Multi-layered polymer film for medical grade products
Abstract
A multiple layer structure comprising a skin layer composed of a polypropylene copolymer with styrene ethylene-butene styrene block copolymer within a range of 0-20% by weight skin layer, and, a radio frequency ("RF") susceptible layer adhered to the skin layer. The RF layer has a first component of a propylene based polymer, a second component of a nonpropylene polyolefin, a third component of a radio frequency susceptible polymer, and a fourth component of a polymeric compatibilizing agent.

Term
No projected expiry on record.
- Priority
- Filed
- Published
- Today
55 claims: 7 independent, 48 dependent
- 1Egy többréteges szerkezet, azzal jellemezve, hogy egy felső réteget; First A multilayer structure, characterized by a top layer; a radio frequency ("RF") sensitive layer which adheres to the top layer and which RF layer comprises a propylene based polymer first component, a non-propylene polyolefin based second component, a radio frequency sensitive polymer third component and a polymer compatibility aid a fourth component; egy radio-frekvenciára („RF”) érzékeny réteget, amely a felső réteghez tapad és amely RF réteg egy propilén alapú polimer első komponenst, egy nem propilén poliolefin alapú második komponenst, egy radio-frekvenciára érzékeny polimer harmadik komponenst és egy polimer kompatibilitást segítő segédanyag negyedik komponenst tartalmaz; amely szerkezet fizikai jellemzői az alábbiak a < 40.000 psi; the physical characteristics of which structure are <40,000 psi; b >= 70%; b> = 70%; c < 30%; c <30%; d > 1,0; d> 1.0; e < 0,1%; e <0.1%; f < 0,1%; f <0.1%; g >= 0,05; g> = 0.05; h <= 60%; h <= 60%; i = 0; i = 0; ahol:where: (a) the mechanical modulus of the formulation, measured in accordance with ASTM D-882;a) a készítmény mechanikai modulusa, amelyet az ASTM D-882 szabvány szerint mérünk;b) a kezdeti 20% deformáció után a készítmény hosszúságának visszanyerést %-a;b)% recovery of composition length after an initial 20% deformation;(c) optical opacity of the product processed into a film of a thickness of 9 mm, as measured according to ASTM D-1003;c) a 9 mm vastagságú filmmé feldolgozott készítmény optikai homályossága az ASTM D-1003 szabvány szerint mérve;d) a készítmény veszteségi tangense 1 Hz érték mellett az olvadási feldolgozási hőmérsékleten;d) a loss tangent of the composition at a melting processing temperature of 1 Hz;(e) mass concentration of the halogen element in the preparation;e) a készítmény halogénelem tömeg értékben megadott koncentrációja;(f) the amount of the low molecular weight water soluble fraction of the composition;f) a készítmény alacsony molekulatömegű vízben oldható frakciójának mennyisége;g) 1 és 60 MHz és 25-250 °C közötti hőmérséklet mellett a készítmény dielektromos vesztesége;g) dielectric loss of the composition at temperatures between 1 and 60 MHz and 25-250 ° C;(h) Flow of sample at 121 ° C for a 1 inch strip formulation h) a minta megfolyása 121 °C hőmérsékleten 1 inch szalag készítmény esetében 27 at psi load and 27 psi terhelés mellett és (i) the preparation does not exhibit tensile whiteness after approx. At 2 inches (50 cm) / min for approx. It is elongated at 100% (twice the original length) and the presence of sign 1 (tension whiteness) is indicated by 0 (absence of tension whiteness). i) a készítmény nem fejt ki húzási fehéredést, miután kis sebességgel kb. 2 inch (50 cm)/perc sebességgel kb. 100% mértékben (az eredeti hossz kétszerese) megnyújtjuk és az 1 jel (húzási fehéredés) jelenlétét a 0 jel (a húzási fehéredés hiányát) jelzi.
- 2Többréteges szerkezet, azzal jellemezve, hogy egy felső réteget tartalmaz, amely propilén-kopolimer egy sztirol-etilén-butén-sztirol blokk kopolimerrel, amelyben a polipropilén tömeg%-a 0-20% közötti;és egy radio-frekvencia („RF”) érzékeny réteget tartalmaz, amely a felső réteghez tapad és amely RF réteg egy első propilén alapú komponenst, egy második nem propilén alapú poliolefin komponenst, egy harmadik radio-frekvencia érzékeny komponenst és egy negyedik polimer kompatibilitást segítő segédanyag komponenst tartalmaz. Second A multi-layer structure comprising an upper layer comprising a propylene copolymer with a styrene-ethylene-butylene-styrene block copolymer in which the percentage by weight of the polypropylene is 0-20%;and a radio frequency ("RF") sensitive layer which adheres to the upper layer and which RF layer comprises a first propylene based component, a second non-propylene based polyolefin component, a third radio frequency sensitive component, and a fourth polymer compatibility aid. contains an excipient component.
- 26Többréteges szerkezet, azzal jellemezve, hogy egy felső réteget, amely polipropilén kopolimer lehet sztirol-etilén-butén-sztirol blokk kopolimerrel, amelynek tömeg%-a a felső rétegben 0-20% közötti és;26th A multilayer structure, characterized in that an upper layer, which can be a polypropylene copolymer with a styrene-ethylene-butene-styrene block copolymer, which in the upper layer is between 0 and 20% by weight;a radio frequency ("RF") sensitive layer which adheres to the upper layer and which RF layer is a first component which is a polypropylene based polymer in an amount of 30-60% by weight based on the amount of the RF layer, a second component which is not propylene polyolefin in an amount of 0-60% by weight relative to the RF layer, a third component which is a radio frequency sensitive polymer at 30-40% by weight based on the RF layer and a fourth component, the polymer compatibility aid comprising from 5 to 40% by weight of the RF layer. egy radio-frekvencia („RF”) érzékeny réteget tartalmaz, amely a felső réteghez tapad és amely RF réteg egy első komponenst, amely polipropilén alapú polimer 30-60 tömeg% mennyiségben, az RF réteg mennyiségre vonatkoztatva, egy második komponenst, amely nem propilén poliolefin 0-60 tömeg% mennyiségben az RF rétegre vonatkoztatva, egy harmadik komponenst, amely radio-frekvenciára érzékeny polimer az RF rétegre vonatkoztatva 30-40 tömeg%-ban és egy negyedik komponenst, amely polimer kompatibilitást segítő segédanyag az RF rétegre vonatkoztatva 5-40 tömeg% mennyiségben tartalmaz.
- 34Többréteges szerkezet, azzal jellemezve, hogy egy felső réteget tartalmaz, amely polipropilén-kopolimer, sztirol-etilén-butén-sztirol blokk kopolimerrel, amelynek tartalma a felső rétegben 0-20 tömeg% közötti;34th A multi-layer structure comprising an upper layer comprising a polypropylene copolymer with a styrene-ethylene-butene-styrene block copolymer having a content of 0-20% by weight in the upper layer;comprising a core layer which adheres to the top layer on one side;and a radio frequency ("RF") sensitive layer which adheres to one side of the core layer on the side opposite to the top layer and which RF layer comprises a first component in an amount of 30-60% by weight of the RF layer, which component is a propylene based polymer, and a second component in the range of 25-50% by weight of the RF layer, which component is a non-propylene polyolefin and a third component, which comprises a radio frequency-sensitive polymer in an amount of from 3 to 40% by weight of the RF layer;and a fourth component, in an amount of 5 to 40% by weight of the RF layer, to aid polymer compatibility. egy magréteget tartalmaz, amely egy oldalán a felső réteghez tapad;és egy radio-frekvencia („RF”) érzékeny réteget tartalmaz, amely a magréteg egyik oldalához a felső réteggel ellenkező oldalon tapad és amely RF réteg egy első komponenst tartalmaz az RF réteg tömegére vonatkoztatva 30-60% mennyiségben, amely komponens propilén alapú polimer, valamint egy második komponenst tartalmaz az RF réteg tömegére vonatkoztatva 25-50%-ban, amely komponens nem propilén poliolefin és egy harmadik komponenst tartalmaz, amely az RF réteg tömegére vonatkoztatva 3-40% mennyiségű radio-frekvenciára érzékeny polimer, valamint egy negyedik komponenst tartalmaz, amely az RF réteg tömegére vonatkoztatva 5-40% mennyiségű és polimer kompatibilitást segítő segédanyag.
