Water soluble film.
Abstract
A water soluble film suitable for packaging caustic chemicals has an outer layer of a water soluble polymeric material, and an inner layer of a polymeric material which is compatible with the contents of a package made from the film. An intermediate layer can optionally be included to contribute to the tensile strength, bulk, or abuse resistance, or some other property of the film. Water soluble fillers such as salt can optionally be added to one or more of the polymeric materials, prior to or during extrusion of the film, to improve the processability of the film or its rate of dissolution in water, or to add a pigment to the film.

Term
Term ended
Projected expiry passed 17 May 2011, 15.4 years ago.
- Priority
- Filed
- Published
- Projected expiry
- Today
18 claims: 7 independent, 11 dependent
- 1A water soluble film comprising an outer layer which comprises a water soluble polymeric material;and an inner layer which comprises a polymeric material compatible with the contents of a package formed from the film.
- 5A film according to any one of the preceding claims wherein the inner layer comprises a water soluble polymeric material.
- 6A film according to any one of the preceding claims wherein the inner layer comprises acid/acrylate copolymer, styrene maleic anhydride copolymer, ethylene acrylic acid copolymer, ionomer, vinyl acrylate copolymer, cellulose, hydroxy propyl cellulose, polyether block amide copolymer, polyhydroxy butyric acid, polyhydroxy valeric acid, polyethylene oxide, polyester, copolyester, polyethyloxazoline, or polyurethane.
- 7A film according to any one of the preceding claims further comprising an intermediate layer comprising a material providing tensile strength, bulk, or abuse resistance to the film.
- 10A film according to any one of the preceding claims wherein at least one of the layers of the film comprises a water soluble salt.
- 14A film according to any one of the preceding claims which is sealed to itself to form an enclosure.
- 15A method for making a film as claimed in any one of claims 1 to 14 comprising the steps of extruding an outer layer of a water soluble polymeric material;extruding an inner layer which comprises a polymeric material compatible with the contents of a package formed from the film;and joining the layers together to make the water soluble film.
Independent claims7
42 paragraphs, as filed
The present invention relates to polymeric film, and more particularly to water soluble film suitable for packaging caustic materials.
Caustic or potentially hazardous materials such as detergents, soaps, pesticides and fertilizers are currently typically packaged in dispensers, such as high density polyethylene bottles, or other containers. After the chemical contents have been used, the dispenser or container must be disposed of in an environmentally safe way. This can be technically difficult and expensive.
Another concern with the use of such caustic or otherwise hazardous chemicals or pesticides is the safety of the user. In installing, using, and disposing of dispensers or containers containing such hazardous chemicals, the safety of the user can be jeopardized if the dispensing or storage system is not properly handled.
It is the object of the present invention to provide a convenient, effective way of storing caustic or potentially hazardous chemicals, pesticides and the like in a manner which satisfies both environmental and safety concerns.
The present invention provides a multilayer film which can effectively and efficiently store a quantity of a chemical, including caustic chemicals, and avoid the need of the end user to open a container to create access to the chemical material.
In one aspect of the invention, a water soluble film comprises an outer layer comprising a water soluble polymeric material; and an inner layer which comprises a polymeric material compatible with the contents of a package formed from the film.
In another aspect of the invention, a method for making a water soluble film comprises the steps of extruding an outerlayer of a water soluble polymeric material; extruding an inner layer of a polymeric material which is compatible with the contents of a package formed from the film; and joining the layers together to make the water soluble film.
In yet another aspect of the invention, a water soluble container comprises a film having an outer layer comprising a water soluble polymeric material; and an inner layer comprising a polymeric material which is compatible with the contents of the package when filled; the film being sealed together to form an enclosure.
The invention may be further understood with reference to the sole drawing, Figure 1, showing a cross-section of a film of the present invention.
Referring to Figure 1, a water soluble film 10 includes an outer layer 12 of a water soluble polymeric material.
This outer layer 12 may be a fully hydrolyzed polyvinyl alcohol (PVA) such as Vinex 1003 available from Air Products.
A feature of the fully hydrolyzed PVA of outer layer 12 is that it is insoluble in cold water but increasingly soluble in water at higher temperatures. Typically, at water temperatures above about 120°F fully hydrolyzed PVA such as the Vinex 1003 resin is fully soluble in water.
