USRE42925E1 - Polyester resin blends with high-level gas barrier properties - Google Patents
Polyester resin blends with high-level gas barrier properties Download PDFInfo
- Publication number
- USRE42925E1 USRE42925E1 US12/313,141 US31314108A USRE42925E US RE42925 E1 USRE42925 E1 US RE42925E1 US 31314108 A US31314108 A US 31314108A US RE42925 E USRE42925 E US RE42925E
- Authority
- US
- United States
- Prior art keywords
- bottle
- specified
- polymeric material
- polyamide
- polyester
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
- C08L67/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
-
- 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
- C08J5/18—Manufacture of films or sheets
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
- C08L77/06—Polyamides derived from polyamines and polycarboxylic acids
-
- 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
- B29C49/00—Blow-moulding, i.e. blowing a preform or parison to a desired shape within a mould; Apparatus therefor
- B29C49/42—Component parts, details or accessories; Auxiliary operations
- B29C49/78—Measuring, controlling or regulating
- B29C49/783—Measuring, controlling or regulating blowing pressure
- B29C2049/7831—Measuring, controlling or regulating blowing pressure characterised by pressure values or ranges
-
- 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
- B29C49/00—Blow-moulding, i.e. blowing a preform or parison to a desired shape within a mould; Apparatus therefor
- B29C49/42—Component parts, details or accessories; Auxiliary operations
- B29C49/78—Measuring, controlling or regulating
- B29C49/786—Temperature
- B29C2049/7861—Temperature of the preform
- B29C2049/7862—Temperature of the preform characterised by temperature values or ranges
-
- 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
- B29C2949/00—Indexing scheme relating to blow-moulding
- B29C2949/07—Preforms or parisons characterised by their configuration
- B29C2949/0861—Other specified values, e.g. values or ranges
- B29C2949/0872—Weight
-
- 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
- B29C2949/00—Indexing scheme relating to blow-moulding
- B29C2949/20—Preforms or parisons whereby a specific part is made of only one component, e.g. only one layer
- B29C2949/22—Preforms or parisons whereby a specific part is made of only one component, e.g. only one layer at neck portion
-
- 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
- B29C2949/00—Indexing scheme relating to blow-moulding
- B29C2949/20—Preforms or parisons whereby a specific part is made of only one component, e.g. only one layer
- B29C2949/24—Preforms or parisons whereby a specific part is made of only one component, e.g. only one layer at flange portion
-
- 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
- B29C2949/00—Indexing scheme relating to blow-moulding
- B29C2949/20—Preforms or parisons whereby a specific part is made of only one component, e.g. only one layer
- B29C2949/26—Preforms or parisons whereby a specific part is made of only one component, e.g. only one layer at body portion
-
- 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
- B29C2949/00—Indexing scheme relating to blow-moulding
- B29C2949/20—Preforms or parisons whereby a specific part is made of only one component, e.g. only one layer
- B29C2949/28—Preforms or parisons whereby a specific part is made of only one component, e.g. only one layer at bottom portion
-
- 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
- B29C2949/00—Indexing scheme relating to blow-moulding
- B29C2949/30—Preforms or parisons made of several components
- B29C2949/3024—Preforms or parisons made of several components characterised by the number of components or by the manufacturing technique
-
- 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
- B29C2949/00—Indexing scheme relating to blow-moulding
- B29C2949/30—Preforms or parisons made of several components
- B29C2949/3032—Preforms or parisons made of several components having components being injected
-
- 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
- B29C49/00—Blow-moulding, i.e. blowing a preform or parison to a desired shape within a mould; Apparatus therefor
- B29C49/0042—Blow-moulding, i.e. blowing a preform or parison to a desired shape within a mould; Apparatus therefor without using a mould
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
- B29K2067/00—Use of polyesters or derivatives thereof, as moulding material
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
- B29K2077/00—Use of PA, i.e. polyamides, e.g. polyesteramides or derivatives thereof, as moulding material
-
- 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
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/78—Preparation processes
- C08G63/80—Solid-state polycondensation
-
- 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
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/91—Polymers modified by chemical after-treatment
- C08G63/914—Polymers modified by chemical after-treatment derived from polycarboxylic acids and polyhydroxy compounds
- C08G63/916—Dicarboxylic acids and dihydroxy compounds
-
- 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
- C08J2367/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
- C08J2367/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
-
- 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
- C08J2377/00—Characterised by the use of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Derivatives of such polymers
- C08J2377/06—Polyamides derived from polyamines and polycarboxylic acids
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/008—Additives improving gas barrier properties
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/09—Carboxylic acids; Metal salts thereof; Anhydrides thereof
- C08K5/092—Polycarboxylic acids
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/13—Hollow or container type article [e.g., tube, vase, etc.]
- Y10T428/1352—Polymer or resin containing [i.e., natural or synthetic]
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/13—Hollow or container type article [e.g., tube, vase, etc.]
- Y10T428/1352—Polymer or resin containing [i.e., natural or synthetic]
- Y10T428/1379—Contains vapor or gas barrier, polymer derived from vinyl chloride or vinylidene chloride, or polymer containing a vinyl alcohol unit
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/13—Hollow or container type article [e.g., tube, vase, etc.]
- Y10T428/1352—Polymer or resin containing [i.e., natural or synthetic]
- Y10T428/139—Open-ended, self-supporting conduit, cylinder, or tube-type article
Definitions
- the present invention relates to biaxially-oriented films and containers provided with high resistance to gas permeability, and to the polymeric materials used to prepare said containers and films.
- This invention more specifically relates to articles made of or comprising a material obtained from compositions comprising a polyester resin and a polyamide wherein they have an oxygen permeability of less than 0.065 ml/bottle/day/atm, measured on a 1.5-liter bottle with a thickness of 225 microns obtained by injection blow molding.
- Aromatic polyester resins are used in ever-increasing amounts in the production of beverage containers and films.
- the barrier properties of aromatic polyester resins are rather limited. In the case of containers for carbonated beverages prepared from said resins, the possibility to preserve the beverages for a sufficiently long time is uncertain.
- Polyamide resins have remarkable mechanical properties, but they have the drawback that they have a high moisture absorption which reduces their properties.
- Polyamide resins are normally used mixed with aromatic polyester resins in order to improve the mechanical characteristics of the latter.
- the presence of polyester resin in the mix reduces the moisture-absorbing tendency of polyamide resins.
- Pyromellitic anhydride is the preferred compound.
- the mechanical properties of the resulting mixtures can be improved further by subjecting the mixtures to a solid-state polycondensation treatment (WO 94/09069).
- polyamides the most commonly used polyamides, such as nylon 6 and 66, have slightly better gas barrier properties than polyester resins such as polyethylene terephthalate (PET) and copolyethylene terephthalates such as polyethylene terephthalate (PET) and copolyethylene terephthalates containing small proportions of units derived from isophthalic acid.
- PET polyethylene terephthalate
- PET copolyethylene terephthalates
- PET polyethylene terephthalate
- copolyethylene terephthalates containing small proportions of units derived from isophthalic acid isophthalic acid
- poly-m-xylylene adipamide poly MXD-6
- gas barrier properties in relation to oxygen and carbon dioxide
- This polyamide is used in mixture (obtained in an extruder) with PET or COPET in order to improve their barrier properties.