- 41Többréteges szerkezet egymásra helyezett rétegekből, azzal jellemezve, hogy egy felső réteget tartalmaz, amely polipropilén-kopolimer, sztirol-etilén-butén-sztirol blokk kopolimerrel, amely a felső réteg 0-20 tömeg% mennyiségét képviseli;41st A multilayer structure of superimposed layers, characterized in that it comprises an upper layer comprising a polypropylene copolymer with a styrene-ethylene-butene-styrene block copolymer representing from 0 to 20% by weight of the upper layer;comprising a radio frequency ("RF") sensitive layer, the RF layer comprising a first component containing from 30 to 60% by weight of the RF layer and a propylene based polymer, a second component containing by weight of the RF layer. -50% and a non-propylene based polyolefin, containing a third component which is 3-40% by weight of the RF layer and is a radio frequency sensitive polymer, further comprising a fourth component comprising from 5% to 40% by weight of the RF layer and a polymer compatibility aid;egy radio-frekvencia („RF”) érzékeny réteget tartalmaz, amely RF réteg egy első komponenst tartalmaz, amely az RF réteg tömegére vonatkoztatva 30-60% mennyiségű és valamely propilén alapú polimer, egy második komponenst tartalmaz, amely az RF réteg tömegére vonatkoztatva 25-50% mennyiségű és valamely nem propilén alapú poliolefin, egy harmadik komponenst tartalmaz, amely az RF réteg tömegére vonatkoztatva 3-40% mennyiségű és egy radio-frekvenciára érzékeny polimer, továbbá egy negyedik komponenst tartalmaz, amely az RF réteg tömegére vonatkoztatva 5-40% mennyiségű és egy polimer kompatibilitást segítő segédanyag;Comprising a first core layer between the top layer and the RF layer;and comprising a layer of waste material attached to the core layer. • · • · · · • · · · • » · · · · » · · ’ - 38egy első magréteget tartalmaz, amely a felső réteg és az RF réteg között helyezkedik el;és egy hulladék anyag réteget tartalmaz, amely a magréteghez csatlakozik.
- 46Többréteges szerkezet, azzal jellemezve, hogy egy felső réteget tartalmaz, amely polipropilén-kopolimer, sztirol-etilén-butén-sztirol blokk kopolimerrel együtt, amelynek mennyisége a felső réteg tömegére vonatkoztatva 0-20%;46th A multilayer structure comprising an upper layer comprising a polypropylene copolymer, in combination with a styrene-ethylene-butene-styrene block copolymer, in an amount of 0 to 20% by weight of the upper layer;comprising a radio frequency ("RF") sensitive layer, the RF layer comprising a first component comprising from 30% to 60% by weight of the RF layer and a propylene based polymer containing a second component based on the weight of the RF layer. -50% and a non-propylene polyolefin, contains a third component, comprising from 3 to 40% by weight of the RF layer and a radio frequency-sensitive polymer, and a fourth component containing from 5 to 40% by weight of the RF layer and a polymer compatibility aid;egy radio-frekvencia („RF”) érzékeny réteget tartalmaz, amely RF réteg egy első komponenst tartalmaz, amely komponens az RF réteg tömegére vonatkoztatva 30-60% mennyiségű és valamely propilén alapú polimer egy második komponenst tartalmaz, amely az RF réteg tömegére vonatkoztatva 25-50% mennyiségű és valamely nem propilén poliolefin, egy harmadik komponenst tartalmaz, amely az RF réteg tömegére vonatkoztatva 3-40% mennyiségű és valamely radio-frekvenciára érzékeny polimer és egy negyedik komponenst tartalmaz, amely az RF réteg tömegére vonatkoztatva 5-40% mennyiségű és valamely polimer kompatibilitást segítő segédanyag;further comprising a first core layer disposed between the top layer and the RF layer;and comprising a passage barrier layer attached to the core layer. továbbá egy első magréteget tartalmaz, amely a felső réteg és az RF réteg között helyezkedik el;és egy áthaladást gátló réteget tartalmaz, amely a magréteghez kapcsolódik.
- 53Többréteges szerkezet, azzal jellemezve, hogy egy felső réteget tartalmaz, amely polipropilén-kopolimer és sztirol-etilén-butén-sztirol blokk kopolimer, amely mennyisége a felső rétegben 0-20 tömeg%;53rd A multi-layer structure comprising an upper layer comprising a polypropylene copolymer and a styrene-ethylene-butylene-styrene block copolymer in an amount of 0 to 20% by weight in the upper layer;comprising a core layer which adheres to the top layer on one side;and a radio frequency ("RF") sensitive layer attached to the core layer on the side opposite to the top layer, the RF layer comprising a high melting and resilient polypropylene component in an amount of 30-60% by weight of the RF layer;containing a radio frequency sensitive polymer in an amount of 5 to 20% by weight of the RF layer and containing a polymer compatibility aid, 5-20% by weight of the RF layer. egy magréteget tartalmaz, amely egyik oldalán a felső réteghez tapad;és egy radio-frekvencia („RF”) érzékeny réteget tartalmaz, amely a magréteghez kapcsolódik a felső réteggel ellenkező oldalon és amely RF réteg egy magas olvadáspontú és rugalmas polipropilén komponenst tartalmaz, amelynek mennyisége az RF réteg tömegére vonatkoztatva 30-60%, továbbá egy radio-frekvenciára érzékeny polimert tartalmaz, amelynek mennyisége az RF réteg tömegére vonatkoztatva 5-20% és egy polimer kompatibilitást segítő segédanyagot tartalmaz, amelynek mennyisége az RF réteg tömegére vonatkoztatva 5-20%.
Independent claims7
277 paragraphs, as filed
The present invention generally relates to materials suitable for the preparation of pharmaceutical grade products, more particularly to the production of a thin film product which can be used e.g. plastic containers or pharmaceutical tubes.
In the field of pharmacy, beneficial agents are stored, processed and collected in containers, as well as transported and finally infused via tubing to patients and have a therapeutic effect. The materials used for the construction of tanks and pipes are of special quality, e.g. they should be visually transparent, since it should be possible to visually detect the presence of particulate impurities in the solutions in the container. In addition, if a solution is infused out of a container, the material will be sufficiently elastic to adequately sink the container without the need to introduce outside air into the container. As a result, one of the requirements for the material used is flexibility. In addition, the material should be thermally resistant within very wide temperature ranges, the material used should exhibit sufficient elasticity at low temperatures, but also sufficient strength, since some solutions, e.g. some premixed drug solutions are stored and transported in tanks at temperatures of up to -25 to -30 ° C to prevent degradation of the drug. In addition, the same materials should be capable of operating at high temperatures since they must be sufficiently resistant to the high temperature of sterilization, which is done prior to shipment for most pharmaceutical and food product packages. The sterilization process is generally performed by exposing the container to a stream of steam, typically at a temperature of 121 ° C or higher. so the requirement for the material is that it is also subject to pressure and temperature.
- * * · "·· ·· ·· · · · · · · ♦ • · ··: ···· ·· be stable without significant deformation (" heat distortion resistance ") occurs..
In order to easily produce suitable devices, it is desirable that the material used be sealed or soldered by radio frequency ("RF"), which frequency is usually approx. 27.12 MHz. Therefore, the material should have the proper dielectric loss characteristic to convert RF energy into thermal energy.
An additional requirement for the material used is that after disposal of the appropriate manufactured device, the level of environmental contamination from the material used should be minimal. For materials that are stored somewhere in the nature as garbage, it is desirable to use as little material as possible in their preparation and to avoid the use of low molecular weight leachable materials. As a result, the material used should be light in weight and of good mechanical strength. In addition, it is necessary to use a material that can be recycled by thermoplastic processing after use to another suitable device.
For containers destined for incineration by incineration, the use of material that promotes the removal of biohazardous materials and minimizes or eliminates the formation of inorganic acids that are hazardous to the environment, irritant and corrosive, or products, which are dangerous, irritant or otherwise harmful during burning.
Above all, it is necessary that the material used be free or contain very low concentrations of low molecular weight additives, e.g. plasticisers, stabilizers and the like. These substances may be released into pharmaceutical formulations or into biological fluids or tissues and may therefore pose a risk to the patient or contaminate such stored or processed active substances or active substances in the devices. For example, if a container is made containing solutions, transfusion solutions, such contamination, the patient may be injected during transfusion and may cause injury, injury or even death to the person being treated.
Conventionally used flexible polyvinyl chloride materials meet some, and in some cases most, of the above requirements. In addition, polyvinyl chloride "PVC" has the particular advantage of being one of the most economical materials used in the manufacture of devices meeting the above requirements. However, PVC incineration produces undesirable amounts of hydrochloric acid (or hydrochloric acid if in contact with water) and causes corrosion of the incinerator. Occasionally, PVC may use a plasticizer, which may be leached into the active ingredient, or into biological fluids or tissues, thereby contaminating materials that come into contact with the PVC holder. It may therefore be necessary to replace PVC with other materials. However, most other applicable materials are too expensive to use and, even with this high price, do not meet all of the above requirements.
Many attempts have been made to develop a film material that can replace PVC, but most attempts have failed for some reason. For example, U.S. Patent No. 4,966,795 discloses a multilayer film composition which is capable of resisting steam sterilization but cannot be welded by radio frequency dielectric heating and therefore cannot be used in a fast, low cost, and reliable process. EP 0 310 143 A1 • ··· ··· ·,.,
......
- 5 Dalmatian applications describe a multilayer film compound that meets most requirements and can be RF welded. However, the components of a given film are crosslinked by radiation (radiation) and thus cannot be recycled by standard thermoplastic processing techniques. In addition, since the process involves an irradiation step, a significant amount of acetic acid is liberated and incorporated into the material. During steam sterilization, acetic acid enters the contents of the container as a contaminant and changes the pH of the contents, and can also act as a potential chemical reactant or serve as a catalyst for the degradation of the contained material.
