CA2369137C - Multilayer containers exhibiting an improved adherence between polymer layers as well as excellent barrier characteristics - Google Patents
Multilayer containers exhibiting an improved adherence between polymer layers as well as excellent barrier characteristics Download PDFInfo
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- CA2369137C CA2369137C CA002369137A CA2369137A CA2369137C CA 2369137 C CA2369137 C CA 2369137C CA 002369137 A CA002369137 A CA 002369137A CA 2369137 A CA2369137 A CA 2369137A CA 2369137 C CA2369137 C CA 2369137C
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- radical
- cycloolefin
- zirconium dichloride
- topas
- polymer
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Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/32—Layered products comprising a layer of synthetic resin comprising polyolefins
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C45/00—Injection moulding, i.e. forcing the required volume of moulding material through a nozzle into a closed mould; Apparatus therefor
- B29C45/16—Making multilayered or multicoloured articles
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B65—CONVEYING; PACKING; STORING; HANDLING THIN OR FILAMENTARY MATERIAL
- B65D—CONTAINERS FOR STORAGE OR TRANSPORT OF ARTICLES OR MATERIALS, e.g. BAGS, BARRELS, BOTTLES, BOXES, CANS, CARTONS, CRATES, DRUMS, JARS, TANKS, HOPPERS, FORWARDING CONTAINERS; ACCESSORIES, CLOSURES, OR FITTINGS THEREFOR; PACKAGING ELEMENTS; PACKAGES
- B65D1/00—Containers having bodies formed in one piece, e.g. by casting metallic material, by moulding plastics, by blowing vitreous material, by throwing ceramic material, by moulding pulped fibrous material, by deep-drawing operations performed on sheet material
- B65D1/02—Bottles or similar containers with necks or like restricted apertures, designed for pouring contents
- B65D1/0207—Bottles or similar containers with necks or like restricted apertures, designed for pouring contents characterised by material, e.g. composition, physical features
- B65D1/0215—Bottles or similar containers with necks or like restricted apertures, designed for pouring contents characterised by material, e.g. composition, physical features multilayered
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B65—CONVEYING; PACKING; STORING; HANDLING THIN OR FILAMENTARY MATERIAL
- B65D—CONTAINERS FOR STORAGE OR TRANSPORT OF ARTICLES OR MATERIALS, e.g. BAGS, BARRELS, BOTTLES, BOXES, CANS, CARTONS, CRATES, DRUMS, JARS, TANKS, HOPPERS, FORWARDING CONTAINERS; ACCESSORIES, CLOSURES, OR FITTINGS THEREFOR; PACKAGING ELEMENTS; PACKAGES
- B65D35/00—Pliable tubular containers adapted to be permanently or temporarily deformed to expel contents, e.g. collapsible tubes for toothpaste or other plastic or semi-liquid material; Holders therefor
- B65D35/02—Body construction
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G61/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
- C08G61/02—Macromolecular compounds containing only carbon atoms in the main chain of the macromolecule, e.g. polyxylylenes
- C08G61/04—Macromolecular compounds containing only carbon atoms in the main chain of the macromolecule, e.g. polyxylylenes only aliphatic carbon atoms
- C08G61/06—Macromolecular compounds containing only carbon atoms in the main chain of the macromolecule, e.g. polyxylylenes only aliphatic carbon atoms prepared by ring-opening of carbocyclic compounds
- C08G61/08—Macromolecular compounds containing only carbon atoms in the main chain of the macromolecule, e.g. polyxylylenes only aliphatic carbon atoms prepared by ring-opening of carbocyclic compounds of carbocyclic compounds containing one or more carbon-to-carbon double bonds in the ring
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29L—INDEXING SCHEME ASSOCIATED WITH SUBCLASS B29C, RELATING TO PARTICULAR ARTICLES
- B29L2031/00—Other particular articles
- B29L2031/712—Containers; Packaging elements or accessories, Packages
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2250/00—Layers arrangement
- B32B2250/24—All layers being polymeric
- B32B2250/242—All polymers belonging to those covered by group B32B27/32
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2439/00—Containers; Receptacles
- B32B2439/70—Food packaging
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2439/00—Containers; Receptacles
- B32B2439/80—Medical packaging
Landscapes
- Engineering & Computer Science (AREA)
- Mechanical Engineering (AREA)
- Chemical & Material Sciences (AREA)
- Polymers & Plastics (AREA)
- Health & Medical Sciences (AREA)
- Manufacturing & Machinery (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Ceramic Engineering (AREA)
- Organic Chemistry (AREA)
- Laminated Bodies (AREA)
- Injection Moulding Of Plastics Or The Like (AREA)
- Containers Having Bodies Formed In One Piece (AREA)
- Processing And Handling Of Plastics And Other Materials For Molding In General (AREA)
- Blow-Moulding Or Thermoforming Of Plastics Or The Like (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
The present invention relates to multilayer containers comprising at least o ne cycloolefin polymer, to a process for producing these multilayer containers and to the use of these multilayer containers.
Description
Description MULTILAYER CONTAINERS EXHIBITING AN IMPROVED ADHERENCE BETWEEN
POLYMER LAYERS AS WELL AS EXCELLENT BARRIER CHARACTERISTICS
The present invention relates to multilayer containers comprising at least one cycloolefin polymer, to a process for producing these multilayer con-tainers and to the use of these multilayer containers.
JP-A-4 276 253 discloses multifayer containers comprising a layer of a thermoplastic saturated norbornene polymer which has been prepared by ring-opening metathesis polymerization and a further layer of a thermo-plastic polymer having good gas barrier properties.
JP-A-9 239 909, JP-A-7 171 858 and JP-A-9 011 416 disclose polyolefin/polycycloolefin multilayer containers which are suitable for the packaging of foods due to a further layer of a thermoplastic polymer having good oxygen barrier properties. The use of a bonding layer which improves adhesion between the different polymer layers is also described.
EP-A-824 067 and JP-A-10 059 343 likewise describe muitilayer containers which are made up of polyolefin layers and polycycloolefin layers and are able to keep in flavors and are thus suitable, for example, for the packaging and storage of toothpaste. In these patent publications, it is stated that the layers of various polymers are joined by means of bonding layers.
It is an object of the present invention to provide multilayer containers having improved adhesion between the layers and also an economical and environmentally friendly process for producing multilayer containers. For the purposes of the present invention, multilayer containers are containers which are made up of two or more layers of polymers.
The object of the present invention is achieved by multilayer containers comprising suitable cycloolefin polymers.
Brief Description of the Drawings Figure 1 shows an injection head used in accordance to produce a multilayer container in an embodiment of this disclosure;
Figure 2 shows an injection head used in accordance to produce a multilayer container in an embodiment of this disclosure;
Figure 3a and 3b show the injection profile for Polyester/Topas 6013; and Figure 4a and 4b shows the injection profile for Trogamid/Topas 6013.
The multilayer containers of the invention comprise at least one cycloolefin polymer which comprises polymerized units derived from at least one cyclic, in particular polycyclic, olefin and, if desired, from at least one acyclic olefin. The term cycloolefin polymer encompasses cycloolefin copolymers as well as cycloolefin homopolymers.
The multilayer containers of the invention comprise two or more polymer layers of which at least one polymer layer comprises at least one cycloolefin polymer comprising from 0.1 to 100% by weight, preferably from 0.1 to 99.9% by weight, particularly preferably from 3 to 75 mol%, based on the total mass of the cycloolefin polymer, of polymerized units derived from at least one polycyclic olefin of the formulae I, II, II', III, IV, V or VI
R
CH
I~H , CH CH R- C i CH
IH
C C H C H \
I~H I CH
. I CH
(11)~
CHR'-C -R
CH
CHS
IH
C H C H, I~H I CH
~ C H : (11), CH3CR, CH- ~
CIH
R
C H C H
I~H CH CH
(111) CH R C- R' I RS- C-R6 I H CH C H C H R
R' CH CH ~ ff C H CH CH CH
CH
H R- C- R' R C-Rf I R- I -Ra I (IV), C
/CH\' CH CH
CH CH CH R
POLYMER LAYERS AS WELL AS EXCELLENT BARRIER CHARACTERISTICS
The present invention relates to multilayer containers comprising at least one cycloolefin polymer, to a process for producing these multilayer con-tainers and to the use of these multilayer containers.
JP-A-4 276 253 discloses multifayer containers comprising a layer of a thermoplastic saturated norbornene polymer which has been prepared by ring-opening metathesis polymerization and a further layer of a thermo-plastic polymer having good gas barrier properties.
JP-A-9 239 909, JP-A-7 171 858 and JP-A-9 011 416 disclose polyolefin/polycycloolefin multilayer containers which are suitable for the packaging of foods due to a further layer of a thermoplastic polymer having good oxygen barrier properties. The use of a bonding layer which improves adhesion between the different polymer layers is also described.
EP-A-824 067 and JP-A-10 059 343 likewise describe muitilayer containers which are made up of polyolefin layers and polycycloolefin layers and are able to keep in flavors and are thus suitable, for example, for the packaging and storage of toothpaste. In these patent publications, it is stated that the layers of various polymers are joined by means of bonding layers.
It is an object of the present invention to provide multilayer containers having improved adhesion between the layers and also an economical and environmentally friendly process for producing multilayer containers. For the purposes of the present invention, multilayer containers are containers which are made up of two or more layers of polymers.