- the oxygen permeability of a 1.5-liter PET bottle is reduced by approximately 50% when the bottle is obtained from a mixture which contains 16% by weight of polyamide and by approximately 20% when it contains 7% polyamide by weight.
- the barrier properties of the 16% polyamide mixture are similar to those of a bottle formed of a two-layer film, one layer being PET and the other one being polyamide.
- Pyromellitic dianhydride is preferred.
- Other dianhydrides that can be used are dianhydrides of 1,2,3,4-cyclobutane tetracarboxylic acid, 3,3′:4,4′-benzophenone tetracarboxylic acid, 2,2 bis-(2,4-dicarboxyphenyl)ether.
- the dianhydrides of aromatic tetracarboxylic acids are preferred.
- the polyester resin is a copolyethylene terephthalate in which up to 25%, preferably 1 to 15%, of the units derived from terephthalic acid are substituted by units or sequences derived from isophthalic acid or from mixtures thereof with naphthalene dicarboxylic acids.
- the polyamide is preferably poly MXD-6.
- Other polyamides that can be used are those obtainable from an aliphatic dicarboxylic acid other than adipic acid containing 6 to 22 atoms of carbon and an arilene diamine, preferably m-xylylene diamine.
- Said dicarboxylic acid is preferably suberic, sebacic and dodecanoic acid.
- Polyamides with crystallization rates similar to those of polyester are preferably used.
- the numeral molecular weight of the starting polyamide is generally between 8000 and 50000.
- the terminal-NH 2 groups of the starting polyamide can be reacted with epoxy compounds in order to increase its dispersion in the polyester matrix.
- Epoxy compounds Epikote from the Shell Italia is an example of usable epoxi compounds.
- the polyamide is used in an amount equal to 5 to 30% by weight on the mixture. Larger amounts can be used depending on the final properties of the mixture.
- a preferred mixing process consists in extruding the polyester resin with the addition of the dianhydride and in subsequently extruding the mixture with the addition of the polyamide.
- the ratio between the viscosity of the polyester and the viscosity of the polyamide is between 0.2:1 and 4:1.
- the microstructure was obtained by scanning electron microscope (S.E.M.) of the fracture surface of injection molded small bars treated with formic acid to extract the polyamide.
- the bars obtained according to example 1 have a microstructure wherein the dispersed phase has a size of less than 0.5 micron.
- the size of the domains in the bars obtained from example 1 but without using PMDA are higher than 1.5 micron as average.
- the microstructure according to the invention is characteristic in particular of the blends of poly MXD-6 with PET or copolyethylene thereftalates containing up to 25% of units deriving from isophtalic isophthalic acid.
- Oxygen permeability in 1.5-liter bottles with an average thickness of 225 microns can be reduced of 4 or more times and CO 2 permeability can be reduced by 2 or more times as a function of the content of the polyamide (pMXD-6).
- the polyester resin is obtained by polycondensation (according to known methods) of terephthalic acid or lower diesters thereof with a diol with 2-12 carbon atoms, such as for example ethylene glycol, 1,4-butanediol and 1,4-cyclohexane dimethylol.
- a diol with 2-12 carbon atoms such as for example ethylene glycol, 1,4-butanediol and 1,4-cyclohexane dimethylol.
- the copolyethylene terephthalate is, as mentioned, the preferred resin for preparing containers.
- the polyethylene terephthalate homopolymer can be conveniently used in the preparation of biaxially-oriented films.
- the starting polyester resin used in the preparation of the compositions according to the invention has an intrinsic viscosity of 0.3 to 0.8 dl/g.
- the initial viscosity can be increased by subjecting the resin, premixed with the dianhydride of the tetracarboxylic acid or the mixture containing the polyester resin, the polyamide and the dianhydride, to a solid-state polycondensation treatment at temperatures between approximately 150 and 230° C. for a time and at temperature conditions sufficient to increase by at least 0.1 units the viscosity of the polyester resin.
- the increase in intrinsic viscosity of the polyester resin in the mixture is considered similar to the increase in the polyester resin when it is treated alone in the same temperature and duration conditions to which the mixture has been subjected.
- the solid-state polycondensation treatment in addition to leading to an increase in the intrinsic viscosity of the polyester resin, allows to improve the mechanical properties of the compositions, particularly impact resistance.
- the treatment applied to the polyester resin added of the dianhydride of the tetracarboxylic acid allows to bring the viscosity of the resin in the melted state to values which are similar to those of the polyamide resin, particularly when the initial polyester resin has relatively low intrinsic viscosity values.
- the mixing of the polyester with the dianhydride and then with the polyamide is performed in a single- or twin-screw extruder. Contrarotating and intermeshing twin-screw extruders are preferred, using residence times of generally less than 180 seconds and working at temperatures above the melting temperatures of the polymeric components, generally between 200° and 300° C.
- biaxially oriented films and containers are prepared according to known methods.
- bottles for beverages are prepared by injection-stretch blow molding;
- biaxially oriented films are prepared with the double-bubble method or by cast-extrusion followed by biaxial stretching.
- the material according to the invention can also be used to prepare multilayer films comprising, as a core layer, a biaxially oriented film obtained from the material according to the invention.
- polyester resin is a copolyethylene therephthalate terephthalate with 10% or more of units from isophthalic acid resides in the preparation by free blowing of preforms of high capacity pouches (51, or more) suitable for being filled with liquids such as soft drinks or others.
- the pouches have high clarity and good mechanical properties. They can be easily folded without breakage or stress withening problems.
- the intrinsic viscosity is measured in solutions of 0.5 g of resin in 100 ml of 60/40 solution by weight of phenol and tetrachloroethane, at 25° C. according to ASTM standard D 4603-86.
- the measurement of the melt viscosity is performed with a Goettfert rheometer equipped with a 2-mm capillary tube, working at 280° C. with a shear rate of 100 sec ⁇ 1 .
- the operating conditions are:
- the resulting pellets were crystallized at 130° C. in a reactor in continuous under nitrogen flow.
- the conditions for preparing the mixture are the same used for the treatment of COPET with the addition of PMDA.
- the IV of the pellets was 0.81 dl/g.
- the pellets are crystallized at 130° C. in a reactor operating continuously in nitrogen.
- pellets are then extruded together with 10% by weight of poly MXD-6 in the conditions of example 1.
- Example 1 The preparation of example 1 (premixing of COPET with PMDA and subsequent extrusion with 10% poly MXD-6) was repeated, with the only difference that the COPET used contained 2% isophthalic acid and had an IV of 0.6 dl/g.
- example 1 The preparation of example 1 was repeated, with the only difference that the mixture contained 70% by weight of poly-MXD-6.
- a composition, prepared according to example 1, by using in place of COPET containing 4.5% IPA a mixture containing 86% by weight of COPET with 2% of IPA (IV 0.8 dl/g) and 14% of polyethylene isophthalate, and in which the percentage of poly-MXD was 7.5% by weight, was used to prepare 40 g preforms.
- the preforms were submitted to free blowing using a Sidel machine equipped with an infrared heater to heat the preforms to 110°.
- the preforms were blown using air at 3 bar pressure.