BACKGROUND OF THE INVENTION The present invention relates to certain thermoplastic materials which, overall, exhibit improved properties over the materials described above than those known and commercially available. Such materials are characterized by flexibility, extensibility, recoverability of tension or strength not only at room temperature but also at room temperature and cooled temperature limits. The material is suitably visually translucent for observation and steam sterilization up to 121 ° C. The material is capable of resisting stress of sufficient magnitude without altering its own strength characteristics, which would mean that they would suffer physical and cosmetic damage. Another feature of the material of the invention is that the material is capable of processing by RF techniques. In addition, the material of the invention is substantially low molecular weight, free from soluble additives, and can be safely disposed of, e.g. can be destroyed by incineration without the formation of significant amounts of corrosive inorganic acid. Another feature of the materials of the invention is that the material can be recycled after use by standard thermoplastic processing.
• ·
<img file="HUT72715A_D0001.tif" />
It is also desirable to be able to incorporate the recycled loss material from the manufacturing process into the material so as to reduce the cost of material as well as the loss in production. Finally, the material represents a low-cost alternative to the various PVC formulations currently used in medical devices.
When more than one polymer is blended to form a blend composition, it is very difficult to meet all of the above requirements simultaneously. For example, in most cases, so-called blend formulations exhibit light scattering; therefore, they do not meet the requirement of optical transparency. The light scattering intensity (measured by the degree of veiling) depends on the size of the components, expressed in micrometres (μ) and depends on the degree of refractive index index of each component. Generally, the components that can be properly processed need to be selected to have very small particle size materials or selected with a minimum refractive index difference between them. This task proves very difficult.
It is an object of the present invention to solve the above and other problematic issues.
The present invention relates to a multilayer polymer based structure. The films in the composition are suitable for the manufacture of pharmaceutical grade pharmaceutical devices, which may be containers for storing medical solutions or blood products, blood bags and the like or other products made of a multilayer structure.
The present invention relates to a method for producing a multilayer film having the following physical characteristics (1) mechanical coefficients of less than 40,000 psi, more preferably less than 25,000 psi, as determined by the measurement required by ASTM D-882, (2) 70% of the length after deformation
<img file="HUT72715A_D0002.tif" />
or more preferably recovering 75% or more, (3) if, for a composition of 9 ml thickness, the optical lattice is determined to be less than 30% and preferably less than 15% by measurement according to ASTM D-1003, (4) ) At a processing temperature of 1 Hz, the tangent loss is greater than 1.0, more preferably greater than 2.0, (5) the elemental halogen content is less than 0.1%, more preferably less than 0.01%, (6) the low molecular weight water-soluble fraction is less than 0.1%, more preferably less than 0.005%, (7) the maximum dielectric loss at 25-250 ° C and at 1-60 MHz is 0.05 or more , more preferably 0.1 or greater, (8) the autoclave resistance, measured by measuring swelling or partitioning of the sample at or below 121 ° C at 27 psi, is less than or equal to 60%, more preferably less than or equal to, and (9) tension whitening when tensioning at low speed is approx.
inch (50 cm) / min. It does not occur at 100% elongation or its absence can be detected.
The multilayer composition of the present invention comprises an upper layer, which preferably consists of polypropylene copolymers formed from styrene and hydrocarbon block copolymers. More preferably, a propylene copolymer is prepared from ethylene-butene-styrene ("SEBS") components which comprise 0-20% by weight of the top layer. In addition, a structure is formed which forms a radio frequency ("RF") sensitive layer and adheres to the upper layer. The RF layer comprises a first component polypropylene polymer, a second component non-propylene polyolefin (a compound that does not contain propylene repeat units), and a third radio frequency sensitive component. In addition, the layer comprises a fourth component, which is a polymer compatibility aid. Alternatively, other layers may be incorporated into the structure, e.g. a core layer as well as a waste layer or barrier layers which are added to the top layer and the RF layers to improve the performance of the resulting film structure.
The RF layer is described in co-pending U.S. Patent Application No. 1417 P030, which is incorporated herein by reference. The multilayer film structure of the present invention provides additional features that the RF layer alone would not provide. Other features of the multilayer film are e.g. that the outer surface is bright and the outer surface of the film layer has less adhesion. In addition, the multilayer film structure has improved moisture-repellent and penetration-inhibiting properties, as well as improved optical translucency and resistance. In addition, the structure is much cleaner optically, and reduced the migration ability of some of its components toward the materials in the container.
The central layer, which contains three components between the outer layer and the RF layer. Preferably, the first component is polypropylene which is ca. 40% of the core layer, the second component is an ultra-low density polyethylene ("ULDPE"), which is ca. 50% by weight, and the third component is a styrene-hydrocarbon block copolymer, more preferably a SEBS block copolymer, having a core layer of about 50%. 10% by weight. The entire central layer is 4.0 mm thick.
Among other things, for economic reasons, it is desirable that the waste material produced during the processing of the film material and re-ground into the film structure composition of the present invention. This results in the use of a sufficiently high percentage by weight of the loss material in the entire laminate film structure, thus greatly reducing the cost of the film product. The re-ground waste is incorporated into the structure described above, either as a separate layer which is somewhere between the top layer and the RF layer, or it can be blended into the central layer as an additional component. In any case, a great deal of costs are saved by recycling the waste material.
In order to increase the gas-permeability properties of the structure, it is desirable to incorporate a barrier layer between the top layer and the RF layer. The barrier layer may be bonded to its exposed layers by athletic bonding layers. The barrier layer may be composed of ethylene vinyl alcohols such as ethylene vinyl alcohols. the product sold under the trade name (Evalca Co.) and may also be highly glassy or crystalline polyamide, e.g. Sclar PA® (Dupont Chemical Co.); and high nitrile-containing acrylonitrile copolymers, e.g. marketed under the trademark Barex® (British Petroleum).
Films with the above structure and composition have been shown to be elastic, optically translucent, non-tearable, and can be sterilized by steam and radiation. In addition, the film compositions of the present invention meet the requirements of pharmaceutical use, since the film components that make up them are of minimal extractibility and thus are not contacted with liquids or stored materials in contact with the composition. In addition, the film composition of the present invention is not environmentally contaminated since it does not result in hazardous decomposition products upon combustion. Last but not least, film compositions of the present invention are similarly economical compared to PVC materials and therefore their competitors.
Further features and advantages of the composition of the present invention will be described in detail below and illustrated in the accompanying drawings.
- 10A brief description of the figures
Figure 1 is a cross-sectional view of a double-layer film structure according to the invention;
Figure 2 is a cross-sectional view of a three-layer film structure according to the invention which differs from the film composition of Figure 1 in that it also includes a central central layer;
Figure 3 is a cross-sectional view of the film structure of Figure 1 with a solution contact layer;
Figure 4 is a cross-sectional view of a four-layer film structure according to the invention, comprising a layer of discarded waste material between the upper layer and the central layers;
Figure 5 is a cross-sectional view of a film structure according to the present invention having a layer formed by re-grinding a separate waste material between the central and RF layers;
Fig. 6 is a cross-sectional view of a film structure according to the invention comprising a layer of recycled material from a separate waste material which divides the central layer into two layers and is located between them;
Fig. 7 is a cross-sectional view of a two-layer film structure according to the invention, comprising a barrier layer and two interconnecting layers between the central and RF layers;
Figure 8 illustrates the structure shown in Figure 6 except that the barrier layer is located between the central layer and the upper layer;
Figure 9 is a cross-sectional view of a film structure according to the invention, wherein the barrier layer divides the central layer into two central layers; and Fig. 10 is a view of a container made of a film structure according to the invention.
<img file="HUT72715A_D0003.tif" />
The compositions of the invention may be embodied in various ways, and are described herein as preferred embodiments, but are intended to be exemplary and unless the principles of the invention are contemplated by all other embodiments thereof, i.e., the examples and embodiments disclosed herein are not intended to be limitation.
The present invention relates to multi-layered film structures which meet the requirements described above.
Figure 1 shows a double layer film structure 10 comprising an upper layer 12 and a radio frequency ("RF") sensitive layer 14. The top layer 12 is heat-resistant and abrasion-resistant and is preferably a polypropylene based copolymer, more preferably a polypropylene copolymer blended with styrene and hydrocarbon block copolymers. More preferably, the top layer 12 is a polypropylene copolymer blended with SEBS block copolymer for approx. 0-20% by weight. The top layer 12 should have a thickness of 0.2 to 3.0 mm.
