EP0437496A1 - Modified poly(ethylene 2,6-naphthalenedicarboxylate) having improved processability - Google Patents

Modified poly(ethylene 2,6-naphthalenedicarboxylate) having improved processability

Info

Publication number
EP0437496A1
EP0437496A1 EP89911495A EP89911495A EP0437496A1 EP 0437496 A1 EP0437496 A1 EP 0437496A1 EP 89911495 A EP89911495 A EP 89911495A EP 89911495 A EP89911495 A EP 89911495A EP 0437496 A1 EP0437496 A1 EP 0437496A1
Authority
EP
European Patent Office
Prior art keywords
pen
polyester
acid
ethylene
mol
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.)
Pending
Application number
EP89911495A
Other languages
German (de)
French (fr)
Inventor
Freddie Allen Shepherd
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Eastman Kodak Co
Original Assignee
Eastman Kodak Co
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Eastman Kodak Co filed Critical Eastman Kodak Co
Publication of EP0437496A1 publication Critical patent/EP0437496A1/en
Pending legal-status Critical Current

Links

Classifications

    • 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
    • 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
    • C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
    • C08G63/12—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from polycarboxylic acids and polyhydroxy compounds
    • C08G63/16—Dicarboxylic acids and dihydroxy compounds
    • C08G63/18—Dicarboxylic acids and dihydroxy compounds the acids or hydroxy compounds containing carbocyclic rings
    • C08G63/181—Acids containing aromatic rings
    • C08G63/185—Acids containing aromatic rings containing two or more aromatic rings
    • C08G63/187—Acids containing aromatic rings containing two or more aromatic rings containing condensed aromatic rings
    • C08G63/189—Acids containing aromatic rings containing two or more aromatic rings containing condensed aromatic rings containing a naphthalene ring
    • 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

