophilic groups, such as hydroxyl groups or carboxylic groups may be useful even though they are reactive with strong bleaches and in particular with chlorine, providing they are coated with a barrier as described herein.
The barrier coating 2 is preferably formed of a Wax or oleaginous substance, for example, a wax selected from the group consisting of hydrocarbon, microcrystalline, animal and vegetable Waxes, saponified fatty acids, saponified fatty acid esters, condensation products of ethylene oxide, esters and mixtures of these and similar substances. The material forming the barrier coating should melt between room temperature of approximately 68 F. and the boiling point of water, 212 F. and preferably should melt in hot water in a melting temperature range preferably of about F. to about F., but this depends upon the specific nature of the coating material. This barrier coating material should be water dispersible. it functions to seal the inner surface of the walls 3 from contact with the bleach material. Since the barrier material which preferably comprises paraffin is itself not water soluble, it should preferably have incorporated or homogeneously dispersed throughout, a dispersing agent which will, upon wetting of the bag, cause the barrier material to disperse in colloidal form. Since the barrier material does not have structural strength, it Will readily break up when the film forming material dissolves in water. The barrier material will thereupon disperse in the water in colloidal form, releasing the contents of the package into the Water. This Wax or oleaginous substance comprises the major portion of the barrier coating and preferably constitutes up to approximately 85 by weight of the coating.
Preferably mixed with the wax or oleaginous substance is an emulsifier, a film forming material, and/ or a softener. The function of the emulsifier is to assure a suitable colloidal dispersion of the barrier coating when the bag is immersed in water so that the barrier coating material will not interfere with the washing process. Preferably a film forming material is incorporated into the barrier coating. This film forming material is intended to assure a uniform and consistent barrier coating which is not likely to break or crack during application or stor-- age. It is also useful to incorporate a softener into the barrier coating, for purposes of assuring flexibility of the barrier coating so that it will not crack or otherwise become defective during handling or storage of the laundry package. Certain materials may have a dual function as such an emulsifier, film forming material or softener.
Suitable emulsifiers comprise, for example, various nonionic surface active agents such as, glycerol monostearate. Other synthetic emulsifiers include salts of fatty acids, as for example, salts of oleic or stearic acids. Triethanclamine has also been found to be a suitable emulsifier. These compounds may also be used in various combinations with one another for specific desired effects. The emulsifier may preferably comprise up to approximately 20% by weight of the barrier coating.
Glycerol monostearate has also been found suitable as a film forming material and may preferably constitute up to approximately 20% of the total weight of the barrier coating.
In place of glycerol monostearate, other nonionic emulsifiers or surface active agents may be used and substituted as emulsifiers. Such materials include materials referred to on page 970 of Merck Index, 7th Edition, copyright 1960 under the definition of Span and Tween. Ionic surface active agents, as for example, salt of fatty acids, such as the reaction product of oleic and/ or stearic acid with triethanolamine and/or morpholine may be used. Such substitutes may be used in the same range as glycerol monostearate.
Suitable softening agents include for example, lanolin and petroleum jelly. Other softening agents may be used in place of petroleum jelly or lanolin, provided they are chemically inert with respect to the chlorine or other bleaches and detergents contained within the package, and provided they are chemically compatible with the paraffin. Such a softener may comprise up to approximately 25% by weight of the barrier coating.
The materials referred to above may perform multiple functions. For example, as indicated, glycerol monostearate may function both as an emulsifier and a film forming material, while lanolin may function both as an emulsifier and as a softener. This multiple utility permits a wide range of compositions in the barrier coating. However, any of the materials used in the barrier coating must be chemically inert with respect to the material contained within the package, and other materials normally encountered in washing. The materials of the barrier coating must be emulsifiable on dissolution of the supporting film and must be flexible or capable of being made flexible in film form.
The composition comprising the barrier coating may comprise merely the wax or oleaginous material. However this composition is not as satisfactory as a composition containing the emulsifier, fllm forming material, and/ or the softener for reasons set forth above.
The barrier coating material should comprise a homogeneous mixture of the materials referred to and may be applied to the flexible walls 3 at a temperature just above melting point of the barrier coating material. The coating operation may be performed in any suitable manner, as for example, by roller coating, or spraying. The thickness of the barrier coating will depend upon the method and temperature used.' A preferred coating temperature is within the range of 130 F. to approximately 160 F. This again will depend upon the specific composition of the barrier coating material.