The dielectric loss of the RF sensitive layer 14 of the present invention is greater than 0.05 within the frequency range of 1 to 60 MHz and within the range of room temperature to 250 ° C. Preferably, the RF layer 14 comprises four components. The RF layer 14 has RF weldability / sealability characteristics, is also resilient to heat deformation and is compatible with the film structure 10. The first component of the RF layer 14 is a polypropylene copolymer, preferably a propylene a-olefin random copolymer ("PPE"). PPE has sufficient strength and softening resistance of approx. At an autoclave temperature of 121 ° C. However, PPE itself is too brittle and thus would not meet the elasticity requirements if mixed with alloying, blending, certain low coefficient polymers to achieve very good elasticity.
<img file="HUT72715A_D0004.tif" />
The low coefficient copolymers that may be used may be ethylene based copolymers such as ethylene copolymers. ethylene-vinyl acetate copolymer ("EVA"), ethylene-α-olefin copolymers or so-called ultra-low density (typically less than 0.90 kg / l) polyethylenes ("ULDPE"). Such ULDPE polymers may be commercially available products such as, e.g. under the tradename TAFMER® (Mitsui Petrochemical Co.) and A48, Exact® (Exxon Chemical Company) and polymers under the trade name and technology of 4023-4024 or Insite® (Dow Chemical Co.). In addition, polybutene-1 compounds ("PB"), such as i.p. PB-8010, PB-8310 from Shell Chemical Company; and thermoplastic elastomers based on SEBS block copolymers (Shell Chemical Company) include polyisobutene ("PIB"), such as Vistanex L-80, L -100, L-120, L-140 (Exxon Chemical Company), ethylene alkyl acrylate, methyl acrylate copolymers ("EMA") such as, e.g. EMAC 2707 and DS-1130 (Chevron) and n-butyl acrylates (ENBA) (Quantum Chemical). Ethylene copolymers, e.g. copolymers of acrylic and methacrylic acid, as well as their partially neutralized salts and ionomeric forms, e.g. PRIMACOR® (Dow Chemical Company) and SURYLN® (El DuPont de Nemours & Company) may also be used. Generally, ethylene-based copolymers have a melting point lower than ca. 110 ° C and therefore not suitable for 121 ° C autoclave treatment. In addition, only the use of a component within certain specific limits is sufficient to meet the requirements of flexibility or autoclave handling.
Preferably, the first component is selected from the group consisting of polypropylene homo and random copolymers formed with? -Olefins, which is about. 30-60% by weight, more preferably 35-45% and most preferably 45% by weight of the film
<img file="HUT72715A_D0005.tif" />
preparation. For example, a random copolymer of polypropylene and ethylene material is one in which the ethylene content is ca. 0 to 6% by weight, more preferably 2 to 6% by weight, based on propylene. This component can be advantageously used in the film as the first component.
The second component of the RF layer 14 is a layer that provides the layer 14 with flexibility and low temperature deformability. This layer consists of polyolefins which do not contain propylene repeat units ("non-propylene-based polyolefins"), which may be ethylene copolymers, e.g. ULDPE, polybutene, butylene-ethylene copolymers, ethylene-vinyl acetate copolymers, wherein the vinyl acetate content is ca. 18-50%, ethylene methyl acrylate copolymers, wherein the methyl acrylate content is ca. 20-40%, ethylene-n-butyl acrylate copolymers, wherein the n-butyl acrylate content is 20-40%, ethylene-acrylic acid copolymers, where the acrylic acid content is greater than about 20%. 15%. Such products which may be used, e.g. Tafmer A-4085 (Mitsui), EMAC DS-1130 (Chevron), Exact 4023, 4024 and 4028 (Exxon). Preferably, the second component is either ULDPE from Mitsui Petrochemical Company, marketed under the tradename TAFMER A-4085, or polybutene-1, PB8010 and PB8310 (Shell Chemical Co.). 25-50% by weight of the film, preferably 35-45% by weight, most preferably 45% by weight of the film.
The first and second components of the RF layer 14 may also be replaced by a single component, which may be a high melting point and a flexible olefin such as. polypropylene, marketed under the name Rexene Company FPO. The component has a melting point greater than 130 ° C and a constant less than 20,000 psi. This component is approx. 30-60% by weight.
·· · «·.. . “ ·· ·· · ······ ·· ··
In order to provide adequate RF dielectric loss for the RF layer 14 to 14, certain high dielectric loss components are incorporated as a third component into the film structure 10. For example, EVA and EMA components having a relatively high comonomer content have a significant dielectric loss characteristic at 27 MHz and therefore allow the compositions or the material to be dielectric weldable. A group of such materials, polyamides and ethylene-vinyl alcohol ("EVOH") copolymers (typically produced by hydrolysis of EVA copolymers) are capable of providing dielectric loss at a suitable temperature. Other active substances which may be used, e.g. copolymers of PVC, vinylidine chlorides and fluorides, bisphenol A and epichlorohydrin, marketed as PHENOXYS® (Unión Carbide). However, the use of large amounts of such chlorine and fluorine-containing components carries environmental properties, since the burning of such materials produces inorganic acids. Therefore, the third component of the RF layer 14 is preferably selected from polyamides.
Preferably, the polyamides used in the composition of the present invention are the aliphatic polyamides prepared by the reaction of C2-13 diamines with their condensation reaction and the aliphatic polyamides obtained by the condensation reaction of C2-13 diacids and the polyamides obtained by the condensation reaction of dimeric fatty acids containing amides (random block or graft polymers).
In addition, nylon materials are widely used as film materials as they impart wear resistance to the film. However, nylon is rarely found in the layer that comes in contact with the medical solution, since they contaminate the contact solution, because I can dissolve in this solution. However, in their experiments we have found that various dimeric fatty acid polyamides can be used for this purpose.
- for 15 purposes, which can be eg. Henkel Corporation's MACROMELT and VERSAMID branded products, as they do not lead to such contamination when applied to the RF layer 14 as the third component and are therefore the most preferred components. The third component has an approx. 3 to 40%, more preferably 7 to 13% and most preferably 10% of the layer.
The fourth component of the RF layer 14 provides matching and compatibility between the polar and non-polar components of the RF layer 14. The fourth component may be a styrene-hydrocarbon block copolymer and preferably a SEBS block copolymer modified with maleic anhydride, epoxy or carboxylate groups. More preferably, the fourth component is a SEBS block copolymer containing maleic anhydride functional groups. Such a product is marketed under the trademark KRATON RP-6509 by Shell Chemical Company. The amount of the fourth component in the RF layer 14 is approx. 5 to 40% by weight, preferably 7 to 13% by weight<sup>0</sup>/) and most preferably 10% by weight.
It may also be desirable to include a fifth component in the RF layer 14, which may be a SEBS block copolymer unmodified with the above functional groups, e.g. is a product of Shell Chemical Company under the trademark KRATON G-1652. The component in the RF layer is 5 to 40% by weight, more preferably 7 to 13% by weight<sup>0</sup>and) and most preferably is present in an amount of 10% by weight.
Preferably, the RF sensitive layer has a thickness of 1 to 9 mm, more preferably 5.0 to 8.0 mm, and most preferably 5.0 mm. The thickness of the top layer is 0.2 to 3.0 mm, more preferably 0.5 mm.
Figure 2 illustrates another embodiment of the composition of the present invention comprising a central layer 16 located between the top layer 12 and the RF layer 14. The central layer 16 provides the structure 10
Up to 16 deformation resistance and flexibility, and this layer ensures compatibility between the individual components of the film structure 10.
Preferably, the central layer has a thickness of 5.0 to 10 mm and most preferably 1 to 4 mm. The central layer 16 comprises three components. The first component is a polyolefin, preferably a polypropylene, in an amount of 20 to 60% by weight of the central layer 16, more preferably 35 to 50% by weight and most preferably 45% by weight.
The second component of the central layer 16 may be selected from compounds which provide the flexibility of the central layer 16, such materials being ULDPE, polybutene copolymers, preferably the second component of the central layer is ULDPE or polybutene-1. crowd<sup>0</sup>), more preferably 40-50% by weight and most preferably 40% by weight.
The third component of the central layer 16 is selected from compounds which provide compatibility between the other components of the central layer 16 and which may be e.g. styrene-hydrocarbon block copolymers, most preferably SEBS block copolymers. In the central layer 16, the third component is generally 5 to 40% by weight, more preferably 7 to 15% by weight, and most preferably 15% by weight.<sup>0</sup>/) in quantities.
It is also possible to add a fourth component to the central layer 16, which fourth component may be made from a ground waste material made from the waste produced during the manufacture of each container. The waste material is dispersed in the central layer 16. The waste material for the central layer 16 is about 1 to about 10 cm. 0 to 50% by weight, more preferably 10 to 30% by weight, and most preferably 3 to 12% by weight.
···
Figure 3 shows a film or plate structure shown in Figure 1 with a contact layer 17 adjacent to the RF layer opposite the top layer 12. In the embodiment, the contact layer 17 comprises three components, which may be the first three components in the same amount by weight of the central layer 16 as described above. Preferably, the thickness of the contact layer 17 is 0.2 to 1.0 mm, most preferably 1.0 mm.
