CA2276728A1 - Single-component adhesive - Google Patents
Single-component adhesive Download PDFInfo
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- CA2276728A1 CA2276728A1 CA 2276728 CA2276728A CA2276728A1 CA 2276728 A1 CA2276728 A1 CA 2276728A1 CA 2276728 CA2276728 CA 2276728 CA 2276728 A CA2276728 A CA 2276728A CA 2276728 A1 CA2276728 A1 CA 2276728A1
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- film
- zirconium dichloride
- coc
- solvent
- films
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/12—Bonding of a preformed macromolecular material to the same or other solid material such as metal, glass, leather, e.g. using adhesives
- C08J5/124—Bonding of a preformed macromolecular material to the same or other solid material such as metal, glass, leather, e.g. using adhesives using adhesives based on a macromolecular component
- C08J5/128—Adhesives without diluent
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- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Materials Engineering (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Laminated Bodies (AREA)
- Blow-Moulding Or Thermoforming Of Plastics Or The Like (AREA)
Abstract
The present invention relates to a process for producing a thermoformable composite film, where a solvent-free adhesive is used to apply at least one thermoplastic film laminated to a film comprising cycloolefin copolymer. The present invention further relates to the use of a solvent-free adhesive, preferably a single-component adhesive, for applying a thermoplastic film to a film comprising cycloolefin copolymer in order to produce a thermoformable composite film.
Description
Ticona GmbH Tic 98/G 012 Single-component adhesive The present invention relates to a process for producing a thermoformable composite film and the use of a solvent-tree adhesive for applying a thermoplastic film to a film comprising cycloolefin copolymer in order to produce a thermoformable composite film.
To produce high-performance packaging, flexible films are molded to the shape of a tray or capsule using the action of heat and pressure and a mechanical ram at super- and/or subatmospheric pressure. The film serves firstly to protect the contents. It has to protect the contents from the effect of the environment. The film must therefore have a high water-vapor, gas and UV barrier. It must have mechanical stability to protect the contents from physical effects and so that it does not itself become damaged by the contents. The quality of the contents must not be impaired by individual constituents being released from within the film.
Blister packs are increasingly frequently chosen as packaging for a wide variety of articles, since this type of pack is available in a wide variety of forms and meets the requirements of mechanized packaging processes.
The starting materials used for blister packs are thermoformable films.
These are plastic films which when heated can be shaped relatively readily by applying super- or subatmospheric pressure pneumatically, or using a ram. Appropriate selection of the molds can thus introduce depressions (blisters) into the film (base film) and these can be matched to the shape of the article to be packed. After this shaping step the article to be packed is introduced into the resulting blister. Once the blister has been filled, a backing film is applied to the base film and encloses the article to be packed within its blister.
If all of the requirements cannot be covered by a single material, the properties required in a film are achieved by combining more than one film to give a composite film. Films produced from cycloolefin copolymers have very good impermeability to water vapor. However, these films have poor resistance to fats. Environmental-stress-cracking corrosion occurs on exposure to unsaturated fatty acids.
To produce high-performance packaging, flexible films are molded to the shape of a tray or capsule using the action of heat and pressure and a mechanical ram at super- and/or subatmospheric pressure. The film serves firstly to protect the contents. It has to protect the contents from the effect of the environment. The film must therefore have a high water-vapor, gas and UV barrier. It must have mechanical stability to protect the contents from physical effects and so that it does not itself become damaged by the contents. The quality of the contents must not be impaired by individual constituents being released from within the film.
Blister packs are increasingly frequently chosen as packaging for a wide variety of articles, since this type of pack is available in a wide variety of forms and meets the requirements of mechanized packaging processes.
The starting materials used for blister packs are thermoformable films.
These are plastic films which when heated can be shaped relatively readily by applying super- or subatmospheric pressure pneumatically, or using a ram. Appropriate selection of the molds can thus introduce depressions (blisters) into the film (base film) and these can be matched to the shape of the article to be packed. After this shaping step the article to be packed is introduced into the resulting blister. Once the blister has been filled, a backing film is applied to the base film and encloses the article to be packed within its blister.
If all of the requirements cannot be covered by a single material, the properties required in a film are achieved by combining more than one film to give a composite film. Films produced from cycloolefin copolymers have very good impermeability to water vapor. However, these films have poor resistance to fats. Environmental-stress-cracking corrosion occurs on exposure to unsaturated fatty acids.
The film most frequently used in blister packs is polyvinyl chloride (PVC).
To increase its barrier properties with respect to gases, in particular water vapor, the amorphous PVC base film is frequently coated with PVDC. Films made from unoriented polypropylene (uPP) give better water-vapor barrier properties than PVC films and are less questionable from an environmental point of view. However, the disadvantage is the poorer thermoformability and higher shrinkage of this partially crystalline material.
The amorphous COC mono- or multilayer films described in EP-A-570 188 and EP-A-631 864, when used as base films, give good processing and good barrier properties.
Relatively new developments in the area of blister packs for pharmaceuticals describe the use of amorphous polyolefins with good processing performance and high water-vapor barriers. For example, EP-A-570 188 and EP-A-631 864 describe the use of polyolefins with cyclic olefins as polymeric building block. These applications describe the use of these polyolefins (cycloolefin copolymers, abbreviated to COC) in the form of mono- or multilayer films for blister packs.
Alongside automated packing and the presentation of the product protected within the blister, for example pharmaceuticals in the form of tablets, capsules or the like, the blister pack can markedly reduce exposure to atmospheric moisture and oxygen and thus increase shelf life.
The object of the present invention is to provide a cost-effective and environmentally friendly process for producing a thermoformable composite film with a high level of barrier properties, very good thermoforming performance and good resistance to fats.
The object of the present invention is achieved by means of a process for producing a thermoformable composite film, where a solvent-free adhesive is used to apply at least one thermoplastic film laminated to a film comprising cycloolefin copolymer.
In particular, the object is achieved by means of a process for producing a thermoformable composite film, where a solvent-free single-component adhesive is used to apply the thermoplastic film laminated to the film comprising cycloolefin copolymer.
' CA 02276728 1999-09-29 The novel feature of the novel process is the use of a solvent-free single-component adhesive for applying a thermoplastic film to a film comprising cycloolefin copolymer in order to produce a thermoformable composite film.
The composite film produced according to the invention is particularly suitable for producing blister packs.
At relative humidity of about 85% and at a temperature of about 23°C, the film has water-vapor permeability of < 0.05 g/m2d, a puncture ~es~stance of < 20 N and a thickness of < 100 Nm.