Outer layer 12 may also be a low melting point, water soluble coating. By "low melting point" is meant a melting point of between about 120 and 180°F, more preferably between about 130 and 170°F, even more preferably between about 140 and 160°F, and most preferably about 150°F.
Inner layer 16 includes a polymeric material which is compatible with the contents of a package made from the film. Layer 16 normally will be the innermost layer of a package formed from the film and therefore will be in contact with the caustic chemical, pesticide, fertilizer, etc. which is packaged. The term "caustic" is used herein to mean a chemical or mixture of chemicals with a pH of 7.0 or higher, i.e. alkaline.
Layer 16 can be any of a variety of polymeric materials, either polymers, copolymers, terpolymers, etc. which are compatible with the contents of a package formed from the film. By the phrase "compatible with" is meant that the composition of inner layer 16 is such that during normal storage and use, the material of layer 16 will not appreciably decompose or degrade as a result of contact with the package contents. Instead, the material of layer 16 will dissolve when the contents of the container are exposed to water. These contents can include highly caustic chemicals and detergents, pesticides, fertilizers, soaps, and other materials which can aggressively attack some packaging materials.
Suitable materials for layer 16 include acid/acrylate copolymers, preferably methacrylic acid/ethyl acrylate copolymer such as that available from Belland as GBC 2580 and 2600; styrene maleic anhydride copolymer (SMA)(available as Scripset (trademark) from Monsanto); ethylene acrylic acid copolymer (EAA), or metal salt neutralized ethylene methacrylic acid copolymer (EMAA) known as ionomer (available from du Pont), in which the acid content of the EAA or EMAA is at least about 20 mole percent; vinyl acrylate copolymer (Vinac (trademark)); cellulose; hydroxy propyl cellulose, such as that available from Aqualon as Kluceo (trademark); polyether block amide copolymer; polyhydroxy butyric acid or polyhydroxy valeric acid (available as Biopol (trademark)resins from Imperial Chemical Industries); polyethylene oxide; water soluble polyester or copolyester; polyethyloxazoline (PEOX 200 from Dow); and water soluble polyurethane.
Non-polymeric materials such as aluminum may be coated or sputtered onto the water-soluble layer 12.
An optional layer 14 can also be advantageously used in the inventive laminate. Intermediate layer 14 includes a polymeric material which contributes to the tensile strength of the overall water soluble film. An especially preferred polymeric material for layer 14 is a partially hydrolyzed PVA such as Vinex 2034 available from Air Products. Preferred partially hydrolyzed PVA materials have a degree of hydrolysis of preferably at least about 60%, and more preferably at least about 70%. Most preferably, such partially hydrolyzed PVA materials are hydrolyzed at between 85 and 98% hydrolysis. Such partially hydrolyzed PVA materials are soluble in both cold and hot water.
An alternative material also suitable for intermediate layer 14 is polyethylene oxide, such as that available from Union Carbide as Poly Ox WSR.
Layer 14 can contribute to the tensile strength of the overall film, but also to such properties as bulk, abuse resistance, and the like.
The invention may be further understood by reference to the following examples.
Example 1
A fully hydrolyzed polyvinyl alcohol (Vinex 1003) was coextruded with a partially hydrolyzed polyvinyl alcohol (Vinex 2034), and a methacrylic acid/ethyl acrylate copolymer (Belland GBC 2580).
The annular coextrusion die was set at 400 to 410°F. The Vinex 1003 ran at a temperature of about 360 to 400°F (extrusion temperature). The Vinex 2034 resin ran at a temperature of about 375 to 420°F. The Belland GBC 2580 ran at a temperature of about 320 to 360°F.
The film of Example 1 had a total thickness of about 4.0 mils, with the outer layer of fully hydrolyzed PVA comprising about 1 mil; the intermediate layer of partially hydrolyzed PVA comprising about 2 mils; and the inner contents-compatible layer having a thickness of about 1 mil.
Example 2
A film like that of Example 1 is made, but including a water soluble filler in the inner layer.
Although the film of the present invention is preferably made by coextrusion techniques well known in the art, resins which are not suitable for coextrusion processes may be brought together by extrusion coating or conventional lamination techniques to produce the final water soluble film. Both discrete layers and coatings can be used for any of the layers of the inventive laminate.