Figure 4 shows another embodiment of a multilayer film structure comprising an upper layer 12, a central layer 16 and an RF layer 14 as described above, further comprising a waste material layer 20 between the upper layer 12 and the central layer 16. . Figure 5 illustrates a layer of separated waste material 20 located between the central layer 16 and the RF layer 20. 6. Fig. 4a shows a layer of waste material 20 which divides the central layer 16 into two portions, thereby forming a first and second central layers 14a and 14b. Preferably, the thickness of the re-ground waste material layer is 0.5 to 5.0 mm, and most preferably 1.0 mm.
Figure 7 illustrates another embodiment of the composition of the invention, wherein the composition comprises seven layers, the upper layer 12, the central layer 16, and the RF layer 14 described above, and the structure further comprises an inhibitor 26. a layer disposed between the central layer 16 and the RF layer 14 and connected thereto by the engaging or adhesive layers 28 located on opposite sides of the barrier layer 26. 8. Fig. 4a shows the barrier layer 26 located between the central layer 16 and the upper layer 12. THE
9th Fig. 4a shows the barrier layer 26 which divides the central layer 14 into two central layers 14a and 14b. The barrier layer 26 increases the gas-resistant properties of the film structure 10. The barrier layer 26 is selected to contain ethylene vinyl alcohol, such as ethylene vinyl alcohol. Evalca (Evalca Co.) is a trademarked material, or is highly glassy or
<img file="HUT72715A_D0006.tif" />
crystalline polyamide materials such as. Sclar PA® (Dupont Chemical Co.) or may be a high nitrile-containing acrylonitrile copolymer, e.g. Barex® (British Petroleum). Preferably, the barrier layer 26 is ethylene vinyl alcohol having a thickness of 0.3 to 1.5 mm, more preferably 1.0 mm.
The adhesive layers 28 are e.g. modified ethylene and propylene copolymers, e.g. the product sold under the trade name Prexar (Quantum Chemical Co.) or under the trade name Bynel (Dupont), such a layer having a thickness of 0.2 to 1.0 mm, most preferably 0.5 mm.
The above layers may be processed by co-extrusion, extrusion coating or other acceptable process. Of course, it is understood that the method of making the film structure is not within the scope of the invention, and thus the scope of the invention is not limited in this respect.
The agents of the invention may be used to prepare intravenous therapeutic containers such as. the container shown in Figure 10, wherein the container is designated 30.
Films made from various combinations of the above components and materials formed by various weight percent are within the scope of the invention and are tested by the test assays shown in the examples below.
(1) Ability to autoclave:
Resistance to autoclaving based on sample flow or increase in sample length for 1 hour
125 At a temperature of 27 ° C and 27 psi. Resistance to autoclave treatment should be less than or equal to 60%.
(2) Low and room temperature extensibility:
(A) Low temperature extensibility
An impact test apparatus equipped with a measuring apparatus equipped with a low temperature jacket cooled with liquid nitrogen was applied to 7x7 inch (18 cm x 18 cm) film samples. The samples are placed in a circular sample holder which holds approx. 6 inches (15 cm) in diameter. A hemispherical stopper is driven at high speed (about 3 m / sec) by pressure sensors to the pre-treated film and loaded at the center. The collision energy temperature increases dramatically at a given point when the fractured sample becomes rigid to soft, in which case high tensile morphology is used to measure the low temperature behavior of the film ("L-temperature").
(B) Mechanical constant and recovery value
An autoclave-treated film sample of a particular geometry is placed on a servo-hydraulically guided mechanical tester equipped with crossheads to extend the sample at a crosshead speed of 10 inches (25 cm / min) and the samples are approx. 20% elongation. At this point we determine the distance of the crossheads during which the specimen is elongated and then their displacement in the opposite direction to the elongation of the specimen. The voltage-to-force behavior is recorded with a digital meter. From the stress-strain curve, determine the elastic coefficient ("E (Kpsi)") from the first slope and determine the degree of recovery from the elongation at stretch, expressed as a percentage.
(3) RF Processability:
Callahan 27.12 MHz connected to a 2 KW radio frequency generator in a brass rectangular approx. 0.25 (6.3 mm) x 4 inch (10 cm) brass tool
<img file="HUT72715A_D0007.tif" />
which is located opposite a flat brass electrode which is also connected to the generator. After closing, two sheets of a given material in the tool are disposed between the two opposing brass plates, the sides of which are opposite each other. Subsequently, RF amplitudes of varying amplitudes are applied to the disks over different time periods. When the RF cycle is complete, the tool is opened and the solder seal strength is manually checked by attempting to pull the two sheets apart. The soldering strength (as opposed to film strength) and the type of seal break (peeling, rupture, or adhesion failure) are suitable for determining the degree of material response to RF.
Alternatively, the film is first coated with 100 angstrom gold or palladium metal plating to make the surface conductive, then cut to circular geometry and placed between parallel electrodes in a dielectric capacity cell. Using a Hewlett Packard 4092 Automatic RF Bridge, the dielectric constant and dielectric loss are determined at various frequencies up to 10 MHz and at various temperatures up to 150 ° C. Dielectric loss allows heat generation below a given RF value to be calculated. Calculations or correlations from RF seal experiments can determine the minimum dielectric loss used for processing.
If we obtain the RF sealing capability from a Callahan solder, use the following scale to evaluate this:
- 21 ·« • · · ·
<td>RF energy</td><td>RF duration</td><td>Sealing strength</td><td>Classification</td>
<td> 80%</td><td> 10</td><td>no</td><td> 0</td>
<td> 80%</td><td> 10</td><td>Peel</td><td> 1</td>
<td> 80%</td><td> 05</td><td>Peel</td><td> 2</td>
<td> 60%</td><td> 03</td><td>Strong</td><td> 3</td>
<td> 50%</td><td> 03</td><td>Strong</td><td> 4</td>
<td> 30%</td><td> 03</td><td>Strong</td><td> 5</td>
(4) Optical transparency:
Post-autoclave-treated film samples were first approx. Cut into 2 x 2 inch (5 x 5 cm) square samples, place the samples in a Hunter Colorimeter, and measure the internal opacity according to ASTM D-1003. Generally, the required internal haze should be less than 30%, preferably less than 30% at these thicknesses ("% haze").
(5) Deformation whitening:
The autoclave-treated film at low speed is approx. At 20 inches (50 cm) / min. It is elongated to 100% elongation (twice the original length) and meanwhile the tensile whiteness (indicated by 1) and the lack of tension whitening (indicated by 0) are measured ("tension whiteness").
(6) Environmental compatibility:
Environmental compatibility includes three important features: (a) material-free low molecular weight plasticizers that can be washed into the environment after disposal, (b) the material is thermoplasticly recyclable into a suitable form for subsequent primary use in medical transport, and (c) disposed of by incineration and produce energy while producing no dangerous inorganic acid ("environmental"). In addition, the composition is less than
<img file="HUT72715A_D0008.tif" />
0.1% by weight of halogen in order to facilitate recycling by melt processing to a loss tangent to the resulting composition greater than 1.0 at 1 Hz at the processing temperature.
(7) Solution Compatibility:
Solubility compatibility means that the solution contained in the film is not contaminated by the components of the film composition ("solution compatibility"). The low molecular weight water soluble fraction of the composition is less than 0.1%.
The following formulations were tested by test assay according to the above procedures and film data is given below.