The films suitable for the purposes of the invention comprise at least one cycloolefin polymer selected from the class consisting of polymers containing from 0.1 to 100% by weight, preferably from 10 to 90% by weight, based on the total weight of the cycloolefin copolymer, of polymerized units of at least one cyclic olefin of the formulae I, II, II', III, IV, V or VI
R~
HC -CN-_ CH~
I (I
HC ' CH ~ CH \\
CH.
HC 'CH _ CH /
a ~ GH II
R3 C R ( ), HC CH-_ ~ H 2 _CH~
To increase its barrier properties with respect to gases, in particular water vapor, the amorphous PVC base film is frequently coated with PVDC. Films made from unoriented polypropylene (uPP) give better water-vapor barrier properties than PVC films and are less questionable from an environmental point of view. However, the disadvantage is the poorer thermoformability and higher shrinkage of this partially crystalline material.
The amorphous COC mono- or multilayer films described in EP-A-570 188 and EP-A-631 864, when used as base films, give good processing and good barrier properties.
Relatively new developments in the area of blister packs for pharmaceuticals describe the use of amorphous polyolefins with good processing performance and high water-vapor barriers. For example, EP-A-570 188 and EP-A-631 864 describe the use of polyolefins with cyclic olefins as polymeric building block. These applications describe the use of these polyolefins (cycloolefin copolymers, abbreviated to COC) in the form of mono- or multilayer films for blister packs.
Alongside automated packing and the presentation of the product protected within the blister, for example pharmaceuticals in the form of tablets, capsules or the like, the blister pack can markedly reduce exposure to atmospheric moisture and oxygen and thus increase shelf life.
The object of the present invention is to provide a cost-effective and environmentally friendly process for producing a thermoformable composite film with a high level of barrier properties, very good thermoforming performance and good resistance to fats.
The object of the present invention is achieved by means of a process for producing a thermoformable composite film, where a solvent-free adhesive is used to apply at least one thermoplastic film laminated to a film comprising cycloolefin copolymer.
In particular, the object is achieved by means of a process for producing a thermoformable composite film, where a solvent-free single-component adhesive is used to apply the thermoplastic film laminated to the film comprising cycloolefin copolymer.
' CA 02276728 1999-09-29 The novel feature of the novel process is the use of a solvent-free single-component adhesive for applying a thermoplastic film to a film comprising cycloolefin copolymer in order to produce a thermoformable composite film.
The composite film produced according to the invention is particularly suitable for producing blister packs.
At relative humidity of about 85% and at a temperature of about 23°C, the film has water-vapor permeability of < 0.05 g/m2d, a puncture ~es~stance of < 20 N and a thickness of < 100 Nm.
The films suitable for the purposes of the invention comprise at least one cycloolefin polymer selected from the class consisting of polymers containing from 0.1 to 100% by weight, preferably from 10 to 90% by weight, based on the total weight of the cycloolefin copolymer, of polymerized units of at least one cyclic olefin of the formulae I, II, II', III, IV, V or VI
R~
HC -CN-_ CH~
I (I
HC ' CH ~ CH \\
CH.
HC 'CH _ CH /
a ~ GH II
R3 C R ( ), HC CH-_ ~ H 2 _CH~
CHz HC ICH--_ CH /
R3 C Rd GHz (~
HG CH _ ~CH~ CHZ
R~
HC'CH-_ CH-~ ~H'CH/
R3 C R4 R5 C Rs ~ ( W ~, HC CH ~ I CH
~CH~ CH' \ RI
R~
HC ~CH_ CHI IH _CH H CH
R3 - Ra p5 - C - ps p - C - R (IV), HC'IH CH~CH~CH\CH~CH~R, R~
(CH~
n HC 'C~ _ CH / CH
HC ' I ~CH _ CH
C I~
1 R~
RZ
t -(CH~ CH
HC ~CH_ CH NCH C /H
R~ C R8 (VII.
Rj C R4 CH
/ ~CH \ ~ ' ~ t 'CH/ CH CH R
I
where R1, R2, R3, R~, R5, R6, R~ and R$ are identical or different and are a hydrogen atom or a C1-CZp-hydrocarbon radical, such as a linear or branched C1-Cg-alkyl radical or Cg-C1g-aryl radical or C7-C2p-alkylenearyi 5 radical, or a cyclic or acyclic C2-C2p-alkenyl radical, or form a saturated, unsaturated or aromatic ring, where the same radicals R1 to R8 in the different formulae I to VI may have different meanings, and n may be from 0 to 5, and from 0 to 99.9 mol%, based on the total composition of the cycloolefin copolymer, of polymerized units which derive from one or more acyclic olefins of the formula VII
g R10 R
C C
(VII), where R9, Rip, R11 and R12 are identical or different and are a hydrogen atom, a linear or branched, saturated or unsaturated C1-C2p-hydrocarbon radical, such as a C1-Cg-alkyl radical, or a Cg-C1g-aryl radical.
The cycloolefin copolymers may also be obtained by ring-opening polymerization of at least one of the monomers with the formulae I to VI, followed by hydrogenation of the products obtained.
The novel elastomeric cycloolefin copolymer may also contain from 0 to 45 mol%, based on the total composition of the cycloolefin copolymer, of polymerized units which derive from one or more monocyclic olefins of the formula VIII
HC CH
(VIII), (CH2)m where m is a number from 2 to 10.
R3 C Rd GHz (~
HG CH _ ~CH~ CHZ
R~
HC'CH-_ CH-~ ~H'CH/
R3 C R4 R5 C Rs ~ ( W ~, HC CH ~ I CH
~CH~ CH' \ RI
R~
HC ~CH_ CHI IH _CH H CH
R3 - Ra p5 - C - ps p - C - R (IV), HC'IH CH~CH~CH\CH~CH~R, R~
(CH~
n HC 'C~ _ CH / CH
HC ' I ~CH _ CH
C I~
1 R~
RZ
t -(CH~ CH
HC ~CH_ CH NCH C /H
R~ C R8 (VII.
Rj C R4 CH
/ ~CH \ ~ ' ~ t 'CH/ CH CH R
I
where R1, R2, R3, R~, R5, R6, R~ and R$ are identical or different and are a hydrogen atom or a C1-CZp-hydrocarbon radical, such as a linear or branched C1-Cg-alkyl radical or Cg-C1g-aryl radical or C7-C2p-alkylenearyi 5 radical, or a cyclic or acyclic C2-C2p-alkenyl radical, or form a saturated, unsaturated or aromatic ring, where the same radicals R1 to R8 in the different formulae I to VI may have different meanings, and n may be from 0 to 5, and from 0 to 99.9 mol%, based on the total composition of the cycloolefin copolymer, of polymerized units which derive from one or more acyclic olefins of the formula VII
g R10 R
C C
(VII), where R9, Rip, R11 and R12 are identical or different and are a hydrogen atom, a linear or branched, saturated or unsaturated C1-C2p-hydrocarbon radical, such as a C1-Cg-alkyl radical, or a Cg-C1g-aryl radical.