The contents ofthe package, preferably comprise in combination, a synthetic detergent and a chlorine containing bleaching agent. In addition, it has been found useful to include an alkaline source, a washing aid, a stabilizing water softener sequestering agent, a soil suspending agent and an optical bleach. The synthetic detergent and chlorine conatining bleaching agent are com,-
bined in such a manner as not to decompose when mixed act with chlorine or chlorine releasing agents. Since chlorine is a strong oxidizing agent, detergents that are oxidizable or strong reducing agents should not be used.
Various suitable detergents include for example, alkali metal salts, ammonium salts and ethanolamine salts of 7 will of course, function only as a bleaching agent. The contents, which includes the detergents and chlorine con- 7 in dry form and packaged within the packaging material.
sulfonated higher alkyl mononuclear aryl hydrocarbons, having from 9 to 18 carbon atoms, for example, sodium dodecylbenzene sulfonate, alkali metal salts of fatty acids such as sodium oleate and sodium palmitate. Other synthetic detergents commercially available may also be used.
Thebleach should be a strong oxidizing agent and preferably comprises a chlorine containing bleaching chemical. This bleach must be solid at room temperature and must decompose water to release the bleaching agent, preferably chlorine. Suitable chlorine donor materials may comprise, for example, dichloroisocyanuric acid and tricmoroisocyanuric acid. Other chlorine releasing agents,
such as lithium hypochlorite and calcium hypochlorite, as
referred to in British Patent No. 606,431, issued to William H. Langdwell, August 13, 1948, are also useful.
A source of alkalinity may be provided from a compound selected from a group consisting of anhydrous sodiurn metasilicate, anhydrous potassium metasilicate, various metal phosphates or polyphosphates, such as sodium or potassium phosphates, or trisodium phosphate anhydrous may be useful. In addition to various other polyphosphates of sodium or potassium, sodium carbonate may also be used as an alkaline source. The alkaline source is optional and is useful primarily as an aid in the washing process. It has been found that soaps or detergents, ionize better in alkaline media. This alkaline source also functions to aid in stabilizing a chlorine containing material in the combination. A suitable washing aid such as anhydrous tripolyphosphate may also if desired, be included in the composition. This washing aid functions to keep complex heavy metal ions from precipitating when the package is dissolved in water.
A similar function is performed by the stabilizing water softener sequestering agent. Such agents may include for example, sodium tetraethylenediamine tetra-- acetic acid. A soil suspending agent, as for example, carboxymethyl cellulose may also be incorporated into the composition, together with an optical bleach such as products marketed under the names Calcofluor and Tinopal. The soil suspending agent and the optical bleach are conventional in washing compounds and their use is not critical. If desired various inert fillers such as sodium sulphate may also be used.
If present, the detergent preferably comprises from about 10% to about 20% by weight of the total mixture;
the alkalinity imparting compound preferably comprises up to about 25 to 35% by weight of the total mixture; the chlorine donor material comprises by weight at least 5% of the total mixture; the washing aid is employed in amounts up to about 25% to about 35% by weight of the total mixture; the stabilizing sequestering agent is used in amounts up to about .10% to about 2.5% by Weight of the total mixture; the soil suspending agent may be used in amounts up to about .5% to 1%, and the optical bleach maybe used in amounts of up to about .2% to .5 Each of these amounts are weights of the total composition.
While the foregoing percentages suggest a preferred range for a combination composition of a detergent and chlorine containing chemical, the package may consist in one embodiment, of the packaging material and a chlorine containing bleaching chemical alone. This composition taining chemical in the preferred embodiment, are mixed In preparing the composition, which includes the detergent and chlorine containing chemical, the constituents are weighed out, dried, and put through a sieve in a mixer, for example a Day-Type. The ingredients are thus mixed together thoroughly, forming a uniform dry powder. There is no mixing problem. T his procedure is carried out in a dry room having for example, less than 50% humidity at room temperature. The exact temperature and humidity is not critical. The mixed composition is then fed to a hopper in the packaging machine which makes the packages and then fills and seals them in a conventional manner. These packages, which are formed of the coated film material previously described, are water soluble and consequently dissolve readily when the package is placed in Water. When the package disintegrates there is no deposit left on the wash.
Various examples will more fully describe the scope of the present invention.
Example 1.The supporting film is formed Of polyvinyl alcohol having a thickness of two mils. ing film composition is a mixture of glycerol monostearate, oleic acid and triethanolamine. The preferred concentration of the glycerol monostearate is 85%, the oleic acid 5% and the triethanolamine However, the permissible range of glycerol monostearate may vary from about to about 85%, the oleic acid, 3% to 10% and the triethanolamine from 1% to 10% by weight of the total composition.