As used herein "water soluble" refers to a film structure which is preferably totally water soluble. However, films which are substantially water soluble but have relatively minor amounts of a material in the film structure which is not water soluble; films with materials which are water soluble only at relatively high water temperatures or only under limited pH conditions; and films which include a relatively thin layer of water insoluble material, are all included in the term "water soluble".
The film of the present invention offers several advantages. The user does not have to open the package and therefore is not exposed to potentially hazardous contents. In addition, the conventional container is not recyclable and therefore can pose a hazard to the environment from residual contents within the container. The present invention offers a water soluble film which can be formed into a biodegradable package which can be used as is, with the appropriate contents within the package, and without the need for attempting to recycle a container.
In some instances, packages can contain premeasured portions so that no measuring is required and the package can be used as is.
Although the water soluble layer 12 of film 10 preferably is soluble only at relatively high water temperatures, other "triggering" mechanisms may be employed. For example, some resin materials may be water soluble at certain ranges of pH. Thus, resins such as the SMA and EAA or EMAA resins can be incorporated into the film structure at relatively low pH conditions, and thereafter formed into a container which is used in a high pH environment where the water soluble layer will decompose.
In instances where a resin is used which is soluble in water at relatively low temperatures, or is soluble in water at a broader range of pH conditions, the film may be protected from accidental failure (i.e. weakening or dissolving by water) by enclosing the package inside an overwrap material. Such overwrap materials in the form of bags, pouches or the like are well known in the art and are typically made up of polyolefin monolayer or multilayer films or laminates. These overwrap materials can also be made from paper, metal, and substances besides synthetic polymers.
In practicing the present invention, two problems can sometimes occur. First, these films can become tacky over time. Second, the rate of dissolution of the film can be slower than desired. These problems can be overcome to some extent by adding a water soluble filler to one or more resins making up the film. This is preferably done by compounding the agent as a powder into the base resin prior to or during extrusion.
Such fillers can solve the tackiness problem by acting as an antiblock, which reduces blocking and improves processing and converting operations.
Such fillers can also dissolve quickly, promoting dispersion of the polymer. This in turn increases the surface area of the material, speeding up dissolution.
When properly selected, these fillers can also function as a pigment.
Water soluble fillers meeting one or more of these properties (antiblock effect, increased dissolution effect, or pigment-bearing) are included in the base resin preferably in a masterbatch or "fully let down" form. The fillers are preferably of sufficiently small particle size for conversion to film. A particle size of about 5 microns or less is preferred.
The water soluble fillers can be compounded into the base resin on conventional compounding equipment such as a twin screw. Stainless steel cooling belts can be used, instead of water, to cool and/or quench the resulting strands. Such belts are commercially available from Sandvik and Berndorf. The compounded resin can then be used in conventional extrusion operations to produce water soluble film.
Suitable water soluble fillers include any material which is water soluble, or substantially so, and capable of being incorporated into the film structures disclosed in this specification. Preferred materials are salts, and more preferably alkali or alkaline earth salts such as sodium carbonate (Na₂CO₃); sodium sulfate (Na₂SO₄); sodium chloride (NaCl); potassium carbonate (K₂CO₃); potassium sulfate (K₂SO₄); and potassium chloride (KCl).
One or more of these water soluble fillers can be included in one or more of the layers of the water soluble film of the invention. The filler can be present in any suitable concentration in a given layer. Optimal concentrations will be governed to some extent by the nature of the filler, the nature of the base resin, the specific end use of the film, processing and packaging equipment, and other factors. A preferred concentration of the filler or fillers for a given layer of the film is between about 100 parts per million (.01%) and 200,000 parts per million (20%) by total weight of the layer. Alternatively, the film as a whole may comprise from 0.01% to 20% by weight of a filler, such as a water soluble salt.
While the present invention has been described with reference to preferred embodiments, those skilled in the art will understand that modifications in resin choice, film structure, and process may be made without departing from the scope of the invention as claimed below.