The cycloolefin copolymers may also be obtained by ring-opening polymerization of at least one of the monomers with the formulae I to VI, followed by hydrogenation of the products obtained.
The novel elastomeric cycloolefin copolymer may also contain from 0 to 45 mol%, based on the total composition of the cycloolefin copolymer, of polymerized units which derive from one or more monocyclic olefins of the formula VIII
HC CH
(VIII), (CH2)m where m is a number from 2 to 10.
The proportion of the polymerized units which derive from cyclic, in particular polycyclic, olefins, is preferably from 3 to 75 mol%, based on the total composition of the cycloolefin copolymer. The proportion of the polymerized units which derive from acyclic olefins is preferably from 5 to 80 mol%, based on the total composition of the cycloolefin copolymer.
The cycloolefin copolymers are preferably composed of polymerized units which derive from one or more polycyclic olefins, in particular from polycyclic olefins of the formulae I or III, and polymerized units which derive from one or more acyclic olefins of the formula VII, in particular a-olefins having from 2 to 20 carbon atoms. Particular preference is given to cycloolefin copolymers which are composed of polymerized units which derive from a polycyclic olefin of the formula I or III and from an acyclic olefin of the formula VII. Preference is also given to terpolymers which are composed of polymerized units which derive from a polycyclic monoolefin of the formula I or III, from an acyclic monoolefin of the formula VII and from a cyclic or acyclic olefin which contains at least two double bonds (polyene), in particular cyclic, preferably polycyclic, dienes, such as norbornadiene, or cyclic, particularly preferably polycyclic, alkenes with a C2-C2p-alkenyl radical, such as vinylnorbornene.
The novel elastomeric cycloolefin copolymers preferably comprise olefins with a basic norbornene structure, particularly preferably norbornene, tetracyclododecene and, if desired, vinylnorbornene or norbornadiene.
Preference is also given to cycloolefin copolymers which contain polymerized units which derive from acyclic olefins with terminal double bonds, such as a-olefins having from 2 to 20 carbon atoms, particularly preferably ethylene or propylene. Particular preference is given to norbornene-ethylene and tetracyclododecene-ethylene copolymers.
Among the terpolymers, particular preference is given to norbornene-vinylnorbornene-ethylene, norbornene-norbornadiene-ethylene, tetracyclododecene-vinylnorbornene-ethylene and tetracyclododecene-vinyltetracyclododecene-ethylene terpolymers. The proportion of the polymerized units which derive from a polyene, preferably vinylnorbornene or norbornadiene, is from 0.1 to 50 mol%, preferably from 0.1 to 20 mol%, and the proportion of the acyclic monoolefin of the formula VII is from 0 to 99.9 mol%, preferably from 5 to 80 mol%, based on the total composition of the cycloolefin copolymer. In the terpolymers described, the proportion of the polycyclic monoolefin is from 0.1 to 99.9 mol%, preferably from 3 to 75 mol%, based on the total composition of the cycloolefin copolymer.
The cycloolefin copolymer according to the invention preferably comprises at least one cycloolefin copolymer containing polymerized units which derive from polycyclic olefins of the formula I and containing polymerized units which derive from acyclic olefins of the formula VII.
The cycloolefin copolymers according to the invention may be prepared at temperatures of from -78 to 200°C and at a pressure of from 0.01 to 200 bar, in the presence of one or more catalyst systems which comprise at least one transition metal compound and, if desired, a cocatalyst and, if desired, a support. Suitable transition metal compounds are metallocenes, in particular stereorigid metallocenes. Examples of catalyst systems suitable for preparing the elastomeric cycloolefin copolymers according to the invention are described in EP-A-407 870, EP-A-485 893 and EP-A-503 422. These publications are expressly incorporated herein by way of reference.
Examples of transition metal compounds used are:
rac-dimethylsilylbis(1-indenyl)zirconium dichloride, rac-dimethylgermylbis(1-indenyl)zirconium dichloride, rac-phenylmethylsilylbis(1-indenyl)zirconium dichloride, rac-phenyivinylsilylbis(1-indenyl)zirconium dichloride, 1-silacyclobutylbis(1-indenyl)zirconium dichloride, rac-diphenylsilylbis(1-indenyl)hafnium dichloride, rac-phenylmethylsilylbis(1-indenyl)hafnium dichloride, rac-diphenylsilylbis(1-indenyl)zirconium dichloride, rac-ethylene-1,2-bis(1-indenyl)zirconium dichloride, dimethylsilyl(9-fluorenyl)(cyclopentadienyl)zirconium dichloride, diphenylsilyl(9-fluorenyl)(cyclopentadienyl)zirconium dichloride, bis(1-indenyl)zirconium dichloride, diphenylmethylene(9-fluorenyl)cyclopentadienylzirconium dichloride, isopropylene(9-fluorenyl)cyclopentadienylzirconium dichloride, rac-isopropylidenebis(1-indenyl)zirconium dichloride, phenylmethylmethylene(9-fluorenyl)cyclopentadienylzirconium dichloride, isopropylene(9-fluorenyl)(1-(3-isopropyl)cyclopentadienyl)zirconium dichloride, isopropylene(9-fluorenyl)(1-(3-methyl)cyclopentadienyl)zirconium dichloride, diphenylmethylene(9-fluorenyl)(1-(3-methyl)cyclopentadienyl)zirconium dichloride, methylphenylmethylene(9-fluorenyl)(1-(3-methyl)cyclopentadienyl)-zirconium dichloride, dimethylsilyl(9-fluorenyl)(1-(3-methyl)cyclopentadienyl)zirconium dichloride, diphenylsilyl(9-fluorenyl)(1-(3-methyl)cyclopentadienyl)zirconium dichloride, diphenylmethylene(9-fluorenyl)(1-(3-tert-butyl)cyclopentadienyl)zirconium dichloride, isopropylene(9-fluorenyl)(1-(3-tert-butyl)cyclopentadienyl)zirconium dichloride, isopropylene(cyclopentadienyl)(1-indenyl)zirconium dichloride, diphenylcarbonyl(cyclopentadienyl)(1-indenyl)zirconium dichloride, dimethylsilyl(cyclopentadienyl)(1-indenyl)zirconium