The glycerol monostearate presumably functions in this example primarily as a film forming material. The oleic acid and the triethanolamine in combination form an emulsifier (oleic acid triethyl ammonium salt). Other surface active agents, nonionic or ionic may be substituted for the oleic acid and triethanolamine. If desired, the composition may include lanolin or petroleum jelly or other softeners to give greater flexibility to the film. If included, such softeners should not exceed about of the total composition by weight. The composition is mixed preferably at -a temperature of 130 F., but a range of 130 F. to 140 F. is satisfactory. The coating material was applied to the supporting film by passing the film over rollers running in a bath of melt at a temperature of about 140 F., with a range of 150 F. to 180 F. being permissible, so that a film having a thickness of approximately .002" is applied to the supporting film. The barrier coating solidifies almost immediately. Supporting film carrying the barrier coating may be led to a package forming and filling machine, and packages are made continuously having dimensions of approximately 2%" in width and about 4 /2" in length, with a heat sealed margin of about The washing compound which fills the bags may contain a combination of a detergent in the range of 10% to 20%, an alkaline source in the range of 25 to a chlorine donating chemical of at least 5%, a washing aid in the range of 25% to 35% and a stabilizing water softener sequestering agent in the range of .l% to .25 all by weight. These materials forming the washing compound are selected from one of the aforementioned compounds.
Example 2.-A package made in accordance with Example 1 was thrown into a washing machine containing water at a temperature of 130 F. The supporting and barrier films of the bag dissolved quickly and released the contents into the wash water.
Example 3.A preferred coating material is made up from the following constituents, the percentages being the weight of the total composition.
Percent Glyceryl monostearate 10 Lanolin 2 Parafiin 65 Petroleum jelly 23 The coat-v form a homogeneous molten mass. A polyvinyl alcohol film was coated with this mass at 160 F. Bags were made from the coated film and filled with detergents and chlorine containing bleach. The bags were tested as described in the previous examples. It was found that the coating material effectively prevented reaction between the chlorine of the washing compound and the polyvinyl alcohol, and that the bags dissolved freely when thrown into the water of a washing machine.
In addition, it has been found that coating made in accordance with the present invention also effectively prevent deterioration of bags containing detergents or other Washing compounds alone, which in the absence of the coating described, would deteriorate the bag over a period of time.
What is claimed is:
1. A film comprising a continuous base film of a watersoluble synthetic organic film-forming material normally reactive with chemical bleaching and washing agents provided with a thin continuous barrier coating capable of being emulsified and having a water-dispersible waxy maerial containing an emulsifier, said waxy material being non-reactive with such agents,
said barrier coating adapted to prevent the reaction of the agents with the substance of the supporting film, said emulsifier being present in sufiicient quantity to act as a dispersing agent for said waxy material,
the composite film being adapted to disperse in water at a temperature in the range of from 68 F. to 212 F.
2. A film in accordance with the film of claim 1 Wherein said water soluble film-forming material is selected from the group consisting of polyvinyl alcohol, methyl cellulose, carboxymethyl cellulose and a water soluble film forming derivative of polyethylene glycol.
3. A film in accordance with the film of claim 1 wherein said barrier coating melts at a temperature in the range of about F. to F.
4. A film in accordance with claim 1 wherein said barrier coating comprises in approximate percentages by weight:
5. A film in accordance with the film of claim 1 wherein said barrier coating comprises in percentage by weight from about 20 to 85% glycerol monostearate, about 3- 10% oleic acid and about 110% triethanolamine.
6. A film in accordance with claim 1 wherein said barrier coating contains a film forming material.
7. A film in accordance with claim 1 wherein said barrier coating contains a film forming material and a softener for said barrier coating.
8. A film in accordance with the film of claim 7 wherein said waxy material is selected from the group consisting of hydrocarbon Waxes, microcrystalline waxes, animal waxes, vegetable waxes, saponified fatty acids, saponified fatty acid esters and condensation products of ethylene oxide.
9. A film in accordance with the film of claim 7 wherein said waxy material is parafiin.
10. A composite film comprising a continuous base supporting film of a water-soluble synthetic organic filmforming material normally reactive with chemical bleaching and washing agents provided with a thin continuous barrier coating capable of being emulsified and having a water dispersible waxy material containing an emulsifier,
said waxy material being non-reactive with such agents,
said barrier coating adapted to prevent the reaction of the agents with the substance of the supporting film,
said emulsifier being present in sufiicient quantity to act as a dispersing agent for said waxy material,
said barrier coating having a thickness of from between approximately 1 to 3 mils,
the composite film being adapted to disperse in Water at a temperature in the range of from 68 F. to 212 F.
References Cited by the Examiner UNITED STATES PATENTS 2,436,433 2/48 Jebens. V 2,495,283 1/50 Werntz 117168 XR 2,655,480 10/53 Spitzer et a1 252--90 2,636,008 4/53 Iurgensen et a1. 25293 2,778,748 1/57 Rowe et 211.
2,841,572 7/58 McMahon 252-90 XR 8 2,995,521 8/61 Estignard-Bluard 252-90 3,079,640 3/63 Kawai et a1.
FOREIGN PATENTS 5 510,555 1/55 Canada.
550,865 12/57 Canada. 7
20,116 1889 Great Britain.
OTHER REFERENCES Elvanol (Polyvinyl' Alcohols), issued by E. I. du Pont de-Nernours and Co., Inc., 1947, p. 17. 7
WILLIAM D. MARTIN, Primary Examiner.
J. FREEMULD, RICHARD D. NEVIUS, Examiners.