- the obtained pouches have a capacity of 5 l. and are highly clear. They can be folded (when empty) and refilled with liquids.
- the pouches filled with 5 l. water can withstand a drop impact of 1 m.
- the preforms were then blown in a 1.5- and 2-liter cavity to produce bottles by stretch-blow molding.
- the thickness of the 1.5-liter bottles was 225 microns (average value) and the thickness of the 2-liter bottles was 195 microns (average value).
- 1.5-liter bottles were prepared by injection-blow molding in the conditions used in examples 6-7.
Abstract
Description
TABLE 1 |
Mixtures |
Com- | |||||
parison | Example | Example | Example | Example | |
2 | 1 | 2 | 3 | 4 | |
% weight | 0 | 10 | 10 | 10 | 70 |
pMXD-6 | |||||
% IPA | 2 | 4.5 | 10 | 2 | 4.5 |
O2 permeability | |||||
1.5-liter bottles | 0.53 | 0.13 | 0.1 | 0.12 | |
ml/bott/d/atm | |||||
2 liter bottles | 0.62 | 0.23 | 0.14 | 0.14 | |
CO2 permeability | 18.2 | 7.25 | 5.31 | 7.02 | 2.7 |
1.5-liter bottles | |||||
ml/bott/d/atm | |||||
Improvement % | |||||
O2 permeability | |||||
1.5-liter bottles | 407 | 550 | 449 | ||
2-liter bottles | 362 | 578 | 567 | ||
CO2 permeability | 251 | 343 | 250 | 670 | |
1-5-liter bottles | |||||
Claims (54)
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US12/313,141 USRE42925E1 (en) | 1998-06-11 | 2008-11-17 | Polyester resin blends with high-level gas barrier properties |
Applications Claiming Priority (4)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
IT1998MI001335A IT1301690B1 (en) | 1998-06-11 | 1998-06-11 | MIXTURES OF POLYESTER RESINS WITH HIGH PROPERTIES OF AIGAS BARRIER. |
ITMI98A1335 | 1998-06-11 | ||
US09/323,000 US6346307B1 (en) | 1998-06-11 | 1999-06-01 | Polyester resin blends with high-level gas barrier properties |
US12/313,141 USRE42925E1 (en) | 1998-06-11 | 2008-11-17 | Polyester resin blends with high-level gas barrier properties |
Related Parent Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US09/323,000 Reissue US6346307B1 (en) | 1998-06-11 | 1999-06-01 | Polyester resin blends with high-level gas barrier properties |
Publications (1)
Publication Number | Publication Date |
---|---|
USRE42925E1 true USRE42925E1 (en) | 2011-11-15 |
Family
ID=11380226
Family Applications (2)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US09/323,000 Ceased US6346307B1 (en) | 1998-06-11 | 1999-06-01 | Polyester resin blends with high-level gas barrier properties |
US12/313,141 Expired - Lifetime USRE42925E1 (en) | 1998-06-11 | 2008-11-17 | Polyester resin blends with high-level gas barrier properties |
Family Applications Before (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US09/323,000 Ceased US6346307B1 (en) | 1998-06-11 | 1999-06-01 | Polyester resin blends with high-level gas barrier properties |
Country Status (15)
Country | Link |
---|---|
US (2) | US6346307B1 (en) |
EP (1) | EP0964031B1 (en) |
JP (2) | JP4412763B2 (en) |
KR (1) | KR100609422B1 (en) |
CN (1) | CN1243848A (en) |
AT (1) | ATE263808T1 (en) |
AU (1) | AU754308B2 (en) |
BR (1) | BR9902233B1 (en) |
CA (1) | CA2273701C (en) |
DE (1) | DE69916174C5 (en) |
ES (1) | ES2217645T3 (en) |
HU (1) | HUP9901942A3 (en) |
IT (1) | IT1301690B1 (en) |
PL (1) | PL333648A1 (en) |
TW (1) | TWI235756B (en) |
Families Citing this family (51)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
TWI250934B (en) | 1997-10-17 | 2006-03-11 | Advancsd Plastics Technologies | Barrier-coated polyester articles and the fabrication method thereof |
US6352426B1 (en) | 1998-03-19 | 2002-03-05 | Advanced Plastics Technologies, Ltd. | Mold for injection molding multilayer preforms |
US20020037377A1 (en) | 1998-02-03 | 2002-03-28 | Schmidt Steven L. | Enhanced oxygen-scavenging polymers, and packaging made therefrom |
IT1301690B1 (en) | 1998-06-11 | 2000-07-07 | Sinco Ricerche Spa | MIXTURES OF POLYESTER RESINS WITH HIGH PROPERTIES OF AIGAS BARRIER. |
IT1318600B1 (en) | 2000-06-28 | 2003-08-27 | Sinco Ricerche Spa | PREPARATION OF POLYESTER RESINS USING DIPOLYLENAMIDE MASTERBATCH. |
CN100400265C (en) | 2000-09-05 | 2008-07-09 | 先进塑胶技术卢森堡股份有限公司 | Multilayer containers and preforms having barrier properties utilizing recycled material |
US7244484B2 (en) | 2000-11-08 | 2007-07-17 | Valspar Sourcing, Inc. | Multilayered package with barrier properties |
US7807270B2 (en) * | 2000-11-08 | 2010-10-05 | Valspar Sourcing, Inc. | Multilayered package with barrier properties |
JP2002255231A (en) * | 2001-02-23 | 2002-09-11 | Yoshino Kogyosho Co Ltd | Synthetic resin container having improved gas barrier properties and heat resistance and manufacturing method therefor |
EP1239008B1 (en) * | 2001-03-05 | 2004-04-14 | Mitsubishi Gas Chemical Company, Inc. | Polyester-based resin composition and shaped articles |
AU784042B2 (en) * | 2001-05-24 | 2006-01-19 | Mitsubishi Gas Chemical Company, Inc. | Polyester based resin composition and molded product therefrom |
ITMI20011510A1 (en) | 2001-07-16 | 2003-01-16 | Sinco Ricerche Spa | POLYESTER RESIN FLEXIBLE BOTTLES |
ATE417896T1 (en) * | 2001-09-28 | 2009-01-15 | Cobarr Spa | TRANSPARENT POLYESTER RESINS AND ARTICLES MADE THEREFROM |
KR100403603B1 (en) | 2002-02-26 | 2003-10-30 | 삼성전자주식회사 | Photoconducting drum structure for image forming apparatus using photoconducting belt |
US20060149001A1 (en) * | 2002-09-16 | 2006-07-06 | Ghatta Hussain A | Transparent polyester resins and articles therefrom |
CN100378149C (en) | 2003-01-31 | 2008-04-02 | M&G聚合物意大利有限公司 | Article comprising light absorbent composition to mask visual haze and related methods |
WO2004090020A1 (en) | 2003-04-02 | 2004-10-21 | Valspar Sourcing, Inc. | Aqueous dispersions and coatings |
EP1504999A1 (en) * | 2003-08-05 | 2005-02-09 | Amcor Limited | Rigid plastic container having gas-barrier properties and high transparency |
UA81055C2 (en) | 2003-08-26 | 2007-11-26 | Інвіста Технолоджіс С.А.Р.Л. | Blend for containers and preform or container |