The object of the present invention is achieved by multilayer containers comprising suitable cycloolefin polymers.
Brief Description of the Drawings Figure 1 shows an injection head used in accordance to produce a multilayer container in an embodiment of this disclosure;
Figure 2 shows an injection head used in accordance to produce a multilayer container in an embodiment of this disclosure;
Figure 3a and 3b show the injection profile for Polyester/Topas 6013; and Figure 4a and 4b shows the injection profile for Trogamid/Topas 6013.
The multilayer containers of the invention comprise at least one cycloolefin polymer which comprises polymerized units derived from at least one cyclic, in particular polycyclic, olefin and, if desired, from at least one acyclic olefin. The term cycloolefin polymer encompasses cycloolefin copolymers as well as cycloolefin homopolymers.
The multilayer containers of the invention comprise two or more polymer layers of which at least one polymer layer comprises at least one cycloolefin polymer comprising from 0.1 to 100% by weight, preferably from 0.1 to 99.9% by weight, particularly preferably from 3 to 75 mol%, based on the total mass of the cycloolefin polymer, of polymerized units derived from at least one polycyclic olefin of the formulae I, II, II', III, IV, V or VI
R
CH
I~H , CH CH R- C i CH
IH
C C H C H \
I~H I CH
. I CH
(11)~
CHR'-C -R
CH
CHS
IH
C H C H, I~H I CH
~ C H : (11), CH3CR, CH- ~
CIH
R
C H C H
I~H CH CH
(111) CH R C- R' I RS- C-R6 I H CH C H C H R
R' CH CH ~ ff C H CH CH CH
CH
H R- C- R' R C-Rf I R- I -Ra I (IV), C
/CH\' CH CH
CH CH CH R
R
R' CH C H I
C I H R'- I_ R' IH iH (V), CH C \\ CH \ R' CH CFt~
R' ( CH CH CH \.' R, I~H CH CH CH
CH R C- R' H H R'_ C-Rb I (VI), CH CH CH I CH \R, R
where R1, R2, R3, R4, R5, R6, R' and R8 are identical or different and are each a hydrogen atom or a Cl-C20-hydrocarbon radical such as a linear or branched Cl-C8-alkyl radical, C6-C18-aryl radical, C7-C20-alkylenaryl radical, a cyclic or acyclic C2-C20-alkenyl radical or form a saturated, unsaturated or aromatic ring, where identical radicals R1 to R8 in the various formulae I to VI may have different meanings and n is from 0 to 5, and from 0 to 99.9% by weight, preferably from 0.1 to 99.9% by weight, particularly preferably from 5 to 80 mol /a, based on the total mass of the cycloolefin polymer, of polymerized units derived from one or more acyclic olefins of the formula VII
Rs R;o õ-- _ ~~~ l= I I), R R,2 where R9, R10~ R11 and R12 are identical or different and are each a hydrogen atom or a linear, branched, saturated or unsaturated Cl-C20-hydrocarbon radical such as a Cl-C8-alkyl radical or a C6-C18-aryl radical.
R' CH C H I
C I H R'- I_ R' IH iH (V), CH C \\ CH \ R' CH CFt~
R' ( CH CH CH \.' R, I~H CH CH CH
CH R C- R' H H R'_ C-Rb I (VI), CH CH CH I CH \R, R
where R1, R2, R3, R4, R5, R6, R' and R8 are identical or different and are each a hydrogen atom or a Cl-C20-hydrocarbon radical such as a linear or branched Cl-C8-alkyl radical, C6-C18-aryl radical, C7-C20-alkylenaryl radical, a cyclic or acyclic C2-C20-alkenyl radical or form a saturated, unsaturated or aromatic ring, where identical radicals R1 to R8 in the various formulae I to VI may have different meanings and n is from 0 to 5, and from 0 to 99.9% by weight, preferably from 0.1 to 99.9% by weight, particularly preferably from 5 to 80 mol /a, based on the total mass of the cycloolefin polymer, of polymerized units derived from one or more acyclic olefins of the formula VII
Rs R;o õ-- _ ~~~ l= I I), R R,2 where R9, R10~ R11 and R12 are identical or different and are each a hydrogen atom or a linear, branched, saturated or unsaturated Cl-C20-hydrocarbon radical such as a Cl-C8-alkyl radical or a C6-C18-aryl radical.
The cyclic olefins also include derivatives of these cyclic olefins containing polar groups such as halogen, hydroxyl, ester, alkoxy, carboxy, cyano, amido, imido or silyl groups.
In addition, the cycloolefin polymers used according to the invention for microstructured components can further comprise from 0 to 45% by weight, based on the total mass of the cycloolefin polymer, of polymerized units derived from one or more monocyclic olefins of the formula VIII
HC CH (Vlll), ~ 210 where m is from 2 to 10.
For the purposes of the present invention, preference is given to cycloolefin polymers which comprise polymerized units derived from polycyclic olefins of the formula I or III and polymerized units derived from acyclic olefins of the formula VII.
Particular preference is given to cycloolefin polymers which comprise polymerized units derived from olefins having a norbornene skeleton, very particularly preferably from norbornene and tetracyclododecene and, if desired, vinyinorbornene or norbornadiene. Particular preference is also given to cycloolefin polymers which comprise polymerized units derived from acyclic olefins having terminal double bonds, e.g. a-olefins having from 2 to 20 carbon atoms, very particularly ethylene or propylene.
Exceptional preference is given to norbornene-ethylene and tetracyclododecene-ethylene copolymers.
The preparation of the cycloolefin polymers can be carried out by means of heterogeneous or homogeneous catalysis by organometallic compounds, as described in many patents.
The cycloolefin polymers used according to the invention can be prepared at temperatures of from -78 to 200 C and 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 appropriate, a cocatalyst and, if appropriate, a support material. Suitable transition metal compounds are metallocenes, in particular stereorigid metallocenes. Examples of catalyst systems which are suitable for the preparation of the cycloolefin polymers used according to the invention are described in EP-A-407 870, 5 EP-A-485 893 and EP-A-503 422.
The cycloolefin polymers used according to the invention can be prepared using a metallocene as transition metal compound and an aluminoxane of the formula IXa R13 ( R13 IX a ~I--O Ai-O AI~
R13 P R,3 for the linear type and/or the formula lXb R1a I IX b J F =2 for the cyclic type, where, in the formulae lXa and lXb, R13 is a CI-C6-alkyl group or phenyl or benzyl and p is an integer from 2 to 50.
The transition metal component can be a metallocene of the formula X
R'a M' x ~17 where M1 is a metal of groups 3 to 10 or the lanthanide series of the Periodic Table of the Elements, preferably titanium, zirconium, hafnium, vanadium, niobium or tantalum, R14 and R15 are identical or different and are each a hydrogen atom, a halogen atom, a Cl-Clp-alkyl group, a Cl-Clp-alkoxy group, a C6-Clp-aryI
group, a C6-Clp-aryloxy group, a C2-Clp-alkenyl group, a C7-C40-arylalkyl group, a C7-C40-alkylaryl group or a C8-C40-arylalkenyl group, R16 and R17 are identical or different and are each a monocyclic or polycyclic hydrocarbon radical which can form a sandwich structure, with the central atom M1, Rie R19 Ri9 Rs R19 R's n ~ 2 I NR-- CR22, ~
I I f 1 1 11i R~0 RZ0 R21 R= R20 R2o R21 BR , AIR , = 1919, -Ge-, -Sn-, -0-, -S-, SO2, NR~9, CO, PR~9 or P(O)R~9 where R19, R20 and R21 are identical or different and are each a hydrogen atom, a halogen atom, a Cl-Clp-alkyl group, a Cl-Clp-fluoroalkyl group, a C6-Clp-fluoroaryl group, a C6-Clp-aryl group, a Cg-Clp-aryloxy group, a Cl-Clp-alkoxy group, a C2-Clp-alkenyl group, a C8-C40-arylalkyl group, a C7-C40-alkylaryl group or a C8-C40-arylalkenyl group or R19, R20 and R21 in each case together with the atoms connecting them form a ring, and M2 is silicon, germanium or tin.