dichloride, isopropylene(methylcyclopentadienyl)(1-indenyl)zirconium dichloride, 4-( rt5-cyclopentadienyl)-4,7,7-trimethyl(r~5-4,5,6,7-tetrahydroindenyl)-zirconium dichloride, [4-( rl5-cyclopentadienyl)-4,7,7-triphenyl( r~5-4,5,6,7-tetrahydroindenyl)]-zirconium dichloride, [4-( rl5-cyclopentadienyl)-4,7-dimethyl-7-phenyl( rl5-4,5,6,7-tetrahydro-indenyl)]zirconium dichloride, [4-( rl -3'-tert-butyicyclopentadienyl)-4,7,7-triphenyl( rl5-4,5,6,7-tetrahydro-indenyl)]zirconium dichloride, [4-( r~5-3'-tent-butylcyclopentadienyl)-4,7-dimethyl-7-phenyl( rl5-4,5,6,5 -tetrahydroindenyl)]zirconium dichloride, [4-( r~ -3'-methylcyclopentadienyl)-4,7,7-trimethyl( r~ -4,5,6,7-tetrahydro-indenyl)]zirconium dichloride, [4-( rt -3'-methylcyclopentadienyl)-4,7,7-triphenyl( ~5-4,5,6,7-tetrahydro-indenyl)]zirconium dichloride, [4-( rl -3'-methylcyclopentadienyl)-4,7-dimethyl-7-phenyl( rl5-4,5,6,7-tetra-hydroindenyl)]zirconium dichloride, [4-( ~5-3'-isopropylcyclopentadienyl)-4,7,7-trimethyl( rt5-4,5,6,7-tetrahydro-indenyl)]zirconium dichloride, [4-( r~5-3'-isopropylcyclopentadienyl)-4,7,7-triphenyl( r~5-4,5,6,7-tetrahydro-indenyl)]zirconium dichloride, [4-( ri5-3'-isopropylcyclopentadienyl)-4,7-dimethyl-7-phenyl( r~5-4,5,6,7-tetrahydroindenyl)]zirconium dichloride, [4-( r~5-cyclopentadienyl)( r~5-4,5-tetr~hydropentalene)]zirconium dichloride, [4-( rl -cyclopentadienyl)-4-methyl( r~ -4,5-tetrahydropentalene)]zirconium dichloride, [4-( rl5-cyclopentadienyl)-4-phenyl( r~5-4,5-tetrahydropentalene)]zirconium dichloride, [4-( rl5-cyclopentadienyl)-4-phenyl( r~5-4,5-tetrahydropentalene)]zirconium dichloride, [4-( rl5-3'-methylcyclopentadienyl)( r~5-4,5-tetrahydropentalene)]zirconium dichloride, [4-( r~5-3'-isopropylcyclopentadienyl)( ~5-4,5-tetrahydropentaiene)]-zirconium dichloride, [4-( rl5-3'-benzylcyclopentadienyl)( r~5-4,5-tetrahydropentalene)]zirconium dichloride, [2,2,4-trimethyl-4-( rl5-cyclopentadienyl)( r~5-4,5-tetrahydropentalene)]-zirconium dichloride, [2,2,4-trimethyl-4-( rl5-(3,4-diisopropyl)cyclopentadienyl)( r~5-4,5-tetrahydro-pentalene)]zirconium dichloride.
The COC films used according to the invention are distinguished by specific mechanical properties. The films can be processed on the machinery used and also have low puncture resistance and a high level of barrier properties, especially to water vapor. Suitable COC films of this type are oriented. They may be monolayer films or have more than one layer.
The films may comprise organic or inorganic fillers in order to reduce light transmission so as to render the contents invisible (childproof packaging) or in order to improve printability or sealing properties.
The cycloolefin copolymers are prepared by heterogeneous or homogeneous catalysis with organometallic compounds as described in many patents. Catalyst systems based on mixed catalysts made from titanium salts and organoaluminum compounds are described in DD-A-109 224 and DD-A-237 070. EP-A-156 464 describes the preparation using catalysts based on vanadium. EP-A-283 164, EP-A-407 870, EP-A-485 893 and EP-A-503 422 describe the preparation of cycloolefin polymers using catalysts based on soluble metallocene complexes. The preparation processes described and the catalyst systems used in these patents for preparing COCs are incorporated herein by way of reference.
Unoriented extruded COC films are brittle, making it difficult to find appropriate processing conditions, and their processing performance is poor, cf. DE-A-4304309. They readily split or break during winding-up and/or unwinding under tension. For this reason their mechanical strength 5 has to be increased. This may be achieved by orientation (mono- or biaxial stretching) of the films. The films oriented in this way are significantly easier to handle and do not have the disadvantages as described in DE-A-4304309. The puncture resistance of oriented films was studied in accordance with DIN 53373. One measure of puncture resistance is 10 penetration energy. It has now been established that orientation increases the puncture resistance of the films. Exceptionally, the values found were larger than those of unoriented films of comparable thickness.
DE-A-4414669 states that 450 N/mm is excessively high for a film to be useful as a backing film for blister packs. Significantly lower values are desirable on blister-packing machinery for fragile pharmaceuticals. The puncture resistances of aluminum foils can be taken as a preliminary guide:
that of a (16 Nm) aluminum film is 90 N/mm. When oriented COC films are used, therefore, it is not possible to ensure easy removal of the pharmaceutical from the blister packs.
Alongside ideal, but not excessively low, puncture resistance, the blister film must have relatively high toughness. Careful balancing of mechanical strength (hardness), flexibility and the force required to compress the compartment is required to enable the contents, such as a tablet, capsule pastille or dragee are to be capable of release from the pack without damage and without unreasonable expenditure of effort. Low expenditure of effort is a particular requirement when elderly people use the product, and also in the clinical sector where medical personnel are continually using pressure to remove tablets and can suffer from fatigue or aching in the fingers.
The water-vapor barrier effectiveness is not significantly affected by organic or inorganic additives. It is from 0.2 to 0.4 g/mZ~d for a film thickness of 100 Nm. The polarity of the surface can be increased by corona-treating the film.
The additives may be organic polymers, such as polypropylene or polyethylene in the form of homo- or copolymers, polyesters, polyamides, polycarbonate, polyacetals, and acrylate and methacrylate polymers.
Inorganic pigments which may be used are titanium dioxide, barium sulfate, calcium sulfate, calcium carbonate and barium carbonate.