DE10352430A1 (en) * | 2003-11-10 | 2005-06-09 | Mitsubishi Polyester Film Gmbh | Peelable polyester film with improved oxygen barrier, process for its preparation and its use |
KR20070010059A (en) | 2004-04-16 | 2007-01-19 | 어드밴스드 플라스틱스 테크놀로지즈 룩셈부르크 에스.에이. | Mono and multi-layer articles and injection molding methods of making the same |
DE102004030980A1 (en) * | 2004-06-26 | 2006-01-19 | Mitsubishi Polyester Film Gmbh | Polyester film containing poly (m-xyleneadipamide) |
ATE513025T1 (en) | 2004-10-20 | 2011-07-15 | Valspar Sourcing Inc | COATING COMPOSITIONS FOR CANS AND COATING PROCESSES |
US20060099362A1 (en) * | 2004-11-05 | 2006-05-11 | Pepsico, Inc. | Enhanced barrier packaging for oxygen sensitive foods |
US7375154B2 (en) * | 2004-12-06 | 2008-05-20 | Eastman Chemical Company | Polyester/polyamide blend having improved flavor retaining property and clarity |
AU2005314117A1 (en) * | 2004-12-06 | 2006-06-15 | Constar International Inc. | Blends of oxygen scavenging polyamides with polyesters which contain zinc and cobalt |
DE602005016714D1 (en) * | 2004-12-06 | 2009-10-29 | Eastman Chem Co | COBALT CONCENTRATES POLYESTER BASED ON OXYGEN-SPILLING COMPOSITIONS |
US7955533B2 (en) | 2005-03-02 | 2011-06-07 | Eastman Chemical Company | Process for the preparation of transparent shaped articles |
US7959998B2 (en) | 2005-03-02 | 2011-06-14 | Eastman Chemical Company | Transparent, oxygen-scavenging compositions containing polyesters comprising a cyclobutanediol and articles prepared therefrom |
US7959836B2 (en) | 2005-03-02 | 2011-06-14 | Eastman Chemical Company | Process for the preparation of transparent, shaped articles containing polyesters comprising a cyclobutanediol |
US7964258B2 (en) | 2005-03-02 | 2011-06-21 | Eastman Chemical Company | Transparent, oxygen-scavenging compositions and articles prepared therefrom |
US7968164B2 (en) | 2005-03-02 | 2011-06-28 | Eastman Chemical Company | Transparent polymer blends and articles prepared therefrom |
US7786252B2 (en) | 2005-03-02 | 2010-08-31 | Eastman Chemical Company | Preparation of transparent multilayered articles |
US7462684B2 (en) | 2005-03-02 | 2008-12-09 | Eastman Chemical Company | Preparation of transparent, multilayered articles containing polyesters comprising a cyclobutanediol and homogeneous polyamide blends |
US7955674B2 (en) | 2005-03-02 | 2011-06-07 | Eastman Chemical Company | Transparent polymer blends containing polyesters comprising a cyclobutanediol and articles prepared therefrom |
DE102005011469A1 (en) * | 2005-03-12 | 2006-09-14 | Mitsubishi Polyester Film Gmbh | Multilayer, transparent polyester film with high oxygen barrier |
CA2617591C (en) | 2005-08-30 | 2013-10-22 | Advanced Plastics Technologies Luxembourg S.A. | Methods and systems for controlling mold temperatures |
US8465818B2 (en) | 2005-10-07 | 2013-06-18 | M & G Usa Corporation | Polyamides and polyesters blended with a lithium salt interfacial tension reducing agent |
AR058817A1 (en) | 2005-10-25 | 2008-02-27 | M & G Polimeri Italia Spa | IMPROVED DISPERSIONS OF POLYAMIDS WITH HIGH CARBOXYL CONTENT IN POLYESTERS, BY USING AN INTERFACE TENSION REDUCING AGENT |
US9018293B2 (en) | 2005-10-25 | 2015-04-28 | M&G Usa Corporation | Dispersions of high carboxyl polyamides into polyesters |
CN100349951C (en) * | 2005-11-04 | 2007-11-21 | 东华大学 | Solid phase polymerization process for preparing ethylene telephthalate and aromatic diamine copolymer |
KR101302924B1 (en) | 2006-03-10 | 2013-09-06 | 미츠비시 가스 가가쿠 가부시키가이샤 | Polyester resin composition, method for producing same and molded body |
PL2416962T3 (en) | 2009-04-09 | 2017-07-31 | Valspar Sourcing, Inc. | Polymer having unsaturated cycloaliphatic functionality and coating compositions formed therefrom |
US8747979B2 (en) | 2009-07-17 | 2014-06-10 | Valspar Sourcing, Inc. | Coating compositions and articles coated therewith |
US9011999B2 (en) | 2009-09-18 | 2015-04-21 | Valspar Sourcing, Inc. | Coating composition including an unsaturated polymer |
JP6017107B2 (en) | 2009-12-28 | 2016-10-26 | ソニー株式会社 | Image sensor, manufacturing method thereof, and sensor device |
JP5006956B2 (en) * | 2010-06-29 | 2012-08-22 | 株式会社 イチキン | Thermoplastic resin composition and method for producing the same |
US10322528B2 (en) | 2011-11-16 | 2019-06-18 | APG Polytech, LLC | Color control of polyester-cobalt compounds and polyester-cobalt compositions |
EP2708574A1 (en) | 2012-09-18 | 2014-03-19 | Clariant International Ltd. | Oxygen scavenging plastic material |
EP2851391A1 (en) * | 2013-09-23 | 2015-03-25 | Anheuser-Busch InBev S.A. | Thermoplastic polyester having enhanced barrier and impact properties |
EP2915842A1 (en) | 2014-03-08 | 2015-09-09 | Clariant International Ltd. | Oxygen scavenging composition for plastic material |
Citations (28)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4123403A (en) | 1977-06-27 | 1978-10-31 | The Dow Chemical Company | Continuous process for preparing aqueous polymer microsuspensions |
EP0039155A1 (en) | 1980-04-08 | 1981-11-04 | Asahi Kasei Kogyo Kabushiki Kaisha | Polyester molding composition, production thereof and molded articles produced therefrom |
EP0051336A1 (en) | 1980-10-31 | 1982-05-12 | Stamicarbon B.V. | Polymer composition |
EP0062901A2 (en) | 1981-04-13 | 1982-10-20 | BASF Aktiengesellschaft | Process for the preparation of impact-resistant thermoplastic mouldings |
EP0092979A2 (en) | 1982-04-22 | 1983-11-02 | Yoshino Kogyosho CO., LTD. | Bottle-shaped container |
JPS60240452A (en) * | 1984-05-16 | 1985-11-29 | 三井化学株式会社 | Polyester laminated molded shape and use application thereof |
JPS63288993A (en) | 1987-05-20 | 1988-11-25 | Sumitomo Electric Ind Ltd | Method for synthesizing diamond in gaseous phase |
US4837115A (en) | 1986-07-30 | 1989-06-06 | Toyo Seikan Kaisha, Ltd. | Thermoplastic polyester composition having improved flavor-retaining property and vessel formed therefrom |