Claims (1)

1. A FILM COMPRISING A CONTINUOUS BASE FILM OF A WATERSOLUBLE SYNTHETIC ORGANIC FILM-FORMING MATERIAL NORMALLY REACTIVE WITH CHEMICAL BLEACHING AND WASHING AGENTS PROVIDED WITH A THIN CONTINUOUS BARRIER COATING CAPABLE OF BEING EMULSIFIED AND HAVING A WATER-DISPERSIBLE WAXY MAERIAL CONTAINING AN EMULSIFIER, SAID WAXY MATERIAL BEING NON-REACTIVE WITH SUCH AGENTS. SAID BARRIER COATING ADAPTED TO PREVENT THE REACTION OF THE AGENTS WITH THE SUBSTANCE OF THE SUPPORTING FILM, SAID EMULSIFIER BEING PRESENT IN SUFFICIENT QUANTITY TO ACT AS A DISPERSING AGENT FOR SAID WAXY MATERIAL, THE COMPOSITE FILM BEING ADAPTED TO DISPERSE IN WATER AT A TEMPERATURE IN THE RANGE OF FROM 68*F. TO 212*F.
US16931662 1961-02-23 1962-01-29 Coated film for laundry package Expired - Lifetime US3186869A (en)

Priority Applications (2)

Application Number Priority Date Filing Date Title
US16931662 US3186869A (en) 1961-02-23 1962-01-29 Coated film for laundry package
US378285A US3322674A (en) 1961-02-23 1964-06-26 Laundry package

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US9095961A 1961-02-23 1961-02-23
US16931662 US3186869A (en) 1961-02-23 1962-01-29 Coated film for laundry package

Publications (1)

Publication Number Publication Date
US3186869A true US3186869A (en) 1965-06-01

Family

ID=26782822

Family Applications (1)

Application Number Title Priority Date Filing Date
US16931662 Expired - Lifetime US3186869A (en) 1961-02-23 1962-01-29 Coated film for laundry package

Country Status (1)

Country Link
US (1) US3186869A (en)