One or both sides of the COC film may be laminated with a film which comprises polymers such as unoriented or oriented polyethylene, polypropylene or polyvinyl chloride. A solvent-free adhesive is preferably used in the lamination, particularly preferably a solvent-free single-component adhesive.
It is preferable to laminate COC with unoriented polypropylene (uPP) or else PVC on one or both sides. Compared with COC, the films produced with unoriented polypropylene and PVC are significantly thinner. COC and uPP, and COC and PVC, give as a laminate a flexible, puncture-resistant composite film of good appearance. A further advantage of a laminate made from PVC and COC for the user, possibly a pharmaceutical blister pack manufacturer, is that it can replace packaging previously composed exclusively of PVC. The novel laminate made from PVC and COC is of high quality and has relatively high impermeability to water vapor, retaining surface contact with the contents via the PVC layer. The approval procedure is thus simplified.
The thickness of the entire film is from 100 to 550 pm, preferably from 200 to 400 Nm. The thickness of the film laminated to the COC film is from 1 to 150 pm, preferably from 1 to 100 pm and particularly preferably from 4 to 50 pm. The thickness of the COC film is from 50 to 400 Nm, preferably from 150 to 350 Nm, particularly preferably from 200 to 300 Nm.
The novel process for producing a thermoformable composite film uses a solvent-free adhesive, preferably a solvent-free, single-component adhesive.
Particularly suitable for this purpose according to the invention is a solvent-free polyurethane-based moisture-curing single-component laminating resin. The laminating resin used differs from conventional laminating adhesives by being supplied and used with 100% solids content. The laminating resin is suitable for producing laminates from aluminum and paper, card or parchment, and for producing laminates from plastic films and paper or aluminum films. According to the invention the novel adhesive is very particularly suitable for producing thermoformable composite films where the novel adhesive is used to apply at least one thermoplastic film laminated to a film comprising cycloolefin copolymer.
Processing takes place on LF laminating plants which have heatable application systems and laminating units. Since the laminating resin is applied without solvent, no drying tunnels are required. A heatable laminating unit is advantageous for varying combinations. The laminating resin has to be heated to 80 - 100°C for application.
The novel thermoformable composite film is used for producing blister packs. The blister pack or PTP (push-through packaging) produced therefrom has very good water-vapor barrier properties, thus increasing the value of the packaged item. It can be used to pack contents such as pharmaceuticals and foodstuffs, in particular pelletized or capsule pharmaceuticals, foods containing rice, cookies, snacks, and also hygroscopic items, such as cigarettes and teabags.
The invention is described in more detail using a drawing and examples.
Drawing The drawing comprises Figures 1 to 3.
Fig. 1 shows the coating plant Fig. 2 shows the set-up of the coating plant Fig. 3 shows the application device in the coating plant.
The coating plant of Fig. 1 comprises an unwind (1 ), application device (2), short-wavelength infrared source (3), medium-wavelength infrared source (4), flotation drier (5), dry-lamination unit (6), corona system (7), web edge-guiding system (8), remoistening equipment (9), cooling unit (10), wind up (11), electron-beam unit (12), wet-lamination unit (13) and UV source (14).
Fig. 2 shows the set-up of the coating plant for the following procedures:
A) thermal drying or UV curing B) thermal drying with shock cooling C) thermal drying with remoistening D) thermal drying with dry lamination E) thermal drying with UV curing.
Fig. 3 shows the application device in the coating plant with application by smooth rollers using 4 rollers (wet). G here indicates a rubber roll and S a steel roll. The rolls here are heated and cooled. Application using smooth rolls is particularly suitable for the lamination of COC with PVC or oPP.
Examples The solvent-free single-component adhesive used, Herberts GmbH 1 K-~F
190X3, has the following physical properties:
Solids (%) 100, Viscosity (100 °C) 850 = 150 mPas Example 1 A COC film 190 Nm thick (194 g/m2) was laminated to both sides of an unoriented polypropylene film 25 Nm thick (22.5 g/m2) using Herberts GmbH 1 K-LF 190X3 solvent-free single-component adhesive. Application was at 1.50 g/m2, with corona treatment at 48 kW. For lamination a width of 810 mm was used, a speed of 50 m/min, and a smooth-roll application system with four rolls and one pass for each laminated side. The thickness of the thermoformable composite film was 210 Nm. The bond strength of the composite film was high, and when this bond strength was measured it was the composite film which broke.
Example 2 A COC film 190 Nm thick (194 g/m2) was laminated to both sides of an unoriented PVC film 35 tlm thick (4.6 g/m2) using Herberts GmbH 1 K-LF
190X3 solvent-free single-component adhesive. Application was at 1.50 g/m2, with corona treatment at 48 kW. For lamination a width of 810 mm was used, a speed of 50 m/min, and a smooth-roll application system with four rolls and one pass for each laminated side. The thickness of the thermoformable composite film was 260 Nm. The bond strength of the composite film was high, and when this bond strength was measured it was the composite film which broke.
Comparative Example The procedure of the example was followed except that both sides of the COC film were laminated to an unoriented polypropylene film. The thickness of the thermoformable composite film was 210 arm.
The cycloolefin copolymers are preferably composed of polymerized units which derive from one or more polycyclic olefins, in particular from polycyclic olefins of the formulae I or III, and polymerized units which derive from one or more acyclic olefins of the formula VII, in particular a-olefins having from 2 to 20 carbon atoms. Particular preference is given to cycloolefin copolymers which are composed of polymerized units which derive from a polycyclic olefin of the formula I or III and from an acyclic olefin of the formula VII. Preference is also given to terpolymers which are composed of polymerized units which derive from a polycyclic monoolefin of the formula I or III, from an acyclic monoolefin of the formula VII and from a cyclic or acyclic olefin which contains at least two double bonds (polyene), in particular cyclic, preferably polycyclic, dienes, such as norbornadiene, or cyclic, particularly preferably polycyclic, alkenes with a C2-C2p-alkenyl radical, such as vinylnorbornene.
The novel elastomeric cycloolefin copolymers preferably comprise olefins with a basic norbornene structure, particularly preferably norbornene, tetracyclododecene and, if desired, vinylnorbornene or norbornadiene.
Preference is also given to cycloolefin copolymers which contain polymerized units which derive from acyclic olefins with terminal double bonds, such as a-olefins having from 2 to 20 carbon atoms, particularly preferably ethylene or propylene. Particular preference is given to norbornene-ethylene and tetracyclododecene-ethylene copolymers.