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-phenylvinylsilylbis(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 dichioride, diphenyisilyl(9-fluorenyl)(cyclopentadienyl)zirconium dichloride, bis(1-indenyl)zirconium dichloride, diphenylmethylene(9-fluorenyl)cyclopentadienylzirconium dichioride, 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 dichioride, 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-(rI5-cyclopentad ienyl)-4,7,7-trimethyl(,q5-4,5,6,7-tetrahyd roindenyl-zirconium dichloride, [4-(115-cyclopentad ienyl)-4,7,7-triphenyl(,q 5-4, 5,6,7-tetrahyd roindenyl)]-zirconium dichloride, [4-(rl5-cyclopentad ienyl)-4,7-d imethyl-7-phenyl(r15-4,5,6,7-tetrahydro-indenyl)]zirconiurn dichloride, [4-(ri5-3'-tert-butylcyclopentad ienyl)-4,7,7-triphenyl(r15-4,5,6,7-tetra-hydroindenyl)]zirconium dichloride, [4-(r15-3'-tert-butylcyclopentadienyl)-4,7-dimethyl-7-phenyl(,n 5-4,5,6,7-tetra-hydroindenyl)]zirconium dichloride, [4-(r15-3'-methylcyclopentad ienyl)-4,7, 7-trimethyl(r15-4,5,6,7-tetrahydro-indenyl)]zirconium dichloride, [4-r15-3'-methylcyclopentadienyl)-4,7,7-trip henyl(,q 5-4,5,6, 7-tetrahydro-indenyl)]zirconium dichioride, [4-(rl 5-3'-methytcyclopentadienyl)-4,7-d imethyl-7-phenyl(r1 5-4,5,6,7-tetra-hydroindenyl)]zirconium dichloride, [4-(ri5-3'-isopropylcyclopentad ienyl)-4,7,7-trimethyl(,q 5-4,5,6,7-tetrahyd ro-indenyl)]zirconium dichloride, [4-(r15-3'-isopropylcyclopentadienyl)-4,7,7-triphenyl(r15-4,5,6,7-tetrahydro-indenyl)]zirconium dichloride, [4-(r15-3'-isopropylcyclopentadienyl)-4,7-dimethyl-7-phenyl(r15-4,5,6,7-tetra-hydroindenyl)]zirconium dichloride, [4-(-q 5-cyclopentadienyl)(r15-4,5-tetrahydropentalene)]zirconium dichloride, [4-(rl -3'-cyclopentadienyl)-4-methyl(ri 5-4,5-tetrahydropentalene)]zirconium dichloride, [4-(r1 5-cyclopentadienyl)-4-phenyl(rt5-4, 5-tetrahyd ropentalene)]zirconium dichioride, [4-(rl5-cyclopentadienyl)-4-phenyl(,15-4,5-tetrahydropentalene)]zirconium dichloride, [4-(r15-3'-methylcyclopentadienyl)(r15-4,5-tetrahydropentalene)]zirconium dichloride, [4-(r15-3'-isopropylcyclopentadienyl)(-q 5 -4,5-tetra hyd rope ntalene)]zircon iu m dichloride, [4-(115-3'-benzylcyclopentadienyl)(r15-4,5-tetrahydropentalene)]zirconium dichloride, [2,2,4-trimethyl-4-rl5-cyclopentadienyl)(r15-4, 5-tetrahydropentalene)J-zirconium dichloride [2,2,4-trimethyl-4-(rlt-3,4-diisopropyl)cyclopentadienyl)(-q 5-4,5-tetrahydro-pentalene)]zirconium dichloride.
The preparation of the cycloolefin polymers can also be carried out in other ways which are briefly outlined below. Catalyst systems based on mixed catalysts comprising titanium salts and organoaluminum compounds are described in DD-A-109 224 and DD-A-237 070. EP-A-156 464 describes the preparation of cycloolefin polymers 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 cycloolefin polymers used according to the invention can be prepared by homopolymerization and/or copolymerization of cyclic, preferably polycyclic, olefins with retention of the rings.
The cycloolefin polymers can also be prepared by ring-opening polymeriza-tion of at least one of the monomers of the formulae I to VI and subsequent hydrogenation of the products obtained. The cycloolefin polymers may also be prepared by ring-opening copolymerization of at least one of the monomers of the formulae I to VI with further monomers, e.g. monocyclic monomers of the formula Vlll, and subsequent hydrogenation of the products obtained. The preparation of cycloolefin polymers is described in the Japanese patents JP-B-3-14882, JP-B-3-122137, JP-B-4-63807, JP-B-2-27424 and JP-B-2-276842. Derivatives of these cyclic olefins containing polar groups such as halogen, hydroxyl, ester, alkoxy, carboxy, cyano, amido, imido or silyl groups are likewise included.
Hydrogenated polymers and copolymers, e.g. those of styrene and dicyclo-pentadiene, are likewise suitable and are likewise referred to as cycloolefin polymers for the purposes of the present application.
The polymerization can also be carried out in a plurality of stages, with block copolymers also being able to be formed (DE-A-42 05 416), Cycloolefin polymers are preferably amorphous, transparent and colorless materials. The heat distortion resistances of the cycloolefin polymers can be set within a wide range. For cycloolefin polymers, the glass transition temperature can be employed as an indication of the heat distortion resistance, as can be determined in accordance with ISO 75 part 1 and part 2 on injection-molded bodies. The cycloolefin polymers described have glass transition temperatures in the range from -50 to 220 C. Preference is given to glass transition temperatures in the range from 0 to 180 C, particularly preferably from 40 to 180 C.
The mean molar mass of the cycloolefin polymers can be controlled in a known manner by addition of hydrogen, variation of the catalyst concentra-tion or variation of the temperature. The cycloolefin polymers present in the microstructured components according to the present invention have mass average molar masses MW of from 1 000 to 10 000 000 g/mol. Preference is given to mass average molar masses Mw in the range from 5 000 to 5 000 000 g/mol, particularly preferably from 10 000 to 1. 200 000 g/mol.
The cycloolefin polymers present in the multilayer containers of the inven-tion have viscosity numbers in the range from 5 to 1 000 mi/g. Preference = CA 02369137 2001-10-09 is given to viscosity numbers in the range from 20 to 500 ml/g, particularly preferably from 30 to 300 milg.
The multilayer containers of the invention can also contain blends of at 5 least one cycloolefin polymer and at least one further polymer in any mixing ratios in one or more layers.
For the blends with cycloolefin polymers, preference is given to using the following polymers: polyethylene, polypropylene, ethylene-propylene 10 copolymers, polybutylene, poly(4-methyl-1 -pentene), polyisoprene, polyisobutylene, natural rubber, poly(1-methyl methacrylate), further polymethacrylates, polyacrylate, acrylate-methacrylate copolymers, polystyrene, styrene-acry lonitrile copolymers, bisphenol A polycarbonate, further polycarbonates, aromatic polyester carbonates, polyethylene terephthalate, polybutylene terephthalate, amorphous polyacrylate, nylon 6, nylon 66, further polyamides, polyaramides, polyether ketones, polyoxymethylene, polyoxyethylene, polyurethanes, polysulfones, polyether sulfones, polyvinylidene fluoride.
For blends of cycloolefin polymers and polyolefins, preference is given to using the following polyolefins: homopolymers of ethylene and propylene and copolymers of these two monomers, copolymers based on ethylene together with linear or branched olefins such as butene, pentene, hexene, heptene, octene, nonene, decene, undecene and dodecene, copolymers based on propylene together with linear or branched olefins such as butene, pentene, hexene, heptene, octene, nonene, decene, undecene and dodecene, terpolymers of ethylene, propylene and linear or branched olefins such as butene, pentene, hexene, heptene, octene, nonene, decene, undecene and dodecene.
The blends can be produced by customary methods, e.g. by coextrusion of the polymer components from the melt, with or without use of further additives, and subsequent granulation.
Cycloolefin polymers can be processed from the melt or from solution.
Suitable solvents are aprotic nonpolar hydrocarbons such as decalin or mixtures of linear or branched hydrocarbons.
The multilayer containers of the invention comprise at least one layer comprising at least one cycloolefin polymer together with at least one further layer of another polymer or a blend of further polymers. Suitable polymers are, for example, polyethylene, polypropylene, ethylene-propylene copolymers, polybutylene, poly(4-methyl-1 -pentene), polyisoprene, polyisobutylene, natural rubber, poly(1-methyl methacrylate), further polymethacrylates, polyacrylate, acrylate-methacrylate copolymers, polystyrene, styrene-acrylonitrile copolymers, polyacrylonitrile, bisphenol A
polycarbonate, further polycarbonates, aromatic polyester carbonates, polyethylene terephthalate, polybutylene terephthalate, further polyesters, amorphous polyacrylates, nylon 6, nylon 66, further polyamides, polyaramides, polyether ketones, polyoxymethylene, polyoxyethylene, polyurethanes, polysulfones, polyether sulfones, polyvinyl chloride, polyvinylidene chloride, polyvinylidene fluoride.
Particularly useful polymers are ones which have good gas barrier properties, e.g. polyesters such as polyethylene terephthalate, polyethylene naphthalate and also liquid-crystalline polyesters, polyacrylonitrile, polyvinyl chloride, polyvinylidene chloride, ethylvinyl alcohol, polyamides and others.
The production of the multilayer containers of the invention can be carried out by multicomponent injection molding, multicomponent injection blow molding and multicomponent injection stretch blow molding.
The production of preforms for multicomponent injection blow molding and multicomponent injection stretch blow molding by multicomponent injection molding leads to multilayer preforms. Multilayer preforms can be produced, for example, by coinjection of two or more materials or by injecting one or more further materials over the first layer of a material.
The production of the multilayer containers of the invention can be carried out using customary amounts of additives such as plasticizers, UV
stabilizers, optical brighteners, antioxidants, antistatics, heat stabilizers or reinforcing additives such as glass fibers, carbon fibers or high-modulus fibers such as polyaramides or liquid-crystalline polyesters or the like.
Furthermore, fillers such as inorganic materials, talc, titanium dioxide or the like can be used. The abovementioned additives and fillers can have been added before the processing of the polymer materials or else can be added during processing.