Cited By (54)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3294224A (en) * 1964-11-04 1966-12-27 Horwitz Harold Package of powdered ingredients for water-base paint
US3360470A (en) * 1963-05-28 1967-12-26 Colgate Palmolive Co Laundering compositions
US3415402A (en) * 1966-08-15 1968-12-10 Webber Robert Louis Container
US3528921A (en) * 1966-07-08 1970-09-15 Colgate Palmolive Co Bleaching packets
US3653958A (en) * 1969-03-25 1972-04-04 Sun Oil Co Method of decreasing wax impregnation time by porous paper products
US3705659A (en) * 1970-09-18 1972-12-12 William L Mackie Erodable material
US3784005A (en) * 1971-12-20 1974-01-08 Us Chem Plastics Inc Additive package and method of compounding resins therewith
US3785479A (en) * 1970-12-04 1974-01-15 D Smith Plaster of paris bandages to make casts of improved strength, water-resistance and physiological properties
US3877928A (en) * 1967-08-08 1975-04-15 Walter A Houston Liquid soluble packet
US3892905A (en) * 1970-08-12 1975-07-01 Du Pont Cold water soluble plastic films
US3902596A (en) * 1970-02-10 1975-09-02 U S Chemicals And Plastics Inc Additive package for compounding resins
EP0079248A2 (en) 1981-11-11 1983-05-18 Unilever N.V. Packaging film and packaging of detergent compositions therewith
EP0132726A2 (en) * 1983-07-21 1985-02-13 Henkel Kommanditgesellschaft auf Aktien Package for a washing, rinsing or cleaning product
WO1985004107A1 (en) * 1984-03-21 1985-09-26 Alcide Corporation Disinfection method and composition therefor
US4558781A (en) * 1980-07-23 1985-12-17 Societe Anonyme D'explosifs Et De Produits Chimiques Cartridge for use in anchor bolting
US4762738A (en) * 1986-12-22 1988-08-09 E. R. Squibb & Sons, Inc. Means for disposal of articles by flushing and ostomy pouches particularly suited for such disposal
US4776455A (en) * 1986-03-07 1988-10-11 Lever Brothers Company Compartmented product for dispensing treatment agents in a washing or dishwashing machine
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
US4830187A (en) * 1986-12-22 1989-05-16 E. R. Squibb & Sons, Inc. Means for disposal of articles by flushing and ostomy pouches particularly suited for such disposal
EP0337568A2 (en) * 1988-04-11 1989-10-18 Colgate-Palmolive Company Detersive article
EP0366231A1 (en) * 1988-09-26 1990-05-02 Zimpro Environmental, Inc. Sealed PVA package with activated carbon and its use in waste water treatment
US4930942A (en) * 1986-12-22 1990-06-05 E. R. Squibb & Sons, Inc. Method of disposal of articles by flushing
US4970008A (en) * 1988-12-20 1990-11-13 Kandathil Thomas V Fabric conditioner comprising a mixture of quaternary ammonium compounds and select tertiary amines
US4986990A (en) * 1984-03-21 1991-01-22 Alcide Corporation Disinfection method and composition therefor
WO1992001037A1 (en) * 1990-07-03 1992-01-23 Ecolab Inc. Detersive system containing water soluble film article
US5100652A (en) * 1984-03-21 1992-03-31 Alcide Corporation Disinfecting oral hygiene compositions and process for using the same
US5160654A (en) * 1989-08-23 1992-11-03 Lever Brothers Company, Division Of Conopco, Inc. Laundry treatment product
US5185161A (en) * 1984-03-21 1993-02-09 Alcide Corporation Disinfection method and composition therefor
US5362413A (en) * 1984-03-23 1994-11-08 The Clorox Company Low-temperature-effective detergent compositions and delivery systems therefor
US6037319A (en) * 1997-04-01 2000-03-14 Dickler Chemical Laboratories, Inc. Water-soluble packets containing liquid cleaning concentrates
US6057015A (en) * 1997-09-02 2000-05-02 Burlington Bio-Medical And Scientific Corporation Containers and methods for waste recycling
US6136776A (en) * 1997-04-01 2000-10-24 Dickler Chemical Laboratories, Inc. Germicidal detergent packet
WO2001007560A1 (en) * 1999-07-21 2001-02-01 Henkel Kommanditgesellschaft Auf Aktien Washing or cleansing product portion and packaging for same
US6204223B1 (en) 1996-01-30 2001-03-20 Zeneca Limited Packaged agrochemical composition
WO2001040432A1 (en) * 1999-12-01 2001-06-07 Henkel Kommanditgesellschaft Auf Aktien Packaged portions of detergent
US20020161088A1 (en) * 2001-01-31 2002-10-31 Kochvar Kelly Ann Rapidly dissolvable polymer films and articles made therefrom
US6509072B2 (en) * 1999-04-27 2003-01-21 P. Scott Bening Multi-layer film with periodic barrier coating and methods of making and using such film
US20040072708A1 (en) * 2001-03-16 2004-04-15 Duffield Paul John Process for producting a water soluble package
US20040144681A1 (en) * 2001-05-17 2004-07-29 Ralf Wiedemann Water-soluble containers with gas release means
US20040189868A1 (en) * 2003-03-24 2004-09-30 Sony Corporation And Sony Electronics Inc. Position and time sensitive closed captioning
US6958313B2 (en) 2000-05-11 2005-10-25 The Procter & Gamble Company Highly concentrated fabric softener compositions and articles containing such compositions
US20060172910A1 (en) * 2005-01-10 2006-08-03 The Procter & Gamble Company Machine cleaner
US20060260973A1 (en) * 2003-06-20 2006-11-23 Plantic Technologies Ltd. Easy open water soluble blister package
US7325688B1 (en) * 2003-09-26 2008-02-05 Gowan Milling Company, L.L.C. Pressurized water-soluble pouch
US20080234169A1 (en) * 2007-03-20 2008-09-25 Jean Pol Boutique Detergent composition
US20090217462A1 (en) * 2008-02-08 2009-09-03 Holzhauer Fred Consumer product packets with enhanced performance
US20090249562A1 (en) * 2008-04-02 2009-10-08 Mark Robert Sivik Fabric color rejuvenation composition
US20100286630A1 (en) * 2009-05-05 2010-11-11 Watson Laboratories, Inc. Method For Treating Overactive Bladders And A Device For Storage And Administration Of Topical Oxybutynin Compositions
US7915209B1 (en) 2007-03-15 2011-03-29 Linda Skaggs Individual liquid-filled soap bar
US7921999B1 (en) 2001-12-20 2011-04-12 Watson Laboratories, Inc. Peelable pouch for transdermal patch and method for packaging
US20130256182A1 (en) * 2010-08-12 2013-10-03 Church & Dwight Co., Inc. Detergent pouch with improved properties
WO2013158364A1 (en) * 2012-04-16 2013-10-24 Monosol, Llc Powdered pouch and method of making same
US10087401B2 (en) 2012-03-16 2018-10-02 Monosol, Llc Water soluble compositions incorporating enzymes, and method of making same
WO2021081475A1 (en) * 2019-10-25 2021-04-29 Monosol, Llc Multilayer water-dispersible articles

Citations (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2436433A (en) * 1943-04-23 1948-02-24 Du Pont Process for coating polyvinyl alcohol film
US2495283A (en) * 1948-05-10 1950-01-24 Du Pont Polymeric polyamine and wax compositions and articles treated therewith
US2636008A (en) * 1949-09-03 1953-04-21 American Mach & Foundry Detergent package and method of making same
US2655480A (en) * 1949-11-02 1953-10-13 Spitzer Lather producing composition
CA510555A (en) * 1955-03-01 C. Miller Robert Detergent compositions
US2778748A (en) * 1952-04-11 1957-01-22 Dictaphone Corp Destaticization of plastic articles
CA550865A (en) * 1957-12-31 J. Vance John Internal barrier for soft gelatin capsules
US2841572A (en) * 1955-12-14 1958-07-01 Wyandotte Chemicals Corp Water-soluble polyesters
US2995521A (en) * 1956-05-24 1961-08-08 Estignard-Bluard Jean Jacques Foam producing compositions
US3079640A (en) * 1958-05-29 1963-03-05 Karashiki Rayon Co Ltd Heat treating polyvinyl alcohol fibers in a molten metal bath