Among the terpolymers, particular preference is given to norbornene-vinylnorbornene-ethylene, norbornene-norbornadiene-ethylene, tetracyclododecene-vinylnorbornene-ethylene and tetracyclododecene-vinyltetracyclododecene-ethylene terpolymers. The proportion of the polymerized units which derive from a polyene, preferably vinylnorbornene or norbornadiene, is from 0.1 to 50 mol%, preferably from 0.1 to 20 mol%, and the proportion of the acyclic monoolefin of the formula VII is from 0 to 99.9 mol%, preferably from 5 to 80 mol%, based on the total composition of the cycloolefin copolymer. In the terpolymers described, the proportion of the polycyclic monoolefin is from 0.1 to 99.9 mol%, preferably from 3 to 75 mol%, based on the total composition of the cycloolefin copolymer.
The cycloolefin copolymer according to the invention preferably comprises at least one cycloolefin copolymer containing polymerized units which derive from polycyclic olefins of the formula I and containing polymerized units which derive from acyclic olefins of the formula VII.
The cycloolefin copolymers according to the invention may be prepared at temperatures of from -78 to 200°C and at a pressure of from 0.01 to 200 bar, in the presence of one or more catalyst systems which comprise at least one transition metal compound and, if desired, a cocatalyst and, if desired, a support. Suitable transition metal compounds are metallocenes, in particular stereorigid metallocenes. Examples of catalyst systems suitable for preparing the elastomeric cycloolefin copolymers according to the invention are described in EP-A-407 870, EP-A-485 893 and EP-A-503 422. These publications are expressly incorporated herein by way of reference.
Examples of transition metal compounds used are:
rac-dimethylsilylbis(1-indenyl)zirconium dichloride, rac-dimethylgermylbis(1-indenyl)zirconium dichloride, rac-phenylmethylsilylbis(1-indenyl)zirconium dichloride, rac-phenyivinylsilylbis(1-indenyl)zirconium dichloride, 1-silacyclobutylbis(1-indenyl)zirconium dichloride, rac-diphenylsilylbis(1-indenyl)hafnium dichloride, rac-phenylmethylsilylbis(1-indenyl)hafnium dichloride, rac-diphenylsilylbis(1-indenyl)zirconium dichloride, rac-ethylene-1,2-bis(1-indenyl)zirconium dichloride, dimethylsilyl(9-fluorenyl)(cyclopentadienyl)zirconium dichloride, diphenylsilyl(9-fluorenyl)(cyclopentadienyl)zirconium dichloride, bis(1-indenyl)zirconium dichloride, diphenylmethylene(9-fluorenyl)cyclopentadienylzirconium dichloride, isopropylene(9-fluorenyl)cyclopentadienylzirconium dichloride, rac-isopropylidenebis(1-indenyl)zirconium dichloride, phenylmethylmethylene(9-fluorenyl)cyclopentadienylzirconium dichloride, isopropylene(9-fluorenyl)(1-(3-isopropyl)cyclopentadienyl)zirconium dichloride, isopropylene(9-fluorenyl)(1-(3-methyl)cyclopentadienyl)zirconium dichloride, diphenylmethylene(9-fluorenyl)(1-(3-methyl)cyclopentadienyl)zirconium dichloride, methylphenylmethylene(9-fluorenyl)(1-(3-methyl)cyclopentadienyl)-zirconium dichloride, dimethylsilyl(9-fluorenyl)(1-(3-methyl)cyclopentadienyl)zirconium dichloride, diphenylsilyl(9-fluorenyl)(1-(3-methyl)cyclopentadienyl)zirconium dichloride, diphenylmethylene(9-fluorenyl)(1-(3-tert-butyl)cyclopentadienyl)zirconium dichloride, isopropylene(9-fluorenyl)(1-(3-tert-butyl)cyclopentadienyl)zirconium dichloride, isopropylene(cyclopentadienyl)(1-indenyl)zirconium dichloride, diphenylcarbonyl(cyclopentadienyl)(1-indenyl)zirconium dichloride, dimethylsilyl(cyclopentadienyl)(1-indenyl)zirconium dichloride, isopropylene(methylcyclopentadienyl)(1-indenyl)zirconium dichloride, 4-( rt5-cyclopentadienyl)-4,7,7-trimethyl(r~5-4,5,6,7-tetrahydroindenyl)-zirconium dichloride, [4-( rl5-cyclopentadienyl)-4,7,7-triphenyl( r~5-4,5,6,7-tetrahydroindenyl)]-zirconium dichloride, [4-( rl5-cyclopentadienyl)-4,7-dimethyl-7-phenyl( rl5-4,5,6,7-tetrahydro-indenyl)]zirconium dichloride, [4-( rl -3'-tert-butyicyclopentadienyl)-4,7,7-triphenyl( rl5-4,5,6,7-tetrahydro-indenyl)]zirconium dichloride, [4-( r~5-3'-tent-butylcyclopentadienyl)-4,7-dimethyl-7-phenyl( rl5-4,5,6,5 -tetrahydroindenyl)]zirconium dichloride, [4-( r~ -3'-methylcyclopentadienyl)-4,7,7-trimethyl( r~ -4,5,6,7-tetrahydro-indenyl)]zirconium dichloride, [4-( rt -3'-methylcyclopentadienyl)-4,7,7-triphenyl( ~5-4,5,6,7-tetrahydro-indenyl)]zirconium dichloride, [4-( rl -3'-methylcyclopentadienyl)-4,7-dimethyl-7-phenyl( rl5-4,5,6,7-tetra-hydroindenyl)]zirconium dichloride, [4-( ~5-3'-isopropylcyclopentadienyl)-4,7,7-trimethyl( rt5-4,5,6,7-tetrahydro-indenyl)]zirconium dichloride, [4-( r~5-3'-isopropylcyclopentadienyl)-4,7,7-triphenyl( r~5-4,5,6,7-tetrahydro-indenyl)]zirconium dichloride, [4-( ri5-3'-isopropylcyclopentadienyl)-4,7-dimethyl-7-phenyl( r~5-4,5,6,7-tetrahydroindenyl)]zirconium dichloride, [4-( r~5-cyclopentadienyl)( r~5-4,5-tetr~hydropentalene)]zirconium dichloride, [4-( rl -cyclopentadienyl)-4-methyl( r~ -4,5-tetrahydropentalene)]zirconium dichloride, [4-( rl5-cyclopentadienyl)-4-phenyl( r~5-4,5-tetrahydropentalene)]zirconium dichloride, [4-( rl5-cyclopentadienyl)-4-phenyl( r~5-4,5-tetrahydropentalene)]zirconium dichloride, [4-( rl5-3'-methylcyclopentadienyl)( r~5-4,5-tetrahydropentalene)]zirconium dichloride, [4-( r~5-3'-isopropylcyclopentadienyl)( ~5-4,5-tetrahydropentaiene)]-zirconium dichloride, [4-( rl5-3'-benzylcyclopentadienyl)( r~5-4,5-tetrahydropentalene)]zirconium dichloride, [2,2,4-trimethyl-4-( rl5-cyclopentadienyl)( r~5-4,5-tetrahydropentalene)]-zirconium dichloride, [2,2,4-trimethyl-4-( rl5-(3,4-diisopropyl)cyclopentadienyl)( r~5-4,5-tetrahydro-pentalene)]zirconium dichloride.