• ·
<img file="HUT72715A_D0009.tif" />
<td>Solution compatibility</td><td></td><td>Yes</td>
<td>Low temperature</td><td></td><td>-35 ° C</td>
<td>Dielectric loss</td><td></td><td>co</td>
<td>Autoclave</td><td></td><td>c Φ CD</td>
<td>Environmental mental</td><td></td><td>Yes</td>
<td>% blur</td><td></td><td>She</td>
<td>Voltage Recovery v Eikpsi) ___</td><td></td><td> 75</td>
<td>Modulus (Psi)</td><td></td><td> 25</td>
<td>Layer composition</td><td>0.5mm-100% Amoco PP Copolymer 8410</td><td>8.0mm-40% Solvay Fortiline PP Copolymer 4208 40% Mitsui Tafmer ULDPE 10% Shell Kraton RP-6509 10% Henkel Macromelt 6301</td>
<td>Layer type</td><td>Upper layer</td><td>RF layer</td>
<td>Reference number</td><td colspan="2">Figure 1</td>
<td></td><td>c CD</td><td></td>
<td></td><td>-40 ° C Ί</td><td></td>
<td></td><td>FIVE</td><td></td>
<td></td><td>c <D FIVE</td><td></td>
<td></td><td>Yes</td><td></td>
<td></td><td>CXJ</td><td></td>
<td></td><td> 75</td><td></td>
<td></td><td> 25</td><td></td>
<td>0.5mm-100% Amoco PP Copolymer 8410</td><td>4.0mm-45% Solvay Fortiline PP Copolymer 4208 40% Mitsui Tafmer ULDPE 15% Shell Kraton G1667</td><td>5.0mm-40% Solvay Fortiline PP Copolymer 4208 40% Mitsui Tafmer ULDPE 10% Shell Kraton RP-6509 10% Henkel Macromelt 6301</td>
<td>Upper layer l</td><td>core Layer</td><td>RF layer</td>
<td colspan="3">Figure 2</td>
• ·
<td>Solution compatibility</td><td></td><td>Yes</td><td></td>
<td>Low temperature</td><td></td><td>She She LD CO., LTD</td><td></td>
<td>Dielectric loss</td><td></td><td> 04</td><td></td>
<td>Autoclave</td><td></td><td>C Φ CD</td><td></td>
<td>Environmental mental</td><td></td><td>Yes</td><td></td>
<td>% blur</td><td></td><td>LD</td><td></td>
<td>Voltage Recovery y E (kpsi) ___</td><td></td><td> 70</td><td></td>
<td>Modulus (Psi)</td><td></td><td> 25</td><td></td>
<td>Layer composition</td><td>0.5mm-100% Amoco PP Copolymer8410</td><td>8.0mm-40% Solvay Fortiline PP Copolymer 4208 40% Mitsui Tafmer ULDPE 10% Shell Kraton RP-6509 10% Henkel Macromelt 6301</td><td>1.0mm-45% Solvay Fortiline PP Copolymer 4208 40% Mitsui Tafmer ULDPE 15% Shell Kraton G1667</td>
<td>Layer type</td><td>Upper layer</td><td>RF layer</td><td>Top layer in contact with solution</td>
<td>Reference number</td><td colspan="3">Figure 3</td>
<img file="HUT72715A_D0010.tif" />
<td>Solution compatibility</td><td></td><td></td><td>Yes</td><td></td>
<td>Low temperature</td><td></td><td></td><td>-35 ° C</td><td></td>
<td>Dielectric loss</td><td></td><td></td><td></td><td></td>
<td>Autoclave</td><td></td><td></td><td>Yes</td><td></td>
<td>Environmental mental</td><td></td><td></td><td>Yes</td><td></td>
<td>% blur</td><td></td><td></td><td>CD</td><td></td>
<td>Voltage recovery _ y E (kps)</td><td></td><td></td><td> 75</td><td></td>
<td>Modulus (Psi)</td><td></td><td></td><td> 25</td><td></td>
<td>Layer composition</td><td>0.5mm-100% Amoco PP Copolymer 8410</td><td>1.0 mm to 100% re-ground material</td><td>3.0mm-45% Solvay Fortiline PP Copolymer 4208 40% Mitsui Tafmer ULDPE 15% Shell Kraton G1667</td><td>5.0mm-40% Solvay Fortiline PP Copolymer 4208 40% Mitsui Tafmer ULDPE 10% Shell Kraton RP-6509 10% Henkel Macromelt 6301</td>
<td>Layer type</td><td>Upper layer</td><td>Re-ground layer</td><td>core Layer</td><td>RF layer</td>
<td>Reference number</td><td colspan="4">Figure 4</td>
<td>c ω _CT></td><td>Yes</td><td></td><td></td>
<td><_> She LO CO t</td><td>-35 ° C</td><td></td><td></td>
<td></td><td></td><td></td><td></td>
<td>Yes</td><td>Yes</td><td></td><td></td>
<td>c 0) _O)</td><td>Yes</td><td></td><td></td>
<td>CD</td><td>CD</td><td></td><td></td>
<td> 75</td><td> 75</td><td></td><td></td>
<td> 25</td><td> 25</td><td></td><td></td>
<td>0.5mm-100% Amoco PP Copolymer 8410</td><td>3.0mm-45% Solvay Fortiline PP Copolymer 4208 40% Mitsui Tafmer ULDPE 15% Shell Kraton G1667</td><td>1.0 mm to 100% re-ground material</td><td>5.0mm-40% Solvay Fortiline PP Copolymer 4208 40% Mitsui Tafmer ULDPE 10% Shell Kraton RP-6509</td>
<td>Upper layer</td><td>core Layer</td><td>Re-ground layer</td><td>RF layer</td>
<td colspan="4">Figure 5</td>
·· ·· ·· • · · · · · ♦*· ·« «» <sub>Λ</sub>· · · · · *· ·♦ ··
<img file="HUT72715A_D0011.tif" />
<td>Solution compatibility</td><td></td><td></td><td>c Φ CT</td><td></td><td></td>
<td>Low temperature</td><td></td><td></td><td>She 0 in co 1</td><td></td><td></td>
<td>Dielectric Loss ____________________________________________________________________________________________________________________________________________________________________________________________________________________________________________1</td><td></td><td></td><td>tt</td><td></td><td></td>
<td>Autoclave</td><td></td><td></td><td>Yes</td><td></td><td></td>
<td>Environmental mental</td><td></td><td></td><td>Yes</td><td></td><td></td>
<td>% blur</td><td></td><td></td><td>CD</td><td></td><td></td>
<td>Voltage Recovery VEŰSPsi)</td><td></td><td></td><td> 75</td><td></td><td></td>
<td>Modulus (Psi)</td><td></td><td></td><td> 25</td><td></td><td></td>
<td>Layer composition</td><td>0.5mm-100% Amoco PP Copolymer 8410</td><td>1.5mm-45% Solvay Fortiline PP Copolymer 4208 40% Mitsui Tafmer ULDPE 15% Shell Kraton G1667</td><td>1.0 mm to 100% re-ground material</td><td>1.5mm-45% Solvay Fortiline PP Copolymer 4208 40% Mitsui Tafmer ULDPE 15% Shell Kraton G1667</td><td>5.0mm-40% Solvay Fortiline PP Copolymer 4208 40% Mitsui Tafmer ULDPE 15% Shell Kraton RP-6509 10% Henkel Macromelt 6301</td>
<td>Layer type</td><td>Upper layer</td><td>core Layer</td><td>Re-ground layer</td><td>core Layer</td><td>RF layer i</td>
<td>Reference number</td><td colspan="5">Figure 6</td>
··
<td>Solution compatibility</td><td></td><td></td><td>c</td><td></td><td></td><td></td>
<td>Low temperature</td><td></td><td></td><td>-20 ° C</td><td></td><td></td><td></td>
<td>Dielectric loss</td><td></td><td></td><td></td><td></td><td></td><td></td>
<td>Autoclave</td><td></td><td></td><td>c Φ o</td><td></td><td></td><td></td>
<td>Environmental mental</td><td></td><td></td><td>Yes</td><td></td><td></td><td></td>
<td>% blur</td><td></td><td></td><td> 20</td><td></td><td></td><td></td>
<td>Voltage recovery YE (kpsi)</td><td></td><td></td><td> 20</td><td></td><td></td><td></td>
<td>Modulus (Psi)</td><td></td><td></td><td> 30</td><td></td><td></td><td></td>
<td>Layer composition</td><td>0.5mm-100% Amoco PP Copolymer 8410</td><td>2.0mm-45% Solvay Fortiline PP Copolymer 4208 40% Mitsui Tafmer ULDPE 15% Shell Kraton G1667</td><td>0.5mm-100% Bynel</td><td>1.0 mm-100% EVOH</td><td>0.5mm-100% Bynel</td><td>5.0mm-40% Solvay Fortiline PP Copolymer 4208 40% Mitsui Tafmer ULDPE 10% Shell Kraton RP-6509 10% Henkel Macromelt 6301</td>
<td>Layer type</td><td>Upper layer</td><td>core Layer</td><td>bonding layer</td><td>Barrier layer</td><td>bonding layer</td><td>RF layer</td>
<td>Reference number</td><td colspan="6">Figure 7</td>
<img file="HUT72715A_D0012.tif" />
» · ···
- 28 ·· • ·
<td>Otdat compatibility</td><td></td><td></td><td></td><td>c Φ O)</td><td></td><td></td>
<td>Low temperature</td><td></td><td></td><td></td><td>ω She cy</td><td></td><td></td>
<td>Dielectric loss</td><td></td><td></td><td></td><td>CO</td><td></td><td></td>
<td>Autoclave</td><td></td><td></td><td></td><td>c Φ _σ></td><td></td><td></td>
<td>Environmental mental</td><td></td><td></td><td></td><td>c Φ SHE)</td><td></td><td></td>
<td>% blur</td><td></td><td></td><td></td><td> 20</td><td></td><td></td>
<td>Voltage Recovery y E (kpsi) ___</td><td></td><td></td><td></td><td> 70</td><td></td><td></td>
<td>Modulus (Psi)</td><td></td><td></td><td></td><td> 30</td><td></td><td></td>
<td>Layer composition</td><td>0.5mm-100% Amoco PP Copolymer 8410</td><td>0.5mm-100% Bynel</td><td>1.0 mm-100% EVOH</td><td>0.5mm-100% Bynel</td><td>2.0mm-45% Solvay Fortiline PP Copolymer 4208 40% Mitsui Tafmer ULDPE 15% Shell Kraton G1667</td><td>5.0mm-40% Solvay Fortiline PP Copolymer 4208 40% Mitsui Tafmer ULDPE 10% Shell Kraton RP-6509 10% Henkel Macromelt 6301</td>
<td>Layer type</td><td>Upper layer</td><td>bonding layer</td><td>Barrier layer</td><td>bonding layer</td><td>Seed layer</td><td>RF layer</td>
<td>Reference number</td><td colspan="6">Figure 8</td>
<td>1 Solution com</td><td>patibility</td><td></td><td colspan="2"></td><td colspan="4"></td><td></td><td>Yes</td><td></td><td colspan="4"></td><td colspan="6"></td><td>false document</td><td>N CU Φ</td>
<td></td><td rowspan="2">temperature</td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td> 03 4—</td><td>> <4 » Φ</td>
<td>co cn Φ <</td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td>ρ ο CXI</td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td>means a</td><td>Φ CD Φ >,</td>
<td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td>Ε</td><td>c 'Φ</td>
<td>She</td><td>N</td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td>ω</td><td> —</td>
<td>2 Φ Φ b</td><td>m <sup>05</sup>§ * Φ ω φ ο * - Ε</td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td>CO</td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td>C Ν φ C</td><td>c ro E</td>
<td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td>CU</td><td>'CU</td>
<td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td>J2</td><td>CU</td>
<td rowspan="2">> 'Φ She</td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td>C</td><td> 4-^</td>