In addition, the cycloolefin polymers used according to the invention for microstructured components can further comprise from 0 to 45% by weight, based on the total mass of the cycloolefin polymer, of polymerized units derived from one or more monocyclic olefins of the formula VIII
HC CH (Vlll), ~ 210 where m is from 2 to 10.
For the purposes of the present invention, preference is given to cycloolefin polymers which comprise polymerized units derived from polycyclic olefins of the formula I or III and polymerized units derived from acyclic olefins of the formula VII.
Particular preference is given to cycloolefin polymers which comprise polymerized units derived from olefins having a norbornene skeleton, very particularly preferably from norbornene and tetracyclododecene and, if desired, vinyinorbornene or norbornadiene. Particular preference is also given to cycloolefin polymers which comprise polymerized units derived from acyclic olefins having terminal double bonds, e.g. a-olefins having from 2 to 20 carbon atoms, very particularly ethylene or propylene.
Exceptional preference is given to norbornene-ethylene and tetracyclododecene-ethylene copolymers.
The preparation of the cycloolefin polymers can be carried out by means of heterogeneous or homogeneous catalysis by organometallic compounds, as described in many patents.
The cycloolefin polymers used according to the invention can be prepared at temperatures of from -78 to 200 C and 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 appropriate, a cocatalyst and, if appropriate, a support material. Suitable transition metal compounds are metallocenes, in particular stereorigid metallocenes. Examples of catalyst systems which are suitable for the preparation of the cycloolefin polymers used according to the invention are described in EP-A-407 870, 5 EP-A-485 893 and EP-A-503 422.
The cycloolefin polymers used according to the invention can be prepared using a metallocene as transition metal compound and an aluminoxane of the formula IXa R13 ( R13 IX a ~I--O Ai-O AI~
R13 P R,3 for the linear type and/or the formula lXb R1a I IX b J F =2 for the cyclic type, where, in the formulae lXa and lXb, R13 is a CI-C6-alkyl group or phenyl or benzyl and p is an integer from 2 to 50.
The transition metal component can be a metallocene of the formula X
R'a M' x ~17 where M1 is a metal of groups 3 to 10 or the lanthanide series of the Periodic Table of the Elements, preferably titanium, zirconium, hafnium, vanadium, niobium or tantalum, R14 and R15 are identical or different and are each a hydrogen atom, a halogen atom, a Cl-Clp-alkyl group, a Cl-Clp-alkoxy group, a C6-Clp-aryI
group, a C6-Clp-aryloxy group, a C2-Clp-alkenyl group, a C7-C40-arylalkyl group, a C7-C40-alkylaryl group or a C8-C40-arylalkenyl group, R16 and R17 are identical or different and are each a monocyclic or polycyclic hydrocarbon radical which can form a sandwich structure, with the central atom M1, Rie R19 Ri9 Rs R19 R's n ~ 2 I NR-- CR22, ~
I I f 1 1 11i R~0 RZ0 R21 R= R20 R2o R21 BR , AIR , = 1919, -Ge-, -Sn-, -0-, -S-, SO2, NR~9, CO, PR~9 or P(O)R~9 where R19, R20 and R21 are identical or different and are each a hydrogen atom, a halogen atom, a Cl-Clp-alkyl group, a Cl-Clp-fluoroalkyl group, a C6-Clp-fluoroaryl group, a C6-Clp-aryl group, a Cg-Clp-aryloxy group, a Cl-Clp-alkoxy group, a C2-Clp-alkenyl group, a C8-C40-arylalkyl group, a C7-C40-alkylaryl group or a C8-C40-arylalkenyl group or R19, R20 and R21 in each case together with the atoms connecting them form a ring, and M2 is silicon, germanium or tin.
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-phenylvinylsilylbis(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 dichioride, diphenyisilyl(9-fluorenyl)(cyclopentadienyl)zirconium dichloride, bis(1-indenyl)zirconium dichloride, diphenylmethylene(9-fluorenyl)cyclopentadienylzirconium dichioride, 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 dichioride, 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-(rI5-cyclopentad ienyl)-4,7,7-trimethyl(,q5-4,5,6,7-tetrahyd roindenyl-zirconium dichloride, [4-(115-cyclopentad ienyl)-4,7,7-triphenyl(,q 5-4, 5,6,7-tetrahyd roindenyl)]-zirconium dichloride, [4-(rl5-cyclopentad ienyl)-4,7-d imethyl-7-phenyl(r15-4,5,6,7-tetrahydro-indenyl)]zirconiurn dichloride, [4-(ri5-3'-tert-butylcyclopentad ienyl)-4,7,7-triphenyl(r15-4,5,6,7-tetra-hydroindenyl)]zirconium dichloride, [4-(r15-3'-tert-butylcyclopentadienyl)-4,7-dimethyl-7-phenyl(,n 5-4,5,6,7-tetra-hydroindenyl)]zirconium dichloride, [4-(r15-3'-methylcyclopentad ienyl)-4,7, 7-trimethyl(r15-4,5,6,7-tetrahydro-indenyl)]zirconium dichloride, [4-r15-3'-methylcyclopentadienyl)-4,7,7-trip henyl(,q 5-4,5,6, 7-tetrahydro-indenyl)]zirconium dichioride, [4-(rl 5-3'-methytcyclopentadienyl)-4,7-d imethyl-7-phenyl(r1 5-4,5,6,7-tetra-hydroindenyl)]zirconium dichloride, [4-(ri5-3'-isopropylcyclopentad ienyl)-4,7,7-trimethyl(,q 5-4,5,6,7-tetrahyd ro-indenyl)]zirconium dichloride, [4-(r15-3'-isopropylcyclopentadienyl)-4,7,7-triphenyl(r15-4,5,6,7-tetrahydro-indenyl)]zirconium dichloride, [4-(r15-3'-isopropylcyclopentadienyl)-4,7-dimethyl-7-phenyl(r15-4,5,6,7-tetra-hydroindenyl)]zirconium dichloride, [4-(-q 5-cyclopentadienyl)(r15-4,5-tetrahydropentalene)]zirconium dichloride, [4-(rl -3'-cyclopentadienyl)-4-methyl(ri 5-4,5-tetrahydropentalene)]zirconium dichloride, [4-(r1 5-cyclopentadienyl)-4-phenyl(rt5-4, 5-tetrahyd ropentalene)]zirconium dichioride, [4-(rl5-cyclopentadienyl)-4-phenyl(,15-4,5-tetrahydropentalene)]zirconium dichloride, [4-(r15-3'-methylcyclopentadienyl)(r15-4,5-tetrahydropentalene)]zirconium dichloride, [4-(r15-3'-isopropylcyclopentadienyl)(-q 5 -4,5-tetra hyd rope ntalene)]zircon iu m dichloride, [4-(115-3'-benzylcyclopentadienyl)(r15-4,5-tetrahydropentalene)]zirconium dichloride, [2,2,4-trimethyl-4-rl5-cyclopentadienyl)(r15-4, 5-tetrahydropentalene)J-zirconium dichloride [2,2,4-trimethyl-4-(rlt-3,4-diisopropyl)cyclopentadienyl)(-q 5-4,5-tetrahydro-pentalene)]zirconium dichloride.
The preparation of the cycloolefin polymers can also be carried out in other ways which are briefly outlined below. Catalyst systems based on mixed catalysts comprising titanium salts and organoaluminum compounds are described in DD-A-109 224 and DD-A-237 070. EP-A-156 464 describes the preparation of cycloolefin polymers 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 cycloolefin polymers used according to the invention can be prepared by homopolymerization and/or copolymerization of cyclic, preferably polycyclic, olefins with retention of the rings.
The cycloolefin polymers can also be prepared by ring-opening polymeriza-tion of at least one of the monomers of the formulae I to VI and subsequent hydrogenation of the products obtained. The cycloolefin polymers may also be prepared by ring-opening copolymerization of at least one of the monomers of the formulae I to VI with further monomers, e.g. monocyclic monomers of the formula Vlll, and subsequent hydrogenation of the products obtained. The preparation of cycloolefin polymers is described in the Japanese patents JP-B-3-14882, JP-B-3-122137, JP-B-4-63807, JP-B-2-27424 and JP-B-2-276842. Derivatives of these cyclic olefins containing polar groups such as halogen, hydroxyl, ester, alkoxy, carboxy, cyano, amido, imido or silyl groups are likewise included.
Hydrogenated polymers and copolymers, e.g. those of styrene and dicyclo-pentadiene, are likewise suitable and are likewise referred to as cycloolefin polymers for the purposes of the present application.
The polymerization can also be carried out in a plurality of stages, with block copolymers also being able to be formed (DE-A-42 05 416), Cycloolefin polymers are preferably amorphous, transparent and colorless materials. The heat distortion resistances of the cycloolefin polymers can be set within a wide range. For cycloolefin polymers, the glass transition temperature can be employed as an indication of the heat distortion resistance, as can be determined in accordance with ISO 75 part 1 and part 2 on injection-molded bodies. The cycloolefin polymers described have glass transition temperatures in the range from -50 to 220 C. Preference is given to glass transition temperatures in the range from 0 to 180 C, particularly preferably from 40 to 180 C.
The mean molar mass of the cycloolefin polymers can be controlled in a known manner by addition of hydrogen, variation of the catalyst concentra-tion or variation of the temperature. The cycloolefin polymers present in the microstructured components according to the present invention have mass average molar masses MW of from 1 000 to 10 000 000 g/mol. Preference is given to mass average molar masses Mw in the range from 5 000 to 5 000 000 g/mol, particularly preferably from 10 000 to 1. 200 000 g/mol.