Patent Citations (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CA510555A (en) * 1955-03-01 C. Miller Robert Detergent compositions
CA550865A (en) * 1957-12-31 J. Vance John Internal barrier for soft gelatin capsules
US2436433A (en) * 1943-04-23 1948-02-24 Du Pont Process for coating polyvinyl alcohol film
US2495283A (en) * 1948-05-10 1950-01-24 Du Pont Polymeric polyamine and wax compositions and articles treated therewith
US2636008A (en) * 1949-09-03 1953-04-21 American Mach & Foundry Detergent package and method of making same
US2655480A (en) * 1949-11-02 1953-10-13 Spitzer Lather producing composition
US2778748A (en) * 1952-04-11 1957-01-22 Dictaphone Corp Destaticization of plastic articles
US2841572A (en) * 1955-12-14 1958-07-01 Wyandotte Chemicals Corp Water-soluble polyesters
US2995521A (en) * 1956-05-24 1961-08-08 Estignard-Bluard Jean Jacques Foam producing compositions
US3079640A (en) * 1958-05-29 1963-03-05 Karashiki Rayon Co Ltd Heat treating polyvinyl alcohol fibers in a molten metal bath

Cited By (84)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3360470A (en) * 1963-05-28 1967-12-26 Colgate Palmolive Co Laundering compositions
US3294224A (en) * 1964-11-04 1966-12-27 Horwitz Harold Package of powdered ingredients for water-base paint
US3528921A (en) * 1966-07-08 1970-09-15 Colgate Palmolive Co Bleaching packets
US3415402A (en) * 1966-08-15 1968-12-10 Webber Robert Louis Container
US3877928A (en) * 1967-08-08 1975-04-15 Walter A Houston Liquid soluble packet
US3653958A (en) * 1969-03-25 1972-04-04 Sun Oil Co Method of decreasing wax impregnation time by porous paper products
US3902596A (en) * 1970-02-10 1975-09-02 U S Chemicals And Plastics Inc Additive package for compounding resins
US3892905A (en) * 1970-08-12 1975-07-01 Du Pont Cold water soluble plastic films
US3705659A (en) * 1970-09-18 1972-12-12 William L Mackie Erodable material
US3785479A (en) * 1970-12-04 1974-01-15 D Smith Plaster of paris bandages to make casts of improved strength, water-resistance and physiological properties
US3784005A (en) * 1971-12-20 1974-01-08 Us Chem Plastics Inc Additive package and method of compounding resins therewith
US4558781A (en) * 1980-07-23 1985-12-17 Societe Anonyme D'explosifs Et De Produits Chimiques Cartridge for use in anchor bolting
EP0079248A2 (en) 1981-11-11 1983-05-18 Unilever N.V. Packaging film and packaging of detergent compositions therewith
US4416791A (en) * 1981-11-11 1983-11-22 Lever Brothers Company Packaging film and packaging of detergent compositions therewith
EP0079248A3 (en) * 1981-11-11 1985-12-11 Unilever Nv Packaging film and packaging of detergent compositions therewith
EP0132726A2 (en) * 1983-07-21 1985-02-13 Henkel Kommanditgesellschaft auf Aktien Package for a washing, rinsing or cleaning product
EP0132726A3 (en) * 1983-07-21 1986-02-12 Henkel Kommanditgesellschaft Auf Aktien Package for a washing, rinsing or cleaning product
WO1985004107A1 (en) * 1984-03-21 1985-09-26 Alcide Corporation Disinfection method and composition therefor
US5100652A (en) * 1984-03-21 1992-03-31 Alcide Corporation Disinfecting oral hygiene compositions and process for using the same
USRE36064E (en) * 1984-03-21 1999-01-26 Alcide Corporation Disinfection method and composition therefor
US4986990A (en) * 1984-03-21 1991-01-22 Alcide Corporation Disinfection method and composition therefor
US5185161A (en) * 1984-03-21 1993-02-09 Alcide Corporation Disinfection method and composition therefor
US5362413A (en) * 1984-03-23 1994-11-08 The Clorox Company Low-temperature-effective detergent compositions and delivery systems therefor
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
US4776455A (en) * 1986-03-07 1988-10-11 Lever Brothers Company Compartmented product for dispensing treatment agents in a washing or dishwashing machine
US4762738A (en) * 1986-12-22 1988-08-09 E. R. Squibb & Sons, Inc. Means for disposal of articles by flushing and ostomy pouches particularly suited for such disposal
US4830187A (en) * 1986-12-22 1989-05-16 E. R. Squibb & Sons, Inc. Means for disposal of articles by flushing and ostomy pouches particularly suited for such disposal
US4930942A (en) * 1986-12-22 1990-06-05 E. R. Squibb & Sons, Inc. Method of disposal of articles by flushing
EP0337568A2 (en) * 1988-04-11 1989-10-18 Colgate-Palmolive Company Detersive article
EP0337568A3 (en) * 1988-04-11 1991-11-06 Colgate-Palmolive Company Detersive article
EP0366231A1 (en) * 1988-09-26 1990-05-02 Zimpro Environmental, Inc. Sealed PVA package with activated carbon and its use in waste water treatment
US4970008A (en) * 1988-12-20 1990-11-13 Kandathil Thomas V Fabric conditioner comprising a mixture of quaternary ammonium compounds and select tertiary amines
US5160654A (en) * 1989-08-23 1992-11-03 Lever Brothers Company, Division Of Conopco, Inc. Laundry treatment product
WO1992001037A1 (en) * 1990-07-03 1992-01-23 Ecolab Inc. Detersive system containing water soluble film article
US5384364A (en) * 1990-07-03 1995-01-24 Ecolab Inc. Stabilized detersive-system containing water soluble film article
US6204223B1 (en) 1996-01-30 2001-03-20 Zeneca Limited Packaged agrochemical composition
US6136776A (en) * 1997-04-01 2000-10-24 Dickler Chemical Laboratories, Inc. Germicidal detergent packet
US6037319A (en) * 1997-04-01 2000-03-14 Dickler Chemical Laboratories, Inc. Water-soluble packets containing liquid cleaning concentrates
US6057015A (en) * 1997-09-02 2000-05-02 Burlington Bio-Medical And Scientific Corporation Containers and methods for waste recycling