<td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td>Yes</td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td>azo</td><td>CO>,</td>
<td> <</td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td>Φ</td>
<td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td>c</td>
<td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td> □</td><td rowspan="2">CU</td>
<td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td>
<td>Φ</td><td>ω</td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td>
<td>N n></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td>C</td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td>ω</td><td>u></td>
<td>> s</td><td><sub>(</sub>c</td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td>ω</td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td> □</td><td>-Q</td>
<td>C</td><td>φ</td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td>CD</td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td>Ε</td><td>'Φ</td>
<td>:SHE</td><td>Ε</td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td>φ</td><td>L.<sup>:</sup>SHE</td>
<td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td>-Q</td><td></td>
<td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td>Γ ~</td><td> >></td>
<td> 1</td><td>CD</td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td>φ</td><td>CD u.</td>
<td> £</td><td> '05</td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td>ω</td><td>'CU</td>
<td>o .c</td><td>ω ω Ο</td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td> 20</td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td>φ 4 » Φ</td><td> 4—»</td>
<td>o ^ ·</td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td>ν</td><td>c 'CU</td>
<td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td>C /)</td><td rowspan="2">E</td>
<td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td>'φ</td>
<td>cn 'Φ</td><td>» Φ</td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td>c</td><td>CO</td>
<td>ω</td><td> >></td><td>(J) Q</td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td>ο</td><td>CO</td>
<td> :□</td><td>φ> φ</td><td>-Ζ</td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td>Ο</td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td rowspan="2">CO</td>
<td>Ν</td><td>Ν tZ ω</td><td>ιχι</td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td>Γ--</td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td>C 0</td>
<td>Φ LL</td><td>σ)></td><td> ></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td>0 'φ</td><td>c.</td>
<td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td>Q.</td><td>She</td>
<td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td>c</td>
<td>(Λ</td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td>'Φ</td>
<td>D</td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td>Ο</td><td>Φ</td>
<td>Z5</td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td>ο</td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td>Ό</td><td></td>
<td>Ό</td><td>ο.</td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td>C0</td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td rowspan="2">C0</td><td>Φ</td>
<td>SHE</td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td>_Q</td>
<td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td>ω</td><td>ω</td>
<td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td rowspan="2">on</td><td></td>
<td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td colspan="2"></td><td colspan="2"></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td>
<td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td>u_</td><td> 4—»</td>
<td></td><td></td><td></td><td> 1</td><td></td><td>Cl.</td><td></td><td>LLI CL Ο</td><td>RCD</td><td></td><td></td><td></td><td>η</td><td></td><td>LU Q. Q</td><td>r <D</td><td>η</td><td></td><td>LU CL Q</td><td>σ> o tn</td><td></td><td></td><td>procedures</td><td>• CO E u.</td>
<td></td><td></td><td></td><td>ο</td><td></td><td> □.</td><td></td><td> __1</td><td> <0</td><td></td><td></td><td></td><td>u_</td><td></td><td>_ι</td><td>CD</td><td>CL</td><td></td><td>-J</td><td rowspan="2">CL tr co</td><td>φ</td><td></td><td><D</td><td>She</td>
<td>Φ Φ 'Φ</td><td></td><td></td><td>Q. ο Ο_</td><td></td><td>φ C Έ</td><td>CO</td><td>ο L- Φ ε</td><td>tone G1</td><td></td><td></td><td></td><td>φ C Έ</td><td>CO</td><td>Ξ> <5 ε</td><td>tone G1</td><td>Φ _c Έ</td><td>CO</td><td>Ό u_ Φ E</td><td>U. ο U. Ο Φ</td><td></td><td>or *</td><td>M— c CÜ >></td>
<td></td><td></td><td></td><td></td><td></td><td>ο</td><td>ο</td><td>Φ</td><td>Φ</td><td></td><td></td><td></td><td>ο</td><td>ο</td><td>Φ</td><td>Φ</td><td>ο</td><td>She</td><td>Φ</td><td>Φ</td><td></td><td></td><td></td><td> “7</td>
<td rowspan="2">Φ IM ω</td><td></td><td></td><td>ο ο</td><td></td><td>υ_ 'Χ</td><td>CM · *}</td><td> 1-</td><td>LL</td><td>φ</td><td>τ</td><td>Φ</td><td>LL >,</td><td>osl</td><td> 1-</td><td></td><td>LL >></td><td>CM</td><td>F-</td><td></td><td>φ</td><td></td><td>> ϊ</td><td>She</td>
<td></td><td></td><td>ο</td><td></td><td> 05</td><td></td><td>Ώ</td><td></td><td>C</td><td>ο</td><td>C</td><td>Φ</td><td></td><td>D</td><td> “77</td><td>Φ</td><td></td><td></td><td> —</td><td></td><td></td><td rowspan="2">Φ</td><td>cv</td>
<td></td><td></td><td></td><td>t</td><td>Ο</td><td> ></td><td>Π)</td><td>ω</td><td>φ</td><td> >></td><td></td><td> >»</td><td> ></td><td>Π)</td><td>ω</td><td>Φ</td><td> ></td><td>Cl)</td><td>U)</td><td>Φ</td><td>c_</td><td></td><td>Φ</td>
<td>CD</td><td></td><td></td><td> <</td><td>τΤ CU</td><td>Sol</td><td>Ε</td><td></td><td>.c ω</td><td>CU</td><td>LU</td><td>CU</td><td>Ο ω</td><td>Ε</td><td>ί</td><td>Sh</td><td>Ο C0</td><td>E</td><td>NEITHER</td><td>X. ω</td><td>φ Τ</td><td></td><td>tm</td><td>Ό c</td>
<td>'Φ oc</td><td></td><td></td><td> 100%</td><td>mer;</td><td>ο ^ ιη -3-</td><td>Ο Q. Ο</td><td>δ? ο</td><td>δ? m</td><td> 100%</td><td> •100%</td><td>δ? ο ο</td><td> 45%</td><td>Ο ο. ο Üd</td><td>δ? ο</td><td> 15%</td><td>-χ® θ'ο 'ct</td><td>o CL o</td><td>δ? o M ·</td><td>ο</td><td>χρ Ο Τ "</td><td> 6301</td><td>N (Λ Φ</td><td>E tn</td>
<td></td><td></td><td></td><td>Ε</td><td></td><td>έ</td><td></td><td></td><td></td><td>ε</td><td>Ε</td><td>έ</td><td>F</td><td></td><td></td><td></td><td>F</td><td></td><td></td><td></td><td></td><td></td><td></td><td>• Φ</td>
<td></td><td></td><td></td><td>Ε</td><td></td><td>ε</td><td></td><td></td><td></td><td>Ε</td><td>ε</td><td>ε</td><td>Ε</td><td></td><td></td><td></td><td>Ε</td><td></td><td></td><td></td><td></td><td></td><td>4-J</td><td rowspan="2">'CU ω</td>
<td></td><td></td><td></td><td>SHOOT</td><td></td><td>Ο</td><td></td><td></td><td></td><td>ιη</td><td>Ο</td><td>ιη</td><td>Ο</td><td></td><td></td><td></td><td>Ο</td><td></td><td></td><td></td><td></td><td></td><td>C</td>
<td></td><td></td><td></td><td>Ο</td><td></td><td></td><td></td><td></td><td></td><td>ο</td><td></td><td>ο</td><td></td><td></td><td></td><td></td><td>m</td><td></td><td></td><td></td><td></td><td></td><td>Φ</td><td rowspan="2">CO N</td>
<td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td>N</td>
<td></td><td></td><td></td><td>CD</td><td></td><td></td><td></td><td></td><td></td><td></td><td>ο</td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td>ω</td><td>She</td>
<td>CD φ <d</td><td>Φ ω □ ο.</td><td></td><td>3 meadows</td><td></td><td>layer</td><td></td><td></td><td></td><td>σ) φ -φ</td><td rowspan="2">Inhibiting meadow</td><td>σ> φ • φ 1-</td><td>layer</td><td></td><td></td><td></td><td>éteg</td><td></td><td></td><td></td><td></td><td></td><td>ent</td><td>STONE Ι- Ο</td>
<td>θ '</td><td></td><td></td><td>top</td><td></td><td>core</td><td></td><td></td><td></td><td>Binding</td><td>Binding</td><td>core</td><td></td><td></td><td></td><td>LL</td><td></td><td></td><td></td><td></td><td></td><td>Iáim</td><td>UAI Φ</td>
<td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td colspan="2"></td><td colspan="2"></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td>CO</td><td>C</td>
<td>m</td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td colspan="2"></td><td colspan="2"></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td>Φ</td>
<td>guard</td><td>Ε</td><td></td><td></td><td></td><td></td><td></td><td></td><td colspan="2"></td><td colspan="2"></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td> <</td><td>L_<sup>:</sup>SHE</td>
<td>Φ</td><td rowspan="2">'05 Ν</td><td></td><td rowspan="2"> 05</td><td></td><td></td><td></td><td></td><td colspan="2"></td><td colspan="2"></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td>
<td>Φ</td><td></td><td></td><td></td><td></td><td></td><td colspan="2"></td><td colspan="2"></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td>
<td>Φ</td><td>(Λ</td><td></td><td>Χ3 '05</td><td></td><td></td><td></td><td></td><td colspan="2"></td><td colspan="2"></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td>CD</td>
<td>QI</td><td></td><td></td><td rowspan="2">cs</td><td></td><td></td><td></td><td></td><td colspan="2"></td><td colspan="2"></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td>CO</td>
<td></td><td></td><td></td><td></td><td></td><td></td><td></td><td colspan="2"></td><td colspan="2"></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td>
does not change basic characteristics.