JPH01272660A (en) | 1988-04-26 | 1989-10-31 | Ube Ind Ltd | Polyamide resin composition |
EP0398075A1 (en) | 1989-05-15 | 1990-11-22 | Unitika Ltd. | Polyester film |
US5068136A (en) | 1987-12-22 | 1991-11-26 | Mitsubishi Gas Chemical Company, Inc. | Five-layered container |
EP0529336A1 (en) | 1991-08-01 | 1993-03-03 | Toppan Printing Co., Ltd. | Method of thermal fusion |
US5250624A (en) | 1992-05-07 | 1993-10-05 | Eastman Kodak Company | Miscible blends of polyamides and vinylphenol containing polymers |
WO1993020147A1 (en) | 1992-04-02 | 1993-10-14 | Eastman Chemical Company | Polyester/polyamide blend having improved flavor retaining property and clarity |
US5281360A (en) | 1990-01-31 | 1994-01-25 | American National Can Company | Barrier composition and articles made therefrom |
US5300572A (en) | 1991-06-14 | 1994-04-05 | Polyplastics Co., Ltd. | Moldable polyester resin compositions and molded articles formed of the same |
JPH06106614A (en) | 1992-09-24 | 1994-04-19 | Toray Ind Inc | Polyester film for magnetic recording |
WO1994009069A1 (en) | 1992-10-15 | 1994-04-28 | M. & G. Ricerche S.P.A. | Polymeric alloys from polyester resins and process for their preparation |
WO1995011801A1 (en) | 1993-10-25 | 1995-05-04 | American National Can Company | Improved barrier compositions and articles made therefrom |
EP0752437A2 (en) | 1995-07-05 | 1997-01-08 | SINCO ENGINEERING S.p.A. | Polyester resins having improved rheological properties |
WO1997005198A1 (en) | 1995-07-28 | 1997-02-13 | Basf Aktiengesellschaft | Transparent, stress-cracking-resistant moulding compounds with improved toughness-rigidity ratio |
JPH107893A (en) | 1996-06-25 | 1998-01-13 | Mitsubishi Gas Chem Co Inc | Resin composition |
EP0819728A2 (en) | 1996-07-15 | 1998-01-21 | SINCO ENGINEERING S.p.A. | Blown polyester film |
US5993712A (en) | 1997-02-25 | 1999-11-30 | Lurgi Zimmer Aktiengesellschaft | Process for the processing of polymer mixtures into filaments |
US6288161B1 (en) | 1990-01-31 | 2001-09-11 | Pechiney Emballage Flexible Europe | Barrier compositions and articles made therefrom |
EP0964031B1 (en) | 1998-06-11 | 2004-04-07 | COBARR S.p.A. | Polyester resin blends with high-level gas barrier properties |
EP1167447B1 (en) | 2000-06-28 | 2006-04-12 | COBARR S.p.A. | Preparation of polyester resins using a masterbatch of polyaryleneamide |
JP6392667B2 (en) | 2011-12-27 | 2018-09-19 | コーニンクレッカ フィリップス エヌ ヴェKoninklijke Philips N.V. | Magnetic resonance thermography: High resolution imaging of thermal anomalies |
Family Cites Families (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH0717825B2 (en) * | 1986-10-08 | 1995-03-01 | 東洋紡績株式会社 | Stretch blow molding thermoplastic resin composition |
JPH07103308B2 (en) * | 1988-08-26 | 1995-11-08 | 宇部興産株式会社 | Polyamide resin composition |
US5266413A (en) * | 1992-05-18 | 1993-11-30 | Eastman Kodak Company | Copolyester/polyamide blend having improved flavor retaining property and clarity |
GB9221217D0 (en) * | 1992-10-09 | 1992-11-25 | Ici Plc | Working fluid composition |
DE4335322A1 (en) * | 1993-10-18 | 1995-04-20 | Basf Lacke & Farben | Solutions of polyimide-forming substances and their use as coating compositions |
JP3512040B2 (en) * | 1993-12-03 | 2004-03-29 | 三菱瓦斯化学株式会社 | Resin composition |
JPH08183092A (en) * | 1994-12-28 | 1996-07-16 | Unitika Ltd | Biaxially oriented polyester film and production thereof |
-
1998
- 1998-06-11 IT IT1998MI001335A patent/IT1301690B1/en active IP Right Grant
-
1999
- 1999-05-28 EP EP99109316A patent/EP0964031B1/en not_active Expired - Lifetime
- 1999-05-28 AT AT99109316T patent/ATE263808T1/en active
- 1999-05-28 DE DE69916174.6T patent/DE69916174C5/en not_active Expired - Lifetime
- 1999-05-28 ES ES99109316T patent/ES2217645T3/en not_active Expired - Lifetime
- 1999-06-01 KR KR1019990020010A patent/KR100609422B1/en not_active IP Right Cessation
- 1999-06-01 US US09/323,000 patent/US6346307B1/en not_active Ceased
- 1999-06-01 TW TW088109069A patent/TWI235756B/en not_active IP Right Cessation
- 1999-06-03 CA CA002273701A patent/CA2273701C/en not_active Expired - Lifetime
- 1999-06-10 BR BRPI9902233-8A patent/BR9902233B1/en not_active IP Right Cessation
- 1999-06-10 HU HU9901942A patent/HUP9901942A3/en unknown
- 1999-06-10 AU AU34976/99A patent/AU754308B2/en not_active Expired
- 1999-06-10 JP JP16350999A patent/JP4412763B2/en not_active Expired - Lifetime
- 1999-06-10 PL PL99333648A patent/PL333648A1/en unknown
- 1999-06-11 CN CN99108436A patent/CN1243848A/en active Pending
-
2008
- 2008-11-17 US US12/313,141 patent/USRE42925E1/en not_active Expired - Lifetime
-
2009
- 2009-09-14 JP JP2009212032A patent/JP5416516B2/en not_active Expired - Lifetime
Patent Citations (32)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4123403A (en) | 1977-06-27 | 1978-10-31 | The Dow Chemical Company | Continuous process for preparing aqueous polymer microsuspensions |
EP0039155A1 (en) | 1980-04-08 | 1981-11-04 | Asahi Kasei Kogyo Kabushiki Kaisha | Polyester molding composition, production thereof and molded articles produced therefrom |
EP0051336A1 (en) | 1980-10-31 | 1982-05-12 | Stamicarbon B.V. | Polymer composition |
EP0062901A2 (en) | 1981-04-13 | 1982-10-20 | BASF Aktiengesellschaft | Process for the preparation of impact-resistant thermoplastic mouldings |
US4421875A (en) | 1981-04-13 | 1983-12-20 | Basf Aktiengesellschaft | Process for the manufacture of impact resistant thermoplastic molding materials |
EP0092979A2 (en) | 1982-04-22 | 1983-11-02 | Yoshino Kogyosho CO., LTD. | Bottle-shaped container |
JPS60240452A (en) * | 1984-05-16 | 1985-11-29 | 三井化学株式会社 | Polyester laminated molded shape and use application thereof |
US4837115A (en) | 1986-07-30 | 1989-06-06 | Toyo Seikan Kaisha, Ltd. | Thermoplastic polyester composition having improved flavor-retaining property and vessel formed therefrom |
JPS63288993A (en) | 1987-05-20 | 1988-11-25 | Sumitomo Electric Ind Ltd | Method for synthesizing diamond in gaseous phase |