US6509072B2 (en) * 1999-04-27 2003-01-21 P. Scott Bening Multi-layer film with periodic barrier coating and methods of making and using such film
WO2001007560A1 (en) * 1999-07-21 2001-02-01 Henkel Kommanditgesellschaft Auf Aktien Washing or cleansing product portion and packaging for same
WO2001040432A1 (en) * 1999-12-01 2001-06-07 Henkel Kommanditgesellschaft Auf Aktien Packaged portions of detergent
US6958313B2 (en) 2000-05-11 2005-10-25 The Procter & Gamble Company Highly concentrated fabric softener compositions and articles containing such compositions
US7115173B2 (en) 2000-05-11 2006-10-03 The Procter & Gamble Company Highly concentrated fabric softener compositions and articles containing such compositions
US7108725B2 (en) 2000-05-11 2006-09-19 The Procter & Gamble Company Highly concentrated fabric softener compositions and articles containing such compositions
US20060168739A1 (en) * 2000-05-11 2006-08-03 Caswell Debra S Highly concentrated fabric softener compositions and articles containing such compositions
US20050250670A1 (en) * 2000-05-11 2005-11-10 Caswell Debra S Highly concentrated fabric softener compositions and articles containing such compositions
US20020161088A1 (en) * 2001-01-31 2002-10-31 Kochvar Kelly Ann Rapidly dissolvable polymer films and articles made therefrom
US6946501B2 (en) 2001-01-31 2005-09-20 The Procter & Gamble Company Rapidly dissolvable polymer films and articles made therefrom
US20050244444A1 (en) * 2001-01-31 2005-11-03 The Procter & Gamble Company Rapidly dissolvable polymer films and articles made therefrom
US7547737B2 (en) 2001-01-31 2009-06-16 The Procter & Gamble Company Rapidly dissolvable polymer films and articles made therefrom
US20040072708A1 (en) * 2001-03-16 2004-04-15 Duffield Paul John Process for producting a water soluble package
US20040144681A1 (en) * 2001-05-17 2004-07-29 Ralf Wiedemann Water-soluble containers with gas release means
US8151987B2 (en) 2001-12-20 2012-04-10 Watson Laboratories, Inc. Peelable pouch for transdermal patch and method for packaging
US7921999B1 (en) 2001-12-20 2011-04-12 Watson Laboratories, Inc. Peelable pouch for transdermal patch and method for packaging
US8911773B2 (en) 2001-12-20 2014-12-16 Watson Laboratories, Inc. Peelable pouch for transdermal patch and method for packaging
US20110174650A1 (en) * 2001-12-20 2011-07-21 Watson Laboratories, Inc. Peelable Pouch for Transdermal Patch and Method for Packaging
US8623404B2 (en) 2001-12-20 2014-01-07 Watson Laboratories, Inc. Peelable pouch for transdermal patch and method for packaging
US20110174651A1 (en) * 2001-12-20 2011-07-21 Watson Laboratories, Inc. Peelable Pouch for Transdermal Patch and Method for Packaging
US20040189868A1 (en) * 2003-03-24 2004-09-30 Sony Corporation And Sony Electronics Inc. Position and time sensitive closed captioning
US20060260973A1 (en) * 2003-06-20 2006-11-23 Plantic Technologies Ltd. Easy open water soluble blister package
US7325688B1 (en) * 2003-09-26 2008-02-05 Gowan Milling Company, L.L.C. Pressurized water-soluble pouch
US20060172910A1 (en) * 2005-01-10 2006-08-03 The Procter & Gamble Company Machine cleaner
US7915209B1 (en) 2007-03-15 2011-03-29 Linda Skaggs Individual liquid-filled soap bar
US7713921B2 (en) * 2007-03-20 2010-05-11 The Procter & Gamble Company Detergent composition
US20080234169A1 (en) * 2007-03-20 2008-09-25 Jean Pol Boutique Detergent composition
US20090217462A1 (en) * 2008-02-08 2009-09-03 Holzhauer Fred Consumer product packets with enhanced performance
US8236747B2 (en) 2008-02-08 2012-08-07 Method Products, Inc. Consumer product packets with enhanced performance
US20090249562A1 (en) * 2008-04-02 2009-10-08 Mark Robert Sivik Fabric color rejuvenation composition
US9259388B2 (en) 2009-05-05 2016-02-16 Watson Pharmaceuticals, Inc. Method for treating overactive bladders and a device for storage and administration of topical oxybutynin compositions
US10449173B2 (en) 2009-05-05 2019-10-22 Allergan Sales, Llc Method for treating overactive bladders and a device for storage and administration of topical oxybutynin compositions
US20100286630A1 (en) * 2009-05-05 2010-11-11 Watson Laboratories, Inc. Method For Treating Overactive Bladders And A Device For Storage And Administration Of Topical Oxybutynin Compositions
US8920392B2 (en) 2009-05-05 2014-12-30 Watson Laboratories, Inc. Method for treating overactive bladders and a device for storage and administration of topical oxybutynin compositions
US9242774B2 (en) * 2010-08-12 2016-01-26 Church & Dwight Co., Inc. Detergent pouch with improved properties
US20130256182A1 (en) * 2010-08-12 2013-10-03 Church & Dwight Co., Inc. Detergent pouch with improved properties
US10087401B2 (en) 2012-03-16 2018-10-02 Monosol, Llc Water soluble compositions incorporating enzymes, and method of making same
CN104220342A (en) * 2012-04-16 2014-12-17 蒙诺苏尔有限公司 Powdered pouch and method of making same
US9394092B2 (en) 2012-04-16 2016-07-19 Monosol, Llc Powdered pouch and method of making same
US9908675B2 (en) 2012-04-16 2018-03-06 Monosol, Llc Powdered pouch and method of making same
WO2013158364A1 (en) * 2012-04-16 2013-10-24 Monosol, Llc Powdered pouch and method of making same
US10696460B2 (en) 2012-04-16 2020-06-30 Monosol, Llc Powdered pouch and method of making same
US11753222B2 (en) 2012-04-16 2023-09-12 Monosol, Llc Powdered pouch and method of making same
WO2021081475A1 (en) * 2019-10-25 2021-04-29 Monosol, Llc Multilayer water-dispersible articles
CN114901736A (en) * 2019-10-25 2022-08-12 蒙诺苏尔有限公司 Multi-layer water-dispersible article