··· ··· ·♦·· ·· ·· ·· ·· ·· ·· *· _ · · · ··
18 sheets
Sheet 1 Sheet 2 Sheet 3 Sheet 4 Sheet 5 Sheet 6 Sheet 7 Sheet 8 Sheet 9 Sheet 10 Sheet 11 Sheet 12 Sheet 13 Sheet 14 Sheet 15 Sheet 16 Sheet 17 Sheet 18
142 members in 31 offices
Priority claims1
| Document | Office | Kind | Date |
|---|---|---|---|
| 15360293 | United States of America | A |
Members142
| Document | Office | Kind | |
|---|---|---|---|
| IL111486D0 | Israel | D0 | |
| IL111487D0 | Israel | D0 | |
| CA2153481A1 | Canada | A1 | |
| WO9513918A1 | World Intellectual Property Organization (WIPO) | A1 | |
| CA2153483A1 | Canada | A1 | |
| WO9514739A2 | World Intellectual Property Organization (WIPO) | A2 | |
| AU1182395A | Australia | A | |
| AU1099895A | Australia | A | |
| ZA948816B | South Africa | B | |
| ZA948817B | South Africa | B | |
| NO952801D0 | Norway | D0 | |
| NO952802D0 | Norway | D0 | |
| WO9514739A3 | World Intellectual Property Organization (WIPO) | A3 | |
| NO952802L | Norway | L | |
| NO952801L | Norway | L | |
| HU9502135D0 | Hungary | D0 | |
| HU9502136D0 | Hungary | D0 | |
| EP0679124A1 | European Patent Office (EPO) | A1 | |
| EP0679170A1 | European Patent Office (EPO) | A1 | |
| TR27954A | Türkiye | A | |
| PL309919A1 | Poland | A1 | |
| TW264498B | Taiwan Province of China | B | |
| PL310403A1 | Poland | A1 | |
| BR9405785A | Brazil | A | |
| CZ174595A3 | Czechia | A3 | |
| CZ174695A3 | Czechia | A3 | |
| KR960700150A | Republic of Korea | A | |
| KR960700305A | Republic of Korea | A | |
| CN1117718A | China | A | |
| CN1118604A | China | A | |
| BR9405786A | Brazil | A | |
| CO4290439A1 | Colombia | A1 | |
| CO4290440A1 | Colombia | A1 | |
| GT199400077A | Guatemala | A | |
| HUT72715AThis record | Hungary | A | |
| HUT73212A | Hungary | A | |
| JPH08506068A | Japan | A | |
| JPH08506380A | Japan | A | |
| CA2195628A1 | Canada | A1 | |
| WO9640512A1 | World Intellectual Property Organization (WIPO) | A1 | |
| EP0775052A1 | European Patent Office (EPO) | A1 | |
| RU95117094A | Russian Federation | A | |
| NZ276644A | New Zealand | A | |
| CN1159167A | China | A | |
| US5686527A | United States of America | A | |
| US5693387A | United States of America | A | |
| AU686285B2 | Australia | B2 | |
| AU686697B2 | Australia | B2 | |
| JPH10503982A | Japan | A | |
| NZ276958A | New Zealand | A | |
| NO302870B1 | Norway | B1 | |
| TW335373B | Taiwan Province of China | B | |
| HK1002389A1 | Hong Kong, China | A1 | |
| HK1002393A1 | Hong Kong, China | A1 | |
| IL111486A | Israel | A | |
| US5849843A | United States of America | A | |
| US5854347A | United States of America | A | |
| EP0679124B1 | European Patent Office (EPO) | B1 | |
| AT175383T | Austria | T | |
| ATE175383T1 | Austria | T1 | |
| DE69415792D1 | Germany | D1 | |
| GR3029456T3 | Greece | T3 | |
| ES2129189T3 | Spain | T3 | |
| SG65537A1 | Singapore | A1 | |
| DE69415792T2 | Germany | T2 | |
| DK0679124T3 | Denmark | T3 | |
| US5993949A | United States of America | A | |
| US5998019A | United States of America | A | |
| EP1008357A2 | European Patent Office (EPO) | A2 | |
| EP1008357A3 | European Patent Office (EPO) | A3 | |
| EP0679170B1 | European Patent Office (EPO) | B1 | |
| AT195754T | Austria | T | |
| ATE195754T1 | Austria | T1 | |
| DK0679170T3 | Denmark | T3 | |
| DE69425649D1 | Germany | D1 | |
| US6168862B1 | United States of America | B1 | |
| SG77527A1 | Singapore | A1 | |
| DE69425649T2 | Germany | T2 | |
| CN1066757C | China | C | |
| US6261655B1 | United States of America | B1 | |
| CA2395063A1 | Canada | A1 | |
| WO0156783A1 | World Intellectual Property Organization (WIPO) | A1 | |
| AU3675601A | Australia | A | |
| EP0775052B1 | European Patent Office (EPO) | B1 | |
| DE69615505D1 | Germany | D1 | |
| KR100311884B1 | Republic of Korea | B1 | |
| CN1077028C | China | C | |
| CN1082889C | China | C | |
| DE69615505T2 | Germany | T2 | |
| US6399704B1 | United States of America | B1 | |
| US6461696B1 | United States of America | B1 | |
| KR20020076288A | Republic of Korea | A | |
| BR0107948A | Brazil | A | |
| US2002164492A1 | United States of America | A1 | |
| WO0156783A8 | World Intellectual Property Organization (WIPO) | A8 | |
| EP1259374A1 | European Patent Office (EPO) | A1 | |
| MXPA02007585A | Mexico | A | |
| CO5241317A1 | Colombia | A1 | |
| CN1396862A | China | A | |
| AR027378A1 | Argentina | A1 |
1 legal event, as the office reported them to INPADOC
Events
| Event | Code | |
|---|---|---|
| Temporary protection cancelled due to non-payment of feeDFD9 | DFD9 |
Numbers
- Application
- 9502136
Titles
- English
- MULTI-LAYERED POLYMER FILM FOR MEDICAL GRADE PRODUCTS
Classification
- CPC, 42
- B32B27/08
- B29C48/08
- C08L23/08
- C08L23/0815
- C08L23/0853
- C08L23/0869
- C08L23/10
- C08L25/04
- C08L53/00
- C08L53/02
- B29C48/185
- Y10T428/2891
- Y10T428/1379
- Y10T428/2848
- Y10T428/1383
- Y10T428/2878
- Y10T428/2896
- Y10T428/2883
- Y10T428/2809
- Y10T428/31757
- Y10T428/31873
- Y10T428/31721
- Y10T428/31917
- Y10T428/31924
- Y10T428/31797
- Y10T428/31859
- Y10T428/31551
- Y10T428/31913
- Y10T428/31938
- Y10T428/31928
- Y10T428/3175
- Y10T428/31931
- Y10T428/31935
- Y10T428/31909
- Y10T428/31743
- Y10T428/31746
- Y10T428/31573
- B32B27/32
- B32B27/18
- B32B2323/10
- B32B2323/046
- B32B2439/80
- IPC, 10
- A23L7 10
- A23L7 196
- A61L31 00
- B32B27 08
- B32B27 32
- C08L23 08
- C08L23 10
- C08L25 04
- C08L53 00
- C08L53 02