The cycloolefin polymers present in the multilayer containers of the inven-tion have viscosity numbers in the range from 5 to 1 000 mi/g. Preference = CA 02369137 2001-10-09 is given to viscosity numbers in the range from 20 to 500 ml/g, particularly preferably from 30 to 300 milg.
The multilayer containers of the invention can also contain blends of at 5 least one cycloolefin polymer and at least one further polymer in any mixing ratios in one or more layers.
For the blends with cycloolefin polymers, preference is given to using the following polymers: polyethylene, polypropylene, ethylene-propylene 10 copolymers, polybutylene, poly(4-methyl-1 -pentene), polyisoprene, polyisobutylene, natural rubber, poly(1-methyl methacrylate), further polymethacrylates, polyacrylate, acrylate-methacrylate copolymers, polystyrene, styrene-acry lonitrile copolymers, bisphenol A polycarbonate, further polycarbonates, aromatic polyester carbonates, polyethylene terephthalate, polybutylene terephthalate, amorphous polyacrylate, nylon 6, nylon 66, further polyamides, polyaramides, polyether ketones, polyoxymethylene, polyoxyethylene, polyurethanes, polysulfones, polyether sulfones, polyvinylidene fluoride.
For blends of cycloolefin polymers and polyolefins, preference is given to using the following polyolefins: homopolymers of ethylene and propylene and copolymers of these two monomers, copolymers based on ethylene together with linear or branched olefins such as butene, pentene, hexene, heptene, octene, nonene, decene, undecene and dodecene, copolymers based on propylene together with linear or branched olefins such as butene, pentene, hexene, heptene, octene, nonene, decene, undecene and dodecene, terpolymers of ethylene, propylene and linear or branched olefins such as butene, pentene, hexene, heptene, octene, nonene, decene, undecene and dodecene.
The blends can be produced by customary methods, e.g. by coextrusion of the polymer components from the melt, with or without use of further additives, and subsequent granulation.
Cycloolefin polymers can be processed from the melt or from solution.
Suitable solvents are aprotic nonpolar hydrocarbons such as decalin or mixtures of linear or branched hydrocarbons.
The multilayer containers of the invention comprise at least one layer comprising at least one cycloolefin polymer together with at least one further layer of another polymer or a blend of further polymers. Suitable polymers are, for example, polyethylene, polypropylene, ethylene-propylene copolymers, polybutylene, poly(4-methyl-1 -pentene), polyisoprene, polyisobutylene, natural rubber, poly(1-methyl methacrylate), further polymethacrylates, polyacrylate, acrylate-methacrylate copolymers, polystyrene, styrene-acrylonitrile copolymers, polyacrylonitrile, bisphenol A
polycarbonate, further polycarbonates, aromatic polyester carbonates, polyethylene terephthalate, polybutylene terephthalate, further polyesters, amorphous polyacrylates, nylon 6, nylon 66, further polyamides, polyaramides, polyether ketones, polyoxymethylene, polyoxyethylene, polyurethanes, polysulfones, polyether sulfones, polyvinyl chloride, polyvinylidene chloride, polyvinylidene fluoride.
Particularly useful polymers are ones which have good gas barrier properties, e.g. polyesters such as polyethylene terephthalate, polyethylene naphthalate and also liquid-crystalline polyesters, polyacrylonitrile, polyvinyl chloride, polyvinylidene chloride, ethylvinyl alcohol, polyamides and others.
The production of the multilayer containers of the invention can be carried out by multicomponent injection molding, multicomponent injection blow molding and multicomponent injection stretch blow molding.
The production of preforms for multicomponent injection blow molding and multicomponent injection stretch blow molding by multicomponent injection molding leads to multilayer preforms. Multilayer preforms can be produced, for example, by coinjection of two or more materials or by injecting one or more further materials over the first layer of a material.
The production of the multilayer containers of the invention can be carried out using customary amounts of additives such as plasticizers, UV
stabilizers, optical brighteners, antioxidants, antistatics, heat stabilizers or reinforcing additives such as glass fibers, carbon fibers or high-modulus fibers such as polyaramides or liquid-crystalline polyesters or the like.
Furthermore, fillers such as inorganic materials, talc, titanium dioxide or the like can be used. The abovementioned additives and fillers can have been added before the processing of the polymer materials or else can be added during processing.
It is possible to join the various polymer layers to one another by use of bonding layers. Materials suitable for this purpose are, for example, polyolefins such as the materials Tafiner AdmerG from Mitsui Chemicals.
However, it has surprisingly been found that the cycloolefin polymers used according to the invention display excellent adhesion to the other layers.
Use of bonding layers can therefore be dispensed with, which is of great economic advantage owing to the lower material costs and the greater simplicity of the production of the multilayer containers.
The cycloolefin copolymers used according to the invention surprisingly display a significant improvement in the mechanical properties in the production of multilayer systems according to the invention without bonding layers.
The adhesion between the various layers of the multilayer containers of the invention can be optimized by matching the shrinkage behavior of the different materials used according to the invention.
Compared to containers produced from only cycloolefin polymers, the multilayer containers of the invention have improved resistance to impacts and also display improved resistance to oils and fats.
Due to their high purity, extraordinarily low water absorption, excellent barrier properties toward gases and moisture, their good blood compatibility, excellent biocompatibility, good sterilizability by means of hot steam, hot air, ethylene oxide gas and high-energy radiation (gamma-rays and electron beams), high resistance to acids, alkalis and polar solvents, the multilayer containers of the invention are very suitable for packaging and storage in the medical, pharmaceutical, cosmetic and food sectors, e.g. in the form of syringes, injectors, cartridges, vials and bottles, tubes and other containers.
Owing to their particular properties, the multilayer containers of the invention are extremely well suited to hot packaging of liquids in these containers, e.g. in the food sector.
The invention is illustrated by the following examples.
However, it has surprisingly been found that the cycloolefin polymers used according to the invention display excellent adhesion to the other layers.
Use of bonding layers can therefore be dispensed with, which is of great economic advantage owing to the lower material costs and the greater simplicity of the production of the multilayer containers.
The cycloolefin copolymers used according to the invention surprisingly display a significant improvement in the mechanical properties in the production of multilayer systems according to the invention without bonding layers.
The adhesion between the various layers of the multilayer containers of the invention can be optimized by matching the shrinkage behavior of the different materials used according to the invention.
Compared to containers produced from only cycloolefin polymers, the multilayer containers of the invention have improved resistance to impacts and also display improved resistance to oils and fats.
Due to their high purity, extraordinarily low water absorption, excellent barrier properties toward gases and moisture, their good blood compatibility, excellent biocompatibility, good sterilizability by means of hot steam, hot air, ethylene oxide gas and high-energy radiation (gamma-rays and electron beams), high resistance to acids, alkalis and polar solvents, the multilayer containers of the invention are very suitable for packaging and storage in the medical, pharmaceutical, cosmetic and food sectors, e.g. in the form of syringes, injectors, cartridges, vials and bottles, tubes and other containers.
Owing to their particular properties, the multilayer containers of the invention are extremely well suited to hot packaging of liquids in these containers, e.g. in the food sector.
The invention is illustrated by the following examples.
Examples Example 1- 2-component injection molding Inlay injection molding of Topas on a tensile bar tool having two cavities The experiments were carried out using a Krauss Maffei model KM 90-210B injection molding machine and a tool for producing DIN
standard tensile bars having two cavities in an S shape.
To prepare for the experiments, tensile bars were produced from all materials and were halved. The part of the tensile bar farthest from the gate was used as inlay for the 2-component injection molding procedure. For this purpose, the halved tensiie bar (inlay) was placed in the tool in its original position and the missing half of the tensile bar was in each case injected onto it using the second polymer (over-injected polymer; see table 1). Tensile tests were then carried out on the resulting tensile bars with joining seam in accordance with ISO 527-1 to determine the rupture stress and elongation at break (see table 1).
The processing conditions are shown in tables 2 and 3.
standard tensile bars having two cavities in an S shape.
To prepare for the experiments, tensile bars were produced from all materials and were halved. The part of the tensile bar farthest from the gate was used as inlay for the 2-component injection molding procedure. For this purpose, the halved tensiie bar (inlay) was placed in the tool in its original position and the missing half of the tensile bar was in each case injected onto it using the second polymer (over-injected polymer; see table 1). Tensile tests were then carried out on the resulting tensile bars with joining seam in accordance with ISO 527-1 to determine the rupture stress and elongation at break (see table 1).
The processing conditions are shown in tables 2 and 3.