US5068136A (en) | 1987-12-22 | 1991-11-26 | Mitsubishi Gas Chemical Company, Inc. | Five-layered container |
JPH01272660A (en) | 1988-04-26 | 1989-10-31 | Ube Ind Ltd | Polyamide resin composition |
EP0398075A1 (en) | 1989-05-15 | 1990-11-22 | Unitika Ltd. | Polyester film |
US5866649A (en) | 1990-01-31 | 1999-02-02 | American National Can Company | Barrier compositions and articles made therefrom |
US5281360A (en) | 1990-01-31 | 1994-01-25 | American National Can Company | Barrier composition and articles made therefrom |
US6288161B1 (en) | 1990-01-31 | 2001-09-11 | Pechiney Emballage Flexible Europe | Barrier compositions and articles made therefrom |
US5300572A (en) | 1991-06-14 | 1994-04-05 | Polyplastics Co., Ltd. | Moldable polyester resin compositions and molded articles formed of the same |
EP0529336A1 (en) | 1991-08-01 | 1993-03-03 | Toppan Printing Co., Ltd. | Method of thermal fusion |
WO1993020147A1 (en) | 1992-04-02 | 1993-10-14 | Eastman Chemical Company | Polyester/polyamide blend having improved flavor retaining property and clarity |
US5250624A (en) | 1992-05-07 | 1993-10-05 | Eastman Kodak Company | Miscible blends of polyamides and vinylphenol containing polymers |
JPH06106614A (en) | 1992-09-24 | 1994-04-19 | Toray Ind Inc | Polyester film for magnetic recording |
WO1994009069A1 (en) | 1992-10-15 | 1994-04-28 | M. & G. Ricerche S.P.A. | Polymeric alloys from polyester resins and process for their preparation |
WO1995011801A1 (en) | 1993-10-25 | 1995-05-04 | American National Can Company | Improved barrier compositions and articles made therefrom |
EP0752437A2 (en) | 1995-07-05 | 1997-01-08 | SINCO ENGINEERING S.p.A. | Polyester resins having improved rheological properties |
WO1997005198A1 (en) | 1995-07-28 | 1997-02-13 | Basf Aktiengesellschaft | Transparent, stress-cracking-resistant moulding compounds with improved toughness-rigidity ratio |
US5969042A (en) | 1995-07-28 | 1999-10-19 | Basf Aktiengesellschaft | Transparent molding materials resistant to stress cracking and having improved toughness/rigidity ratio |
JPH107893A (en) | 1996-06-25 | 1998-01-13 | Mitsubishi Gas Chem Co Inc | Resin composition |
EP0819728A2 (en) | 1996-07-15 | 1998-01-21 | SINCO ENGINEERING S.p.A. | Blown polyester film |
US5993712A (en) | 1997-02-25 | 1999-11-30 | Lurgi Zimmer Aktiengesellschaft | Process for the processing of polymer mixtures into filaments |
EP0964031B1 (en) | 1998-06-11 | 2004-04-07 | COBARR S.p.A. | Polyester resin blends with high-level gas barrier properties |
DE69916174T2 (en) | 1998-06-11 | 2005-04-14 | Cobarr S.P.A., Anagni | Polyester resin blends with high gas barrier properties |
EP1167447B1 (en) | 2000-06-28 | 2006-04-12 | COBARR S.p.A. | Preparation of polyester resins using a masterbatch of polyaryleneamide |
JP6392667B2 (en) | 2011-12-27 | 2018-09-19 | コーニンクレッカ フィリップス エヌ ヴェKoninklijke Philips N.V. | Magnetic resonance thermography: High resolution imaging of thermal anomalies |
Non-Patent Citations (58)
Title |
---|
"Atomic force microscopic study on blend morphology and clay dispersion in polyamide-6 / polypropylene / organo clay systems", Journal of Polymer Science, Part B: Polymer Physics, 43, 1198-1204 (2005), Exhibit K 39. |
"DAK Americas Sample Summary Report", Exhibit K 43, Dec. 16, 2010. |
"Declaration by Prof Hatsuo Ishida," Case Western University, Cleveland, Jan. 8, 2010, Exhibit K 23 of Schwabe brief, 68 total pages, 9 pages of English Declaration, 9 pgs of German Translation from Hoffmann Eitle, and pp. 457-506 from White et al, Advances in SEM of Polymers, Rubber Chemistry and Technology vol. 57 (1984). |
"Declaration in lieu of oath by Stefan C. Swallart", Mar. 2, 2009 and Hoffmann Eitle, "Translation of declaration in lieu of oath by Stefan C. Swallart", Exhibit K10b of Schwabe brief. |
"Improvement in gas permeability of biaxially stretched PET film blended with high barrier polymers: The role of chemistry and processing conditions." European Polymer Journal, 46,226-237 (2010), Note: declaration from Author Dr. Cakmak added by Applicants. |
"Manipulating the phase morphology in PPS / PA6 blends using clay", Journal of Applied Polymer Science, 106, 2238-250 (2007), Exhibit K 40. |
"The Wiley Encyclopedia of Packaging Technology", 1986, pp. 512-515, Exhibit K6 of Schwabe brief. |
"Wikipedia, Polyethylene Terephthalate", http://en.wikipedia.org/wili/Polyethylene-terephthalate, Nov. 21, 2008, six pages, Exhibit K6 of Schwabe brief. |
Aspy, Paul, "Modern Plastics", "Crystallization control of PET Copolyesters", , pp. 74-76, Volume AUG, No. 1983, Published in: USA, Exhibit K2 of Schwabe brief. |
Boehmert & Boehmert, Hoffmann Eitle "Translation of Nullity Action by Boehmert & Boehmert", Mar. 25, 2009, Includes exhibits which are not patents or NPL documents disclosed elsewhere. |
BP Amoco Chemical Co, "Environmental Assessment for Food Additive Petition Terephthalate-lsophthalate Polymers", Sep. 14, 1999, Published in: USA, Exhibit K3 of Schwabe brief. |
Bundle of Exhibits: Excerpt from Wikipedia with regard to the key word: "average"; excerpt from Dr. Ing.. Richard Erns "Worterbuch der industriellen Technik", vol. 1, Oscor Brandstetter, as published in Berlag AG, Weisbaden 1974 regardin the key word "average"-Exhibit K26 of Swchabe brief. |
Chemical Abstracts, vol. 113, No. 25, Dec. 17, 1990-Columbus, Ohio, US; abstract No. 232752, XP002126791 *abstract* & JP 01 272660 A (Ube Ind., Ltd.) Oct. 31, 1989. |
Database WPI, Section Ch, Week 198603, Derwent Publications Ltd., London, GB; AN 1986-017548-XP002126792 & JP 60 240452 A (Mitsui Petrochem Ind Co Ltd), Nov. 29, 1985 *abstract*. |
Declaration # 1 of Delane Nagel Richardson, Feb. 1, 2011, 3 pages. |
Declaration of Arianna Giovannini, Apr. 11, 2010, 2 pages, notes imaging software has smaller reading than hand measurements (pts 9-11) . |
Declaration of Dr. Mukerrem Cakmak, Feb. 2, 2011, 4 pages. |