The COC films used according to the invention are distinguished by specific mechanical properties. The films can be processed on the machinery used and also have low puncture resistance and a high level of barrier properties, especially to water vapor. Suitable COC films of this type are oriented. They may be monolayer films or have more than one layer.
The films may comprise organic or inorganic fillers in order to reduce light transmission so as to render the contents invisible (childproof packaging) or in order to improve printability or sealing properties.
The cycloolefin copolymers are prepared by heterogeneous or homogeneous catalysis with organometallic compounds as described in many patents. Catalyst systems based on mixed catalysts made from titanium salts and organoaluminum compounds are described in DD-A-109 224 and DD-A-237 070. EP-A-156 464 describes the preparation using catalysts based on vanadium. EP-A-283 164, EP-A-407 870, EP-A-485 893 and EP-A-503 422 describe the preparation of cycloolefin polymers using catalysts based on soluble metallocene complexes. The preparation processes described and the catalyst systems used in these patents for preparing COCs are incorporated herein by way of reference.
Unoriented extruded COC films are brittle, making it difficult to find appropriate processing conditions, and their processing performance is poor, cf. DE-A-4304309. They readily split or break during winding-up and/or unwinding under tension. For this reason their mechanical strength 5 has to be increased. This may be achieved by orientation (mono- or biaxial stretching) of the films. The films oriented in this way are significantly easier to handle and do not have the disadvantages as described in DE-A-4304309. The puncture resistance of oriented films was studied in accordance with DIN 53373. One measure of puncture resistance is 10 penetration energy. It has now been established that orientation increases the puncture resistance of the films. Exceptionally, the values found were larger than those of unoriented films of comparable thickness.
DE-A-4414669 states that 450 N/mm is excessively high for a film to be useful as a backing film for blister packs. Significantly lower values are desirable on blister-packing machinery for fragile pharmaceuticals. The puncture resistances of aluminum foils can be taken as a preliminary guide:
that of a (16 Nm) aluminum film is 90 N/mm. When oriented COC films are used, therefore, it is not possible to ensure easy removal of the pharmaceutical from the blister packs.
Alongside ideal, but not excessively low, puncture resistance, the blister film must have relatively high toughness. Careful balancing of mechanical strength (hardness), flexibility and the force required to compress the compartment is required to enable the contents, such as a tablet, capsule pastille or dragee are to be capable of release from the pack without damage and without unreasonable expenditure of effort. Low expenditure of effort is a particular requirement when elderly people use the product, and also in the clinical sector where medical personnel are continually using pressure to remove tablets and can suffer from fatigue or aching in the fingers.
The water-vapor barrier effectiveness is not significantly affected by organic or inorganic additives. It is from 0.2 to 0.4 g/mZ~d for a film thickness of 100 Nm. The polarity of the surface can be increased by corona-treating the film.
The additives may be organic polymers, such as polypropylene or polyethylene in the form of homo- or copolymers, polyesters, polyamides, polycarbonate, polyacetals, and acrylate and methacrylate polymers.
Inorganic pigments which may be used are titanium dioxide, barium sulfate, calcium sulfate, calcium carbonate and barium carbonate.
One or both sides of the COC film may be laminated with a film which comprises polymers such as unoriented or oriented polyethylene, polypropylene or polyvinyl chloride. A solvent-free adhesive is preferably used in the lamination, particularly preferably a solvent-free single-component adhesive.
It is preferable to laminate COC with unoriented polypropylene (uPP) or else PVC on one or both sides. Compared with COC, the films produced with unoriented polypropylene and PVC are significantly thinner. COC and uPP, and COC and PVC, give as a laminate a flexible, puncture-resistant composite film of good appearance. A further advantage of a laminate made from PVC and COC for the user, possibly a pharmaceutical blister pack manufacturer, is that it can replace packaging previously composed exclusively of PVC. The novel laminate made from PVC and COC is of high quality and has relatively high impermeability to water vapor, retaining surface contact with the contents via the PVC layer. The approval procedure is thus simplified.
The thickness of the entire film is from 100 to 550 pm, preferably from 200 to 400 Nm. The thickness of the film laminated to the COC film is from 1 to 150 pm, preferably from 1 to 100 pm and particularly preferably from 4 to 50 pm. The thickness of the COC film is from 50 to 400 Nm, preferably from 150 to 350 Nm, particularly preferably from 200 to 300 Nm.
The novel process for producing a thermoformable composite film uses a solvent-free adhesive, preferably a solvent-free, single-component adhesive.
Particularly suitable for this purpose according to the invention is a solvent-free polyurethane-based moisture-curing single-component laminating resin. The laminating resin used differs from conventional laminating adhesives by being supplied and used with 100% solids content. The laminating resin is suitable for producing laminates from aluminum and paper, card or parchment, and for producing laminates from plastic films and paper or aluminum films. According to the invention the novel adhesive is very particularly suitable for producing thermoformable composite films where the novel adhesive is used to apply at least one thermoplastic film laminated to a film comprising cycloolefin copolymer.
Processing takes place on LF laminating plants which have heatable application systems and laminating units. Since the laminating resin is applied without solvent, no drying tunnels are required. A heatable laminating unit is advantageous for varying combinations. The laminating resin has to be heated to 80 - 100°C for application.
The novel thermoformable composite film is used for producing blister packs. The blister pack or PTP (push-through packaging) produced therefrom has very good water-vapor barrier properties, thus increasing the value of the packaged item. It can be used to pack contents such as pharmaceuticals and foodstuffs, in particular pelletized or capsule pharmaceuticals, foods containing rice, cookies, snacks, and also hygroscopic items, such as cigarettes and teabags.
The invention is described in more detail using a drawing and examples.
Drawing The drawing comprises Figures 1 to 3.
Fig. 1 shows the coating plant Fig. 2 shows the set-up of the coating plant Fig. 3 shows the application device in the coating plant.