Table I
Over-injected polymer Test specimen initially Rupture Elongation placed in the tool stress at break MPa %
LLDPE Innovex To as 6013 Lot 74093 3.9 11.8 HostalenO PPR 1042 Topas 6013 Lot 74093 3.7 3.6 Im etO PET TS6 To as 6013 Lot 74093 8.3 4.4 Nylon MXD6 To as 6013 Lot 74093 - -Ba er PC CD 2005 To as 6013 Lot 74093 - -DSM Stanylan LDPE- To as@ 8007 Lot 54028 2.4 8.1 Hostalen PPR 1042 To asO 8007 Lot 54028 9.2 7.0 Im et@ PET T86 To asO 8007 Lot 54028 8.7 5.3 Nylon MXD6 To asO 8007 Lot 54028 990 6.3 Ba er@ PC CD 2005 To as@ 8007 Lot 54028 - -TopasO 6013 Lot 74093 DSM Stanylan LDPE 6.8 53.1 To as 6013 Lot 74093 Hostaten PPR 1042 1.0 0.85 To asO 6013 Lot 74093 Im et PET T86 3.3 2.6 To as 6013 Lot 74093 Nylon MXD6 3.7 2.7 To as@ 6013 Lot 74093 Ba er PC CD 2005 - -To as 8007 Lot 54028 DSM Stanylan LDPE 4.4 16.9 To asO 8007 Lot 54028 Hostalen PPR 1042 8.5 6.6 To asg 8007 Lot 54028 Im et(D PET T86 4.8 3.3 To as@ 8007 Lot 54028 Nylon MXD6 5.0 3.2 To asO 8007 Lot 54028 Ba er@ PC CD 2005 6.0 3.9 c O
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Q ~ ~ i ~ ~ ~ ~ i ~
E V O C) O 0 0 O O O O 0 O O
f- 1- f~ !- 1~ 1- c'') C'M Cr) CM M N
~ ~ N N N N N N N N N N N N
W u) W ~ Ln Nj C C _ a O O d O O
0 O r (O N O Q O
r Cfl N O U) o C a F- ~ O C 00 O) V) ~ N c0 p ~ ~p C~ Q' tp O U R~
O W p V ~- c W p Q 0- a X a (9) N E~ iv c ~ tU
~
S n in , O ' a) ~
o~ M Q c~ _OE z Q
m c~ o i~ z m E
E c~ c~) M M M c'M oo Co Cp op ap ~~ O
O O O O O O N N N N N ln 0 O 0 0 O 0 0 O O O O 0 O O f/) ~ N
E V d 'V d d V d ~7 ~ ~ ~ d N
C~ _A t' 1~ f- 1~ f~ 1+ t1~ tn tl) ln U) f~ ~ t ~ O 0 0 0 0 0 0 0 0 0 0 0 O
Cl ~ J J J J J J J J J J J~ p~
O r ~~ i- r- O O p 0 0 O ~ O C) M 0 0 O O 0 0 0 C) O 0 0 O O aLf) r' 4) O CO CO CO f0 (O Cfl 00 00 OO 00 00 O
o o ~
F~- > a a a a a Q. a ~ a Q a a ~ F - 1~ 1- 10 F - 1- H F - F- F0 - F - F- *~*
Example 2 - 2-component injection molding Coinjection of TopasO by injection molding using a multi-part mold This was carried out using a 3-component Kl'ockner Ferromatik injection molding machine and a centrally gated plate (300 x 215 x 3 mm).
Using a special injection head having controlled and sprung needle valves, the injection head nozzle was selected by means of a preceding 2-component distributor disk so that the core component was injected centrally into the cavity and the second melt exiting coaxially around it was injected simultaneously or, if desired, after an interval (see fig. 1).
Mixing of the two streams of material was avoided by selection of the respective fluidities and, in particular, by selection of the injection sequence/process conditions.
Formation of the core layer, here component B, was monitored in the case of transparent or slightly colored materials. As colorant, a TopasO 5013 (cycloolefin copolymer/Ticona ; HDT/B (0.45 N/mm2) = 130 C; melt index MVR at 260 C, 2.16 kg,.
= 56 ml/min)/Sandoplast BIauCD B masterbatch was added in a concentration of about 2%.
Selection of the component A of the outer layer and the component B of the core layer is summarized in table 4.
Table 4: Material combinations:
Component B Component A
Topas Cycloolefin copolymer/Ticona HDT/B (0.45 Metocen(D PP X50081 Transparent 8007 N/mm2) = 75 C melt index MVR at 260 C, 94-2710/Tagor polypropylene 2.16 kg = 30 mI/min Topas Cycloolefln copolymer/Ticona HDT/B (0.45 K-Resin KR-01/ Phillips Styrene-8007 N/mm2) = 75 C melt index MVR at 260 C, butadiene 2.16 kg = 30 mi/min copolymer TopasU Cycloolefin copolymer/Ticona HDT/B (0.45 PET Polyester T86 Transparent 6013 N/mm2) = 130 C melt index MVR at 260 C, W03/Kosa polyester 2.16 kg = 13 ml/min Topas Cycloolefin copolymer/Ticona HDT/B (0.45 Grilamid TR90/ Transparent 6013 N/mm2) = 130 C melt index MVR at 260 C, EMS-Chemie polyamide 2.16 kg = 13 mi/min Topas Cycloolefin copolymer/Ticona HDT/B (0.45 Nylon MXD 6/Mitsui Transparent 6013 N/mm2) = 130 C melt index MVR at 260 C, polyamide 2.16 kg = 13 ml/min Topas Cycloolefin copolymer/Ticona HDT/B (0.45 Trogamid CX7323/ Transparent 6013 N/mm) = 130 C melt index MVR at 260 C, Degussa-Huls polyamide 2.16 kg = 13 mI/min Topas Cycloolefin copolymer/Ticona HDT/B (0.45 Metocen(ED PP X50081 Transparent 6013 N/mm2) = 130 C melt index MVR at 260 C, 94/2710/Tagor polypropylene 2.16kg=13mI/min Procedure:
-~-,-.-r-_--The various material combinations were each processed for two different injection profiles.
The profiles differed in the sequence of injection of the enveloping component (component A) and the core component (component B).
Example 2a:
In the case of injection profile 2a, the time delay between commencement of injection of the component B and the component A was about two seconds, at which time 82 percent of the amount of component A had already been injected. The injection profile 2a is shown by way of example in figs. 3a and 3b for polyester/Topas 6013.
Example 2b:
In the case of the injection profile 2b, the time delay between commencement of injection of component B and component A was only about 0.5 seconds. After this time, about 90 percent of the remaining amounts were injected simst(taneQusly.
The injection profile 2b is shown by way of example in figs. 4a and 4b for Trogamid /Topas 6013.
In both cases, the sprue is sealed with the component A at the end of the respective injection procedure. Further processing parameters for the experiments are shown in table 6.
Breakthrough of the enveloping layer through the core component was not observed, even when using very fluid enveloping material such as Metocen PP X50081.
The layer thickness distribution can be influenced via the respective injection volumes, injection pressures and injection rates of the 2 independently regulatable injection molding units, while the position of the core layer can be shifted by means of the temperature of the tool.
Uniform layer thickness distributions and good transparency of the plates can be achieved under the above-described process conditions. In addition, the plates were assessed in respect of adhesion of the layers and distortion tendency (see table 5).
Table 5: Experimental results:
Injection Material combination Adhesion Clouding Distortion molding Component A/ between tendency profile layers Component B
2a I Metocen PP / Topas 8007 ++ o -2b I Metocen PP / Topas 8007 ++ +0 -2a II K-Resin / Topas@ 8007 + +0 +0 2b II K-Resin / Topas 8007 + + +0 2a III Metocen PP / Topas@ 6013 + o -2b III Metocen PP / Topas@ 6013 + +0 -2a IV Trogamid / Topas@ 6013 +0 + +0 2b IV Trogamid / Topas 6013 +0 ++ +0 2a V GrilamidO / Topas@ 6013 0 + +
2b V Grilamid / Topas 6013 0 + +
2a VI PET Polyester / Topas 6013 - 0- +
2b VI PET Polyester / Topas 6013 - o +
2a VII Nylon MXD6 / Topas 6013 0- o- +
2b VII Nylon MXD6 / Topas@ 6013 0- 0 +
~ d ~ 0 O 0 OV ~ 0 ~ ~ 0 ~ O 0 0 0 C) LO
d X == CO M N N N N N N N ~ qT CD N
-o m M
~ U) 2 X ~ O O ~ 0) 0) O 0 d ~ ) O O O 0 O O LO
H U '. Cfl cM N N N M M N c'M CO CO ~ r t0 N
Cfl N
~
C _ p 0 cl a M 0 0 0 >+ 0 O c ~ ~ ti 0 0 000 0 a0 )( 0 U-) lf) M tn Z ~ ~(fl ce) N N N N N N N fY) Cr) LO ~ ~- N
i f) N
(D
~ f=M- ~ C) (M N N N N N N N OV (V LO ~ COO N
~ N
E 0) 0 Q ~
CY) 12 3 ~ M N N N N N N 0) -O [') ~ L[) 0 N
O O O 0 0 O 00 00 C) OM) O O O L1') ~ (p cf) cY) M co co M m N ~ U3 U) N N
a a c ~
o "
~ ~
~
~ C) 0 O 0 t~ ~ 0 0 ~ 0 O O O 0 COO N
N X ~ ~O M N N N N N N N ~t tt i f6 a O O ~ ~ ~ ~ v~i ~ O O LO LO
Y Y ~ QO Ce) N N N N N N LO LO N
cn o 0 0 ~ n ~ n ~ n ~ c) l n ~ n 0 0 C) o 0 LO
F- 00 ~ M N N N N N N U) Lf) V) N (O N
Q
~ uUi r- N c~) 'It ~ p) N 0 C ~ ~ C C X ~
0 4m, 0 ti N N N N N~~ C7 W
a M
E
EL N
=H ~
~-.