Declaration of Geoffrey R. Scantlebury, #1, Re: EP 0 964 031, Exhibit SH 10, 6 pgs, Jan. 14, 2011. |
Declaration of Geoffrey R. Scantlebury, #2, Re: EP 0 964 031, Exhibit SH 9, 8 pgs. Purports to be another rework but is not a valid comparison, see explanation on submission sheet. |
Dr. Stena Kettl, Ph.D., "Statistische Analyse der mittleren Grosse der dispergierten Domanen in PET-Flaschen," Sep. 29, 2008, Exhibit K 18 of Schwabe brief, Original English Version Included, 17 pgs. |
Dr. Thiele, "Gutachten," Nov. 16, 2009, Exhibit K 24 of Schwabe brief,8pgs Eng Translation. includes 5 pgs of ASTM D 3576-98, Standard Test Method for Cell Size of Rigid Cellular Plastics, Jan. 1999 and DE 197 07 447 to Thiele.et al. (Zimmer). Corresponds to US 5993712 cited in this submission. See claim 2 and col. 7, lines 11-22 for technique to determine domain distirbution of on polymer dispersed in another. |
Dr. Thiele, "Gutachten," Nov. 16, 2009, Exhibit SH 4, Already entered as Exhibit 24 of Schwabe brief,However, this submission only contained the declaration report and did not contain the patent or the ASTM standard. 8pgs Eng Translation. This Copy is not Submitted as it has already been submitted as a different entry. |
Dr.-Ing. Bauer, "Letter to Alpla Hard Technical Center and Hoffmann Eitle"Translation of Declaration to Alpla Hard Technical Center, Feb. 26, 2009, Exibit K10a of Schwabe brief. |
Dupont, "Selar PT Polyesters for Packaging Applications", Oct. 3, 1992, and Hoffmann Eitle Translation Exhibit K10c of Schwabe brief. |
EPO, "Communication to Sinco Ricerche S.p.A.", Jul. 22, 2002, Exhibit K13 of Schwabe brief. |
Exhibit K 38 is EP 1 167 447, see above, (in foreign patent documents section). |
Fraunhofer Institute for Applied Polymer Research dated Jan. 18, 2011 "Examination of the etching behaviour of PET bottles", Exhibit K 37, English Translation Provided as SH2, IDS item 29. |
Fraunhofer Institute for Applied Polymer Research dated Jan. 18, 2011 "Examination of the etching behaviour of PET bottles", Exhibit SH 2, English Translation Provided 8pgs. Report is same as that submitted by Shwabae, K 37, IDS item 20. |
Fraunhofer Institute for Applied Polymer Research dated Oct. 26, 2010 Exhibit K 35, in German, English translation provided. This document is to rebut the accuracy of the Proplast report (K17) establishing infringement. |
Fraunhofer, "Test Report Regarding Pore Distribution in injection molding of a polyethylene terephthalate-polyamide composite." Jan. 17, 2001. 2 pages. Exhibit SH 7. The document purports to be a rework of Example in Table 3 of WO 95/11801. The rework is not even a close comparison to establish an inherent disclosure. See attached comparison establishing inability to recreate a working example. |
Hoffmann Eitle, "Cobarr S.P.A. v. Alpa Werke," Domain measurements, Jan. 25, 2010, Exhibit K 19 of Schwabe brief, 15 pgs. |
Hoffmann Eitle, "Cobarr S.P.A. v. Alpa Werke," Domain measurements, Jan. 25, 2010, Exhibit K 20 of Schwabe brief, 10 pgs. |
Hoffmann Eitle, "Cobarr S.P.A. v. Alpa Werke," Domain measurements, Jan. 25, 2010, SH 6 and Exhibit K 19 of Schwabe brief, 16 pgs. Note: because the files differ by 1 page, the whole of SH 6 is being submitted. |
Hoffmann Eitle, "Cobarr S.P.A. v. Alpa Werke," Domain measurements, Jan. 28, 2010, Exhibit K 21 of Schwabe brief, 14 pgs. |
Hoffmann Eitle, "Cobarr S.P.A. v. Alpa Werke," Domain measurements, Jan. 28, 2010, Exhibit K 22 of Schwabe brief, 9 pgs. |
ISO, "Representation of results of particle size analysis, Part 5: Methods of calculation relating to particle size analyses using logarithmic normal probability distribution," First edition, Aug. 1, 2005, Exhibit K 34 of Schwabe brief. |
Judgment as issued by the Federal Patent Court and pronounced on Feb. 8, 2011 (Document in German). |
Karayannidis et al., "Journal of Applied Polymer Science", "Thermal Behavior and Tensile Properties of Poly(ethylene terephthalate-co-ethylene isophthalate)", Dec. 16, 1999, pp. 200-207, vol. 78, Exhibit K10f of Schwabe brief. |
Kirk-Othmer, "Encyclopedia of Chemical Technology, 4th Edition", 1996, vol. 19, pp. 618-621, Exhibit K1 of Schwabe brief. |
Klusmann, Hoffmann-Eitle submission brief to Federal Patent Court Dec. 27, 2010. 17 pgs. |
Limpert, Stahel & ABBT, "Log-normal Distributions Across the Sciences: Keys and Clues," BioScience, vol. 51, No. 5, May 2001, Exhibit K 33 of Schwabe brief. |
M&G, "M&G Website", 2009; http://www.gruppomg.com/pag.php?mi=200&mod=userpage&pI=1077 and http://www,gruppomg.com/history.php?mi=201, Exhibit K4 of Schwabe brief. |
MGC, Nylon MXD6 Grades and Uses, 2 pgs, copyright 2007. |
Paul and Bucknall, Polymer Blends, 2000, pp. 369-371. Exhibit SH 11, copyright 2000. |
Pictures of domains from DE 7 (Infringement Suit). Exact Same submission as Schwabe, K21 entered as IDS 6, see item 6 of this IDS. |
Scantlebury, Geoffrey, "Declaration of Geoffrey R. Scantlebury," Jan. 8, 2010, Exhibit K 28 of Schwabe brief, Mr. Scantlebury argues that the word average means D50 and not arithmetic mean pointing to prior art EP 0051336, EP0062901 (, EP0842222 and US 4123403-however by his own description on point 12, none of this art discloses nylon dispersed in polyester. |
Scantlebury, Geoffrey, "Declaration of Geoffrey R. Scantlebury," Jun. 24, 2010, Exhibit K 25 of Schwabe brief, regarding the examination of raw data of the infringement case. |
Scantlebury, Geoffrey, "Erklarung von Geoffrey R. Scantlebury," Jan. 8, 2010, Exhibit K 29 of Schwabe brief, is the German Translation of Exhibit 28 above, IDS entry 13. Note: exhibits 30-32 are patent literature. |
Schwabe, Sandmair, Marx, "Nullity Action against the German Pat, 699 16 174, of European Patent 0 964 031," Jan. 19, 2011, on behalf of Alpla Werke and Hoffmann Elite English translation 21 pgs; references new exhibits K35-K43 described on p. 21. |