The coating plant of Fig. 1 comprises an unwind (1 ), application device (2), short-wavelength infrared source (3), medium-wavelength infrared source (4), flotation drier (5), dry-lamination unit (6), corona system (7), web edge-guiding system (8), remoistening equipment (9), cooling unit (10), wind up (11), electron-beam unit (12), wet-lamination unit (13) and UV source (14).
Fig. 2 shows the set-up of the coating plant for the following procedures:
A) thermal drying or UV curing B) thermal drying with shock cooling C) thermal drying with remoistening D) thermal drying with dry lamination E) thermal drying with UV curing.
Fig. 3 shows the application device in the coating plant with application by smooth rollers using 4 rollers (wet). G here indicates a rubber roll and S a steel roll. The rolls here are heated and cooled. Application using smooth rolls is particularly suitable for the lamination of COC with PVC or oPP.
Examples The solvent-free single-component adhesive used, Herberts GmbH 1 K-~F
190X3, has the following physical properties:
Solids (%) 100, Viscosity (100 °C) 850 = 150 mPas Example 1 A COC film 190 Nm thick (194 g/m2) was laminated to both sides of an unoriented polypropylene film 25 Nm thick (22.5 g/m2) using Herberts GmbH 1 K-LF 190X3 solvent-free single-component adhesive. Application was at 1.50 g/m2, with corona treatment at 48 kW. For lamination a width of 810 mm was used, a speed of 50 m/min, and a smooth-roll application system with four rolls and one pass for each laminated side. The thickness of the thermoformable composite film was 210 Nm. The bond strength of the composite film was high, and when this bond strength was measured it was the composite film which broke.
Example 2 A COC film 190 Nm thick (194 g/m2) was laminated to both sides of an unoriented PVC film 35 tlm thick (4.6 g/m2) using Herberts GmbH 1 K-LF
190X3 solvent-free single-component adhesive. Application was at 1.50 g/m2, with corona treatment at 48 kW. For lamination a width of 810 mm was used, a speed of 50 m/min, and a smooth-roll application system with four rolls and one pass for each laminated side. The thickness of the thermoformable composite film was 260 Nm. The bond strength of the composite film was high, and when this bond strength was measured it was the composite film which broke.
Comparative Example The procedure of the example was followed except that both sides of the COC film were laminated to an unoriented polypropylene film. The thickness of the thermoformable composite film was 210 arm.
Claims (8)
1. A process for producing a thermoformable composite film, where a solvent-free adhesive is used to apply at least one thermoplastic film laminated to a film comprising cyclolefin copolymer.
2. The process as claimed in claim 1, where a solvent-free single-component adhesive is used to apply the thermoplastic film laminated to the film comprising cycloolefin copolymer.
3. The process as claimed in claim 1 or 2, where a solvent-free single-component adhesive is used to apply a laminated thermoplastic film comprising uPP or PVC.
4. The process as claimed in one or more of claims 1 to 3, where the thickness of the film laminated to the COC film is from 1 to 150 µm and the thickness of the COC film is from 50 to 400 µm.
5. The process as claimed in one or more of claims 1 to 4, where the thickness of the film laminated to the COC film is from 1 to 100 µm and the thickness of the COC film is from 150 to 350 µm.
6. The process as claimed in one or more of claims 1 to 5, where the thickness of the film laminated to the COC film is from 4 to 50 µm and the thickness of the COC film is from 175 to 300 µm.
7. The use of a solvent-free adhesive, preferably a single-component adhesive, for applying a thermoplastic film to a film comprising cycloolefin copolymer in order to produce a thermoformable composite film.
8. The use of a thermoformable composite film produced as claimed in one or more of claims 1 to 6 for producing blister packs.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE1998128857 DE19828857A1 (en) | 1998-06-29 | 1998-06-29 | One-component adhesive |
| DE19828857.3 | 1998-06-29 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA2276728A1 true CA2276728A1 (en) | 1999-12-29 |
Family
ID=7872315
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA 2276728 Abandoned CA2276728A1 (en) | 1998-06-29 | 1999-06-29 | Single-component adhesive |
Country Status (4)
| Country | Link |
|---|---|
| EP (1) | EP0968819A3 (en) |
| JP (1) | JP2000037833A (en) |
| CA (1) | CA2276728A1 (en) |
| DE (1) | DE19828857A1 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US11939131B2 (en) | 2021-06-03 | 2024-03-26 | Tekni-Plex,. Inc. | Recyclable blister package |
Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0838293B1 (en) * | 1996-10-28 | 2004-07-28 | Ticona GmbH | Mono- or multilayer film |
| DE19832500A1 (en) * | 1998-07-20 | 2000-01-27 | Ticona Gmbh | Thermoformable composite film |
| DE19915715A1 (en) | 1999-04-08 | 2000-10-19 | Ticona Gmbh | Microstructured components |
| DE10026714A1 (en) * | 2000-05-30 | 2001-12-13 | Hueck Folien Gmbh | Composite film, process for its production and its use |
| DE50110601D1 (en) * | 2000-12-06 | 2006-09-14 | Huhtamaki Deutschland Gmbh & C | Method for producing a composite film |
| GB0225621D0 (en) | 2002-11-02 | 2002-12-11 | Glaxo Group Ltd | Medicament carrier |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR100235089B1 (en) * | 1992-05-14 | 1999-12-15 | Mitsui Chemicals Inc | Ptp or blister packaging articles and packaging material therefor |
| CA2134320C (en) * | 1993-10-26 | 2001-01-09 | Toshiyuki Hirose | Polyolefin multilayer laminate and use thereof |
| KR100316898B1 (en) * | 1994-07-05 | 2002-06-27 | 나까니시 히로유끼 | Multilayer Laminates and Their Applications |
| KR100220961B1 (en) * | 1996-04-11 | 1999-09-15 | 사또 아끼오 | Laminated film and packaging material |
-
1998
- 1998-06-29 DE DE1998128857 patent/DE19828857A1/en not_active Withdrawn
-
1999
- 1999-06-21 EP EP99111882A patent/EP0968819A3/en not_active Withdrawn
- 1999-06-29 JP JP11183104A patent/JP2000037833A/en active Pending
- 1999-06-29 CA CA 2276728 patent/CA2276728A1/en not_active Abandoned
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US11939131B2 (en) | 2021-06-03 | 2024-03-26 | Tekni-Plex,. Inc. | Recyclable blister package |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2000037833A (en) | 2000-02-08 |
| DE19828857A1 (en) | 1999-12-30 |
| EP0968819A2 (en) | 2000-01-05 |
| EP0968819A3 (en) | 2000-04-05 |
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