N
~ E UN
Q (,D FL
a~
a N
~ o o Q.~ o a~
a a c = Z
~ o E ai U 1 , u~i m d ~ U
1- U U F- U~ ,...
Over-injected polymer Test specimen initially Rupture Elongation placed in the tool stress at break MPa %
LLDPE Innovex To as 6013 Lot 74093 3.9 11.8 HostalenO PPR 1042 Topas 6013 Lot 74093 3.7 3.6 Im etO PET TS6 To as 6013 Lot 74093 8.3 4.4 Nylon MXD6 To as 6013 Lot 74093 - -Ba er PC CD 2005 To as 6013 Lot 74093 - -DSM Stanylan LDPE- To as@ 8007 Lot 54028 2.4 8.1 Hostalen PPR 1042 To asO 8007 Lot 54028 9.2 7.0 Im et@ PET T86 To asO 8007 Lot 54028 8.7 5.3 Nylon MXD6 To asO 8007 Lot 54028 990 6.3 Ba er@ PC CD 2005 To as@ 8007 Lot 54028 - -TopasO 6013 Lot 74093 DSM Stanylan LDPE 6.8 53.1 To as 6013 Lot 74093 Hostaten PPR 1042 1.0 0.85 To asO 6013 Lot 74093 Im et PET T86 3.3 2.6 To as 6013 Lot 74093 Nylon MXD6 3.7 2.7 To as@ 6013 Lot 74093 Ba er PC CD 2005 - -To as 8007 Lot 54028 DSM Stanylan LDPE 4.4 16.9 To asO 8007 Lot 54028 Hostalen PPR 1042 8.5 6.6 To asg 8007 Lot 54028 Im et(D PET T86 4.8 3.3 To as@ 8007 Lot 54028 Nylon MXD6 5.0 3.2 To asO 8007 Lot 54028 Ba er@ PC CD 2005 6.0 3.9 c O
~ E co U) tn U) LO 10 d rn O O U O Q C) O 0 C) C) O C) O C) O
0 E (D co Ln U) v LO cD c0 Cfl c0 c0 LO
A A A A A A A A A A A A
o v~ *
U (n a) ~ ,Q m a) O O (0 Q) ~ M
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4) Co 0 O O O O 0 O O 0 O O O~
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:-. U) O m ~f V' '~fi ~ U M M M (y) M O
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O
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m f2 s- r r r e- s- ~-- r r ~- ~-- r O
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CM d r r r M cr ~f ~ ~f V
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_ N N N N N N CV N N N N N
Q ~ ~ i ~ ~ ~ ~ i ~
E V O C) O 0 0 O O O O 0 O O
f- 1- f~ !- 1~ 1- c'') C'M Cr) CM M N
~ ~ N N N N N N N N N N N N
W u) W ~ Ln Nj C C _ a O O d O O
0 O r (O N O Q O
r Cfl N O U) o C a F- ~ O C 00 O) V) ~ N c0 p ~ ~p C~ Q' tp O U R~
O W p V ~- c W p Q 0- a X a (9) N E~ iv c ~ tU
~
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m c~ o i~ z m E
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E V d 'V d d V d ~7 ~ ~ ~ d N
C~ _A t' 1~ f- 1~ f~ 1+ t1~ tn tl) ln U) f~ ~ t ~ O 0 0 0 0 0 0 0 0 0 0 0 O
Cl ~ J J J J J J J J J J J~ p~
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o o ~
F~- > a a a a a Q. a ~ a Q a a ~ F - 1~ 1- 10 F - 1- H F - F- F0 - F - F- *~*
Example 2 - 2-component injection molding Coinjection of TopasO by injection molding using a multi-part mold This was carried out using a 3-component Kl'ockner Ferromatik injection molding machine and a centrally gated plate (300 x 215 x 3 mm).
Using a special injection head having controlled and sprung needle valves, the injection head nozzle was selected by means of a preceding 2-component distributor disk so that the core component was injected centrally into the cavity and the second melt exiting coaxially around it was injected simultaneously or, if desired, after an interval (see fig. 1).
Mixing of the two streams of material was avoided by selection of the respective fluidities and, in particular, by selection of the injection sequence/process conditions.
Formation of the core layer, here component B, was monitored in the case of transparent or slightly colored materials. As colorant, a TopasO 5013 (cycloolefin copolymer/Ticona ; HDT/B (0.45 N/mm2) = 130 C; melt index MVR at 260 C, 2.16 kg,.
= 56 ml/min)/Sandoplast BIauCD B masterbatch was added in a concentration of about 2%.
Selection of the component A of the outer layer and the component B of the core layer is summarized in table 4.
Table 4: Material combinations:
Component B Component A
Topas Cycloolefin copolymer/Ticona HDT/B (0.45 Metocen(D PP X50081 Transparent 8007 N/mm2) = 75 C melt index MVR at 260 C, 94-2710/Tagor polypropylene 2.16 kg = 30 mI/min Topas Cycloolefln copolymer/Ticona HDT/B (0.45 K-Resin KR-01/ Phillips Styrene-8007 N/mm2) = 75 C melt index MVR at 260 C, butadiene 2.16 kg = 30 mi/min copolymer TopasU Cycloolefin copolymer/Ticona HDT/B (0.45 PET Polyester T86 Transparent 6013 N/mm2) = 130 C melt index MVR at 260 C, W03/Kosa polyester 2.16 kg = 13 ml/min Topas Cycloolefin copolymer/Ticona HDT/B (0.45 Grilamid TR90/ Transparent 6013 N/mm2) = 130 C melt index MVR at 260 C, EMS-Chemie polyamide 2.16 kg = 13 mi/min Topas Cycloolefin copolymer/Ticona HDT/B (0.45 Nylon MXD 6/Mitsui Transparent 6013 N/mm2) = 130 C melt index MVR at 260 C, polyamide 2.16 kg = 13 ml/min Topas Cycloolefin copolymer/Ticona HDT/B (0.45 Trogamid CX7323/ Transparent 6013 N/mm) = 130 C melt index MVR at 260 C, Degussa-Huls polyamide 2.16 kg = 13 mI/min Topas Cycloolefin copolymer/Ticona HDT/B (0.45 Metocen(ED PP X50081 Transparent 6013 N/mm2) = 130 C melt index MVR at 260 C, 94/2710/Tagor polypropylene 2.16kg=13mI/min Procedure:
-~-,-.-r-_--The various material combinations were each processed for two different injection profiles.
The profiles differed in the sequence of injection of the enveloping component (component A) and the core component (component B).
Example 2a:
In the case of injection profile 2a, the time delay between commencement of injection of the component B and the component A was about two seconds, at which time 82 percent of the amount of component A had already been injected. The injection profile 2a is shown by way of example in figs. 3a and 3b for polyester/Topas 6013.
Example 2b:
In the case of the injection profile 2b, the time delay between commencement of injection of component B and component A was only about 0.5 seconds. After this time, about 90 percent of the remaining amounts were injected simst(taneQusly.
The injection profile 2b is shown by way of example in figs. 4a and 4b for Trogamid /Topas 6013.
In both cases, the sprue is sealed with the component A at the end of the respective injection procedure. Further processing parameters for the experiments are shown in table 6.
Breakthrough of the enveloping layer through the core component was not observed, even when using very fluid enveloping material such as Metocen PP X50081.
The layer thickness distribution can be influenced via the respective injection volumes, injection pressures and injection rates of the 2 independently regulatable injection molding units, while the position of the core layer can be shifted by means of the temperature of the tool.
Uniform layer thickness distributions and good transparency of the plates can be achieved under the above-described process conditions. In addition, the plates were assessed in respect of adhesion of the layers and distortion tendency (see table 5).
Table 5: Experimental results:
Injection Material combination Adhesion Clouding Distortion molding Component A/ between tendency profile layers Component B
2a I Metocen PP / Topas 8007 ++ o -2b I Metocen PP / Topas 8007 ++ +0 -2a II K-Resin / Topas@ 8007 + +0 +0 2b II K-Resin / Topas 8007 + + +0 2a III Metocen PP / Topas@ 6013 + o -2b III Metocen PP / Topas@ 6013 + +0 -2a IV Trogamid / Topas@ 6013 +0 + +0 2b IV Trogamid / Topas 6013 +0 ++ +0 2a V GrilamidO / Topas@ 6013 0 + +
2b V Grilamid / Topas 6013 0 + +
2a VI PET Polyester / Topas 6013 - 0- +
2b VI PET Polyester / Topas 6013 - o +
2a VII Nylon MXD6 / Topas 6013 0- o- +
2b VII Nylon MXD6 / Topas@ 6013 0- 0 +
~ d ~ 0 O 0 OV ~ 0 ~ ~ 0 ~ O 0 0 0 C) LO
d X == CO M N N N N N N N ~ qT CD N
-o m M
~ U) 2 X ~ O O ~ 0) 0) O 0 d ~ ) O O O 0 O O LO
H U '. Cfl cM N N N M M N c'M CO CO ~ r t0 N
Cfl N
~
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i f) N
(D
~ f=M- ~ C) (M N N N N N N N OV (V LO ~ COO N
~ N
E 0) 0 Q ~
CY) 12 3 ~ M N N N N N N 0) -O [') ~ L[) 0 N
O O O 0 0 O 00 00 C) OM) O O O L1') ~ (p cf) cY) M co co M m N ~ U3 U) N N
a a c ~
o "
~ ~
~
~ C) 0 O 0 t~ ~ 0 0 ~ 0 O O O 0 COO N
N X ~ ~O M N N N N N N N ~t tt i f6 a O O ~ ~ ~ ~ v~i ~ O O LO LO
Y Y ~ QO Ce) N N N N N N LO LO N
cn o 0 0 ~ n ~ n ~ n ~ c) l n ~ n 0 0 C) o 0 LO
F- 00 ~ M N N N N N N U) Lf) V) N (O N
Q
~ uUi r- N c~) 'It ~ p) N 0 C ~ ~ C C X ~
0 4m, 0 ti N N N N N~~ C7 W
a M
E
EL N
=H ~
~-.