Schwabe, Sandmair, Marx, "Nullity Action against the German Pat, 699 16 174, of European Patent 0 964 031," Jul. 5, 2010, on behalf of Alpla Werke and Hoffmann Elite English translation pp. 1-36; references exhibits K16-K34 described on p. 36, addressed in accompanying document with this submission to the USPTO. |
Schwabe, Sandmair, Marx, "Partial Nullity Action on behalf of Alpla Werke", and Hoffmann Eitle "Translation of the relevant parts of Partial Nullity Action on behalf of Alpla Werke", Apr. 24, 2009, the whole document. |
Schwabe, Sandmair, Marx, Brief dated Oct. 28, 2010 in the parallel infringement appeal proceedings, Exhibit K 36, in German, English translation provided. Cites WO 95/11801, JP 8-183092, JP 63-92667 as destroying novelty. This art was already produced for review as items 9, 6, and 8 respectively in the IDS dated Jul. 28, 2009. |
Scrivia., "Average Size of the Dispersed Domains in the Injection Molded Portion of Carpe Diem Bottles," Test Report From PROPLAST, Oct. 21, 2008, Exhibit K17 (Original English and German Translation) and K17a (8 pgs) (domain measurements) of Schwabe brief. K16 is not submitted with this IDS as it is merely digital images of the photographs used to print the pictures. |
Scrivia., "Average Size of the Dispersed Domains in the Injection Molded Portion of Carpe Diem Bottles," Test Report From Proplast, Oct. 21, 2008, Exhibit SH 5. This only contains the first 41 pages of the report submitted as Schwabe K17, IDS item 2. To avoid Duplication, nothing is submitted as SH 5, IDS Item 32 as it is already submitted elsewhere. |
Statement of Dr. Scantlebury dated Jan. 18, 2011, Exhibit K 42. |
Translation of Judgment as issued by the Federal Patent Court and pronounced on Feb. 8, 2011. |
Wallan (Dupont), "Letter to Valspar Corporation", Mar. 11, 2009, Exhibit K10d of Schwabe brief. |
Yoshitsugu Maruhashi and Setsuko Iida, "Transparency of Polymer Blends," Polymer Engineering and Science, Nov. 2001, vol. 41, No. 11, pp. 1987-1995. |
Also Published As
Publication number | Publication date |
---|---|
KR100609422B1 (en) | 2006-08-03 |
AU754308B2 (en) | 2002-11-14 |
JP2009298487A (en) | 2009-12-24 |
CA2273701C (en) | 2008-02-12 |
PL333648A1 (en) | 1999-12-20 |
ITMI981335A1 (en) | 1999-12-13 |
BR9902233A (en) | 2000-05-02 |
EP0964031B1 (en) | 2004-04-07 |
EP0964031A3 (en) | 2000-03-01 |
DE69916174D1 (en) | 2004-05-13 |
HU9901942D0 (en) | 1999-08-30 |
BR9902233B1 (en) | 2009-01-13 |
EP0964031A2 (en) | 1999-12-15 |
DE69916174T2 (en) | 2005-04-14 |
TWI235756B (en) | 2005-07-11 |
AU3497699A (en) | 1999-12-23 |
JP2000034357A (en) | 2000-02-02 |
JP5416516B2 (en) | 2014-02-12 |
HUP9901942A3 (en) | 2001-06-28 |
US6346307B1 (en) | 2002-02-12 |
HUP9901942A2 (en) | 2001-05-28 |
ES2217645T3 (en) | 2004-11-01 |
CA2273701A1 (en) | 1999-12-11 |
DE69916174C5 (en) | 2015-07-30 |
CN1243848A (en) | 2000-02-09 |
JP4412763B2 (en) | 2010-02-10 |
ATE263808T1 (en) | 2004-04-15 |
KR20000005804A (en) | 2000-01-25 |
IT1301690B1 (en) | 2000-07-07 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
USRE42925E1 (en) | Polyester resin blends with high-level gas barrier properties | |
US5650469A (en) | Polyester/polyamide blend having improved flavor retaining property and clarity | |
EP0939095B1 (en) | Polyester pellets and process for preparing the same | |
US5068136A (en) | Five-layered container | |
EP1784300B1 (en) | Polyester-polyamide blends having low haze | |
KR100883295B1 (en) | Transparent polyester resins and articles therefrom | |
JPS6172051A (en) | Polyester composition and container made thereof | |
JP3737302B2 (en) | New polyester pellets and method for producing polyester pellets | |
AU2002338703A1 (en) | Transparent polyester resins and articles therefrom | |
JPS63213529A (en) | Hollow molded article of polyester | |
MXPA99005413A (en) | Polyester resin mixtures with high ni gas barrier properties | |
JP3790046B2 (en) | Polyester resin composition | |
JP4140991B2 (en) | Polyester resin bottle | |
JP3808631B2 (en) | Polyester bottle manufacturing method | |
JP2000119496A (en) | Polycondensation copolymer and molded product | |
JPH1120009A (en) | Polyester preform | |
JPH1121435A (en) | Polyester resin composition and production thereof | |
JPH09302205A (en) | Polyester resin composition and hollow molding made therefrom | |
JPH106386A (en) | Hollow molded object made of polyester | |
US20060149001A1 (en) | Transparent polyester resins and articles therefrom | |
JPH01154733A (en) | Hollow polyester molding |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
FPAY | Fee payment |
Year of fee payment: 12 |
|
AS | Assignment |
Owner name: M&G USA CORPORATION, WEST VIRGINIA Free format text: ASSIGNMENT OF ASSIGNORS INTEREST;ASSIGNOR:COBARR S.R.L.;REEL/FRAME:035981/0028 Effective date: 20130927 |
|
AS | Assignment |
Owner name: TRIMONT REAL ESTATE ADVISORS, LLC, GEORGIA Free format text: SECURITY INTEREST;ASSIGNOR:M&G USA CORPORATION;REEL/FRAME:044930/0245 Effective date: 20171220 |
|
AS | Assignment |
Owner name: FE POLYTECH, LLC, DELAWARE Free format text: ASSIGNMENT OF ASSIGNORS INTEREST;ASSIGNOR:M&G USA CORPORATION;REEL/FRAME:045567/0652 Effective date: 20180301 Owner name: M&G USA CORPORATION, WEST VIRGINIA Free format text: RELEASE BY SECURED PARTY;ASSIGNOR:UNITED STATES BANKRUPTCY COURT FOR DISTRICT OF DELAWARE;REEL/FRAME:045567/0597 Effective date: 20180201 |
|
AS | Assignment |
Owner name: APG POLYTECH, LLC, DELAWARE Free format text: CHANGE OF NAME;ASSIGNOR:FE POLYTECH, LLC;REEL/FRAME:045819/0235 Effective date: 20180323 |
|
AS | Assignment |
Owner name: M&G USA CORPORATION, DELAWARE Free format text: RELEASE BY SECURED PARTY;ASSIGNOR:TRIMONT REAL ESTATE ADVISORS, LLC;REEL/FRAME:046067/0127 Effective date: 20180301 |
|
AS | Assignment |
Owner name: M&G USA CORPORATION, WEST VIRGINIA Free format text: RELEASE BY SECURED PARTY;ASSIGNOR:TRIMONT REAL ESTATE ADVISORS, LLC;REEL/FRAME:048000/0890 Effective date: 20181228 |