1 sheet
Sheet 1
Every citation, both ways
| Document | Relation | Office | Cited during |
|---|---|---|---|
| WO2016160449A1 | Cited by | World Intellectual Property Organization (WIPO) | International search |
| WO03097723A1 | Cited by | World Intellectual Property Organization (WIPO) | International search |
| US8728449B2 | Cited by | United States of America | Applicant |
| US5624034A | Cited by | United States of America | Search report |
| CN107428974A | Cited by | China | Search report |
| US7057008B2 | Cited by | United States of America | Applicant |
| US6406797B1 | Cited by | United States of America | Applicant |
| EP0514172A1 | Cited by | European Patent Office (EPO) | Search report |
| EP0513692A1 | Cited by | European Patent Office (EPO) | Search report |
| WO9615903A1 | Cited by | World Intellectual Property Organization (WIPO) | International search |
| US6984067B2 | Cited by | United States of America | Applicant |
| US5362532A | Cited by | United States of America | Search report |
| US6440508B1 | Cited by | United States of America | Applicant |
| US5786092A | Cited by | United States of America | Search report |
| US5863885A | Cited by | United States of America | Search report |
| US5429874A | Cited by | United States of America | Search report |
| US5280835A | Cited by | United States of America | Search report |
| US5429242A | Cited by | United States of America | Search report |
| EP0518689A1 | Cited by | European Patent Office (EPO) | Search report |
| EP0513692A1 | Cited by | European Patent Office (EPO) | Search report |
| US6244746B1 | Cited by | United States of America | Applicant |
| EP1848759B2 | Cited by | European Patent Office (EPO) | Opposition |
| US7364359B2 | Cited by | United States of America | Applicant |
| EP1844091B2 | Cited by | European Patent Office (EPO) | Opposition |
| WO9615903A1 | Cited by | World Intellectual Property Organization (WIPO) | International search |
| GB2392446A | Cited by | United Kingdom | Search report |
| US5316688A | Cited by | United States of America | Search report |
| EP0514172A1 | Cited by | European Patent Office (EPO) | Search report |
| US6471401B1 | Cited by | United States of America | Applicant |
| EP0142950A2 | Cites | European Patent Office (EPO) | Search report |
| DE3017246A1 | Cites | Germany | Search report |
| US3790067A | Cites | United States of America | Search report |
15 members in 9 offices
Priority claims8
| Document | Office | Kind | Date |
|---|---|---|---|
| 525440 | United States of America | – | |
| 52544090 | United States of America | A | |
| 601494 | United States of America | – | |
| 60149490 | United States of America | A | |
| 525440 | – | – | – |
| 601494 | – | – | – |
| US19900525440 | – | – | – |
| US19900601494 | – | – | – |
Members15
| Document | Office | Kind | |
|---|---|---|---|
| CA2042700A1 | Canada | A1 | |
| AU7706291A | Australia | A | |
| EP0457600A2This record | European Patent Office (EPO) | A2 | |
| ZA903650B | South Africa | B | |
| EP0457600A3 | European Patent Office (EPO) | A3 | |
| JPH04232046A | Japan | A | |
| AU649039B2 | Australia | B2 | |
| NZ238180A | New Zealand | A | |
| EP0457600B1 | European Patent Office (EPO) | B1 | |
| AT143309T | Austria | T | |
| DE69122302D1 | Germany | D1 | |
| DE69122302T2 | Germany | T2 | |
| JP3034980B2 | Japan | B2 | |
| CA2042700C | Canada | C | |
| US6406797B1 | United States of America | B1 |
47 legal events, as 4 offices reported them to INPADOC
Over the term
Point at a mark for the eventEvents
| Event | Code | Office | |
|---|---|---|---|
| Lapsed in a contracting state [announced via postgrant information from national office to epo]LapsedPG25 | PG25 | EP | |
| Notification of lapseLapsedST | ST | FR | |
| Nl: lapsed or anulled due to non-payment of the annual feeLapsedNLV4 | NLV4 | EP | |
| Lapsed in a contracting state [announced via postgrant information from national office to epo]LapsedPG25 | PG25 | EP | |
| Gb: european patent ceased through non-payment of renewal feeCeasedGBPC | GBPC | EP | |
| Lapsed in a contracting state [announced via postgrant information from national office to epo]LapsedPG25 | PG25 | EP | |
| Lapsed in a contracting state [announced via postgrant information from national office to epo]LapsedPG25 | PG25 | EP | |
| Be: lapsedLapsedBERE | BERE | EP | |