N
~ E UN
Q (,D FL
a~
a N
~ o o Q.~ o a~
a a c = Z
~ o E ai U 1 , u~i m d ~ U
1- U U F- U~ ,...
Claims (3)
PROPERTY OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:
1. The use of a multilayer container comprising two outer layers A and a core layer B which comprises at least one cycloolefin polymer comprising 0.1-100% by weight, based on the total mass of the cycloolefin polymer, of polymerized units derived from at least one polycyclic olefin of the formula I, II, II', III, IV, V or VI
where R1, R2, R3, R4, R5, R6, R7 and R8 are identical or different and are each a hydrogen atom or a C1-C20-hydrocarbon radical or form a saturated, unsaturated or aromatic ring, where identical radicals R1 to R8 in the various formulae I to VI have the same or different meanings and n is from 0 to 5, and from 0 to 99.9% by weight, based on the total mass of the cycloolefin polymer, of polymerized units derived from one or more acyclic olefins of the formula VII
where R9, R10, R11 and R12 are identical or different and are each a hydrogen atom or a linear, branched, saturated or unsaturated C1-C20-hydrocarbon radical or a C6-C18-aryl radical, and from 0 to 45% by weight, based on the total composition of the cycloolefin polymer, of polymerized units derived from one or more monocyclic olefins of the formula VIII
where m is from 2 to 10, for hot packaging of liquids.
where R1, R2, R3, R4, R5, R6, R7 and R8 are identical or different and are each a hydrogen atom or a C1-C20-hydrocarbon radical or form a saturated, unsaturated or aromatic ring, where identical radicals R1 to R8 in the various formulae I to VI have the same or different meanings and n is from 0 to 5, and from 0 to 99.9% by weight, based on the total mass of the cycloolefin polymer, of polymerized units derived from one or more acyclic olefins of the formula VII
where R9, R10, R11 and R12 are identical or different and are each a hydrogen atom or a linear, branched, saturated or unsaturated C1-C20-hydrocarbon radical or a C6-C18-aryl radical, and from 0 to 45% by weight, based on the total composition of the cycloolefin polymer, of polymerized units derived from one or more monocyclic olefins of the formula VIII
where m is from 2 to 10, for hot packaging of liquids.
2. The use according to claim 1, wherein the C1-C20-hydrocarbon radical of R1, R2, R3, R4, R5, R6, R7 or R8 is a linear or branched C1-C8-alkyl radical, C6-C18-aryl radical, C7-C20-alkylenearyl radical or a cyclic or acyclic C2-C20-alkenyl radical.
3. The use according to claim 1 or 2, wherein the C1-C20-hydrocarbon radical of R9, R10, R11 or R12 is a C6-C18-aryl radical.
Applications Claiming Priority (5)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE19916141A DE19916141A1 (en) | 1999-04-09 | 1999-04-09 | Multi-layer container for packaging medical and pharmaceutical products, cosmetics and food has at least one layer containing at least one cyclo-olefin polymer |
| DE19943545A DE19943545A1 (en) | 1999-04-09 | 1999-09-10 | Multi-layer container with improved adhesion between the polymer layers and excellent barrier properties |
| DE19916141.0 | 1999-09-10 | ||
| DE19943545.6 | 1999-09-10 | ||
| PCT/EP2000/002666 WO2000061370A1 (en) | 1999-04-09 | 2000-03-27 | Multilayer containers exhibiting an improved adherence between polymer layers as well as excellent barrier characteristics |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CA2369137A1 CA2369137A1 (en) | 2000-10-19 |
| CA2369137C true CA2369137C (en) | 2008-10-28 |
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ID=26052838
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA002369137A Expired - Lifetime CA2369137C (en) | 1999-04-09 | 2000-03-27 | Multilayer containers exhibiting an improved adherence between polymer layers as well as excellent barrier characteristics |
Country Status (6)
| Country | Link |
|---|---|
| EP (1) | EP1177096B1 (en) |
| JP (1) | JP2002540997A (en) |
| AU (1) | AU4110700A (en) |
| CA (1) | CA2369137C (en) |
| DE (2) | DE19943545A1 (en) |
| WO (1) | WO2000061370A1 (en) |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| DE19915715A1 (en) | 1999-04-08 | 2000-10-19 | Ticona Gmbh | Microstructured components |
| US6372816B1 (en) * | 1999-06-25 | 2002-04-16 | Dentsply Detrey Gmbh | Dental materials packaging and method of use |
| DE10144892B4 (en) * | 2001-09-12 | 2005-09-08 | Disetronic Licensing Ag | Multilayer plastic body |
| DE10238515A1 (en) * | 2002-08-21 | 2004-03-04 | Ticona Gmbh | Polyolefin multilayer film, a process for producing this film and its use |
| DE10238516A1 (en) * | 2002-08-21 | 2004-03-04 | Ticona Gmbh | Polyolefin multilayer film, process for its production and its use |
| FR2848196B1 (en) * | 2002-12-10 | 2005-08-05 | Valois Sas | FLUID PRODUCT TANK AND DISPENSING DEVICE COMPRISING SUCH A TANK |
| TWI409057B (en) | 2004-09-27 | 2013-09-21 | Nipro Corp | Medical container |
| US20070026173A1 (en) | 2005-07-27 | 2007-02-01 | Owens-Illinois Healthcare Packaging Inc. | Multilayer containers and methods of manufacture |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP3227709B2 (en) * | 1991-03-04 | 2001-11-12 | 日本ゼオン株式会社 | Medical or food packaging containers |
| CA2134320C (en) * | 1993-10-26 | 2001-01-09 | Toshiyuki Hirose | Polyolefin multilayer laminate and use thereof |
| JPH07171858A (en) * | 1993-12-21 | 1995-07-11 | Toppan Printing Co Ltd | Moistureproof multilayered injection molded article |
| JP3075144B2 (en) * | 1995-06-26 | 2000-08-07 | 東洋製罐株式会社 | Perfumery packaging |
| DE19540356A1 (en) * | 1995-10-30 | 1997-05-07 | Hoechst Ag | Cyclo:olefin copolymer foam with high heat distortion temperature and chemical resistance |
| JPH09239909A (en) * | 1996-03-11 | 1997-09-16 | Kishimoto Akira | Multilayer plastic container with good preservative property |
| JP3876020B2 (en) * | 1996-08-12 | 2007-01-31 | 東洋製罐株式会社 | Fragrance plastic multilayer container |
| JP3721646B2 (en) * | 1996-08-12 | 2005-11-30 | 東洋製罐株式会社 | Plastic multilayer container and manufacturing method thereof |
| DE19828867A1 (en) * | 1998-06-29 | 1999-12-30 | Ticona Gmbh | Extrusion coated film |
| JP4254058B2 (en) * | 1998-06-30 | 2009-04-15 | 日本ゼオン株式会社 | Container and blow molded body |
| US6270869B1 (en) * | 1998-12-02 | 2001-08-07 | Alusuisse Technology & Management Ltd. | Cold formable laminate films |
-
1999
- 1999-09-10 DE DE19943545A patent/DE19943545A1/en not_active Withdrawn
-
2000
- 2000-03-27 EP EP00920584A patent/EP1177096B1/en not_active Expired - Lifetime
- 2000-03-27 DE DE50008124T patent/DE50008124D1/en not_active Expired - Lifetime
- 2000-03-27 CA CA002369137A patent/CA2369137C/en not_active Expired - Lifetime
- 2000-03-27 WO PCT/EP2000/002666 patent/WO2000061370A1/en active IP Right Grant
- 2000-03-27 AU AU41107/00A patent/AU4110700A/en not_active Abandoned
- 2000-03-27 JP JP2000610675A patent/JP2002540997A/en active Pending
Also Published As
| Publication number | Publication date |
|---|---|
| CA2369137A1 (en) | 2000-10-19 |
| EP1177096A1 (en) | 2002-02-06 |
| DE50008124D1 (en) | 2004-11-11 |
| WO2000061370A1 (en) | 2000-10-19 |
| EP1177096B1 (en) | 2004-10-06 |
| AU4110700A (en) | 2000-11-14 |
| DE19943545A1 (en) | 2001-03-15 |
| JP2002540997A (en) | 2002-12-03 |
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| EEER | Examination request | ||
| MKEX | Expiry |
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