Similar Documents

Publication Publication Date Title
US3186869A (en) Coated film for laundry package
US3322674A (en) Laundry package
US4972017A (en) Rinse soluble polymer film composition for wash additives
US4801636A (en) Rinse soluble polymer film composition for wash additives
CA1095662A (en) Multiple coated bleaching agent
US4130392A (en) Bleaching process
EP0686189B1 (en) Shaped solid comprising oxidant bleach with encapsulate source of bleach
EP0079712B1 (en) Borate solution soluble polyvinyl alcohol films
EP0143476B1 (en) Dosing unit comprising a detergent and/or bleaching agent
US3198740A (en) Packet of water-soluble film of polyvinyl alcohol filled with detergent composition
US4327151A (en) Encapsulated bleaches and methods for their preparation
US4348293A (en) Water-insoluble, water-permeable bag having a water-soluble or water-dispersable protective layer and containing a particulate detergent composition
US4626372A (en) Borate solution soluble polyvinyl alcohol films
US3413229A (en) Polyvinyl alcohol compositions
US3945936A (en) Bleaching article
BR112015023216B1 (en) Water-soluble package and method for manufacturing a package of delayed solubility and delayed release of an alkaline component therein in hot water
JPS5865798A (en) Controlled release laundry bleaching agent products
CH639419A5 (en) DETERGENT PRODUCTS.
SE439780B (en) SUPPLY UNIT CONTAINING A DETERGENT COMPOSITION INCLUDED IN A PHASE AND PHASE FOR PREPARATION OF THE SUPPLY UNIT
JPH04187508A (en) Stable sodium percarbonate granule and production thereof
US5196139A (en) Bleach article containing polyacrylate or copolymer of acrylic and maleic
EP0011968A1 (en) Particulate detergent composition contained within a closed bag of sheet material
CN105518069B (en) The dispersible film of water for packing High water cut preparation
US1717553A (en) Manufacture of soap
US2571690A (en) Detergent composition