| Lapsed in a contracting state [announced via postgrant information from national office to epo]LapsedPG25 | PG25 | EP | |
| Lapsed in a contracting state [announced via postgrant information from national office to epo]LapsedPG25 | PG25 | EP | |
| Lapsed in a contracting state [announced via postgrant information from national office to epo]LapsedPG25 | PG25 | EP | |
| Annual fee paid to national office [announced via postgrant information from national office to epo]GrantedPGFP | PGFP | EP | |
| Annual fee paid to national office [announced via postgrant information from national office to epo]GrantedPGFP | PGFP | EP | |
| Annual fee paid to national office [announced via postgrant information from national office to epo]GrantedPGFP | PGFP | EP | |
| Annual fee paid to national office [announced via postgrant information from national office to epo]GrantedPGFP | PGFP | EP | |
| Annual fee paid to national office [announced via postgrant information from national office to epo]GrantedPGFP | PGFP | EP | |
| Annual fee paid to national office [announced via postgrant information from national office to epo]GrantedPGFP | PGFP | EP | |
| European patent in force as of 2002-01-01IF02 | IF02 | GB | |
| Nl: assignments of ep-patentsNLS | NLS | EP | |
| No opposition filedOpposition26N | 26N | EP | |
| No opposition filed within time limitOppositionORIGINAL CODE: 0009261PLBE | PLBE | EP | |
| Information on the status of an ep patent application or granted ep patentGrantedSTATUS: NO OPPOSITION FILED WITHIN TIME LIMITSTAA | STAA | EP | |
| Annual fee paid to national office [announced via postgrant information from national office to epo]GrantedPGFP | PGFP | EP | |
| Patent ceasedCeasedPL | PL | CH | |
| Fr: translation filedET | ET | EP | |
| Lapsed in a contracting state [announced via postgrant information from national office to epo]LapsedPG25 | PG25 | EP | |
| Lapsed in a contracting state [announced via postgrant information from national office to epo]LapsedPG25 | PG25 | EP | |
| Corresponds to:REF | REF | EP | |
| It: translation for a ep patent filedITF | ITF | EP | |
| It: translation for a ep patent filedITF | ITF | EP | |
| Designated contracting statesAK | AK | EP | |
| Lapsed in a contracting state [announced via postgrant information from national office to epo]LapsedPG25 | PG25 | EP | |
| Lapsed in a contracting state [announced via postgrant information from national office to epo]LapsedPG25 | PG25 | EP | |
| Lapsed in a contracting state [announced via postgrant information from national office to epo]LapsedPG25 | PG25 | EP | |
| Lapsed in a contracting state [announced via postgrant information from national office to epo]LapsedPG25 | PG25 | EP | |
| Lapsed in a contracting state [announced via postgrant information from national office to epo]LapsedPG25 | PG25 | EP | |
| Corresponds to:REF | REF | EP | |
| (expected) grantORIGINAL CODE: 0009210GRAA | GRAA | EP | |
| Despatch of communication of intention to grant a patentORIGINAL CODE: EPIDOS IGRAGRAH | GRAH | EP | |
| Despatch of communication of intention to grant a patentORIGINAL CODE: EPIDOS IGRAGRAH | GRAH | EP | |
| Despatch of communication of intention to grantORIGINAL CODE: EPIDOS AGRAGRAG | GRAG | EP | |
| First examination report despatched17Q | 17Q | EP | |
| Request for examination filed17P | 17P | EP | |
| Designated contracting statesAK | AK | EP | |
| Search report despatchedORIGINAL CODE: 0009013PUAL | PUAL | EP | |
| Designated contracting statesAK | AK | EP | |
| Public reference made under article 153(3) epc to a published international application that has entered the european phaseORIGINAL CODE: 0009012PUAI | PUAI | EP |
Numbers
- Publication
- 0457600
- Publication, DOCDB
- 0457600
- Publication, EPODOC
- EP0457600
- Application
- 91304438
- Application, DOCDB
- 91304438
- Application, EPODOC
- EP19910304438
Titles3
- German
- Wasserlöslicher Film
- English
- Water soluble film
- French
- Film soluble dans l'eau
Classification
- CPC, 8
- B32B27/08
- B32B27/285
- B32B27/306
- B32B27/36
- B32B27/40
- B32B37/153
- B32B2307/7166
- B32B2439/00
- IPC, 7
- B29C47 04
- B29K29 00
- B29L9 00
- B32B27 00
- B32B27 08
- B32B27 30
- B65D65 40
Designated states14
- Contracting states, 14
- Austria
- Belgium
- Switzerland
- Germany
- Denmark
- Spain
- France
- United Kingdom
- Greece
- Italy
- Liechtenstein
- Luxembourg
- Netherlands (Kingdom of the)
- Sweden