Definitions

  • the present invention relates to a novel poly(ethylene 2,6-naphthalenedicarboxylate) , sometimes referred herein as PEN, having improved processability. More specifically, it relates to PEN having a reduced melt viscosity which is more easily processed.
  • Poly(ethylene terephthalate) is well known as a packaging material.
  • polyesters made from naphthalene-2,6-dicarboxylic acid show superior resistance to gas permeability to those made from much more commonly available, and much less costly, terephthalic acid.
  • the polyester formed from NDA and ethylene glycol, i.e., PEN is superior to PET in the retention of gaseous molecules in hot-filled food and beverage containers utilizing a monolayer of these polyesters or f bricated from these polyesters. That is, gaseous diffusion rates for oxygen and other gases across barriers of PEN are less than the rates 'for similar configurations of PET.
  • PEN may be processed by injection stretch blow molding, reheat stretch blow molding or extrusion blow molding in order to obtain useful containers of PEN having a relatively high melting point, i.e., 510°F (265°C) and high melt viscosity.
  • the high temperature required to process PEN frequently results in excessive drops in molecular weight during processing.
  • processing temperatures typically of 575°F (300°C) to more that 600°F (315°C) are required for PEN processing.
  • it is necessary to produce higher molecular weight materials than are actually required so that one may end up with the desired molecular weight in the PEN containers actually produced.
  • the higher molecular weights usually result in higher melt viscosity which in turn requires higher processing temperatures. Processing of PEN is therefore cumbersome and molecular weights are difficult to control.
  • one object of the present invention is to provide PEN having a reduced melting point and therefore capable of being more easily processed.
  • the invention is also directed to a method of reducing the melting point of PEN by modifying PEN with 0.1 to 10 mol % of at least one comonomer as specified herein.
  • the invention further provides articles made from PEN.
  • PEN having up to 10 mol % of monomer units from 2,7-naphthalenedicarboxylic acid are preferred.
  • the modified PEN described herein is referred to as a polymer.
  • the modified PEN is actually a copolymer.
  • the modified PEN will be referred to herein as a polymer.
  • the polyester is produced from 100 mol % of a dicarboxylic acid component and 100 mol % of a glycol component. Either may be modified with 0.1 to 10 mol % of the acids or glycols specified.
  • the modifier also may be a combination of at least one acid and at least one glycol as specified herein, wherein the modification would be 0.1 to 10 mol % out of the total 200 mol %.
  • the modified PEN of the present invention has an inherent viscosity (I.V.) of from 0.60 to 0.90 dl/g, preferably from 0.70 to 0.80 dl/g.
  • This modified PEN has melting points which are reduced by 10° to 18°C relative to unmodified PEN and therefore can be processed at lower temperatures than the modified PEN.
  • the PEN of the present invention is prepared by conventional methods for condensation polymerization well known by those skilled in the art.
  • the PEN may be bulk polymerized by reacting the monomers in batches or in an extruder, to produce pellets of the PEN.
  • Polymers which are initially produced by bulk polymerization may be further modified by solid-phase polymerization to effect a molecular weight increase.
  • the conventional polymer processing techniques which may be used in the preparation of the present polyester are well known to those skilled in the art.
  • the PEN according to this invention may be used to mold (e.g., conventional injection blow molding) articles such as containers, extruded into a packaging film, and the like.
  • Conventional additives such as stabilizers, plasticizers, colorants,, etc., may be used.
  • the lower melting points and inherent viscosities are obtained from the copolymers, while at the same time retaining the desired barrier, strength and thermal properties.
  • Table 1 presents the physical characteristics for PEN films containing varying amounts of 2,7-naphthalenedicarboxylic acid, diethylene glycol, 1,4-cyclohexanedimethanol, terephthalic acid and isophthalic acid monomer units as well as the control, i.e., an unmodified PEN film. It can be seen from Table 1 that the inherent viscosity of the
  • 2,7-naphthalenedicarboxylic acid monomer unit-containing PEN is substantially below the inherent viscosity of the control PEN.
  • the melting point of each of the modified PEN films is below the melting point of the control, as well.
  • the oxygen permeability, water vapor transmission rate, tensile strength, elongation and flexural modulus properties remain substantially similar to the control. Applicants have therefore discovered modified polyesters in which the melting points and inherent viscosities are selectively lowered without causing serious decreases in the desired barrier, thermal and strength properties.
  • 2,6-Dimethyl naphthalenedicarboxylate is reacted with ethylene glycol to produce pellets of poly(ethylene 2,6-naphthalenedicarboxylate) which has an I.V. of 0.50 dl/g.
  • the pellets are crystallized at 200°C and then solid-phase polymerized at 220°C to an inherent viscosity of 0.72 dl/g.
  • This material is dried at 220°C in a desiccant dryer for a minimum of 16 hours and used in a 3/4 inch Brabender Extruder to produce 20 mil film having an inherent viscosity of 0.60 dl/g. A portion of this film is biaxially oriented at 140°C with a T. M. Long Film Stretcher. See Table 1 for film properties.
  • Ethylene glycol is reacted with mixtures of 2,6-dimethyl naphthalenedicarboxylate/2,7-dimethyl naphthalenedicarboxylate wherein the 2,7 isomer is either 5 or 10 mol % of the reaction mixture to produce pellets of PEN which have an inherent viscosity of 0.50 dl/g.
  • These samples are crystallized and solid-phase polymerized as described in Example 1 to obtain a material having an inherent viscosity of
  • Example 3 PEN is produced as described in Examples 1 and 2 but contains 10 mol % of either diethylene glycol (DEG) or 1,4-cyclohexanedimethanol (CHDM) in the reaction mix to obtain samples of copol (ethylene/diethylene 2,6-naphthalenedicarboxylate and copoly(ethylene/1,4- ⁇ yclohexanedimethanol 2,6-naphthalenedicarbox late having an inherent viscosity of 0.73 and 0.82 dl/g, respectively. Film samples are produced as described in Example 1 and properties obtained.
  • DEG diethylene glycol
  • CHDM 1,4-cyclohexanedimethanol
  • PEN is produced as described in Example 1 and 2 but contains 10 mol % of either dimethyl terephthalate (DMT) or dimethyl isophthalate (DMI) in the reaction mix to obtain samples of copoly(ethylene 2,6-naphthalene dicarboxylate/terephthalate or copol (ethylene 2,6-naphthalenedicarboxylate/isophthalate) each having an inherent viscosity of 0.75 dl/g. Film samples are produced as described in Example 1 and properties obtained.
  • DMT dimethyl terephthalate
  • DMI dimethyl isophthalate
  • the inherent viscosity is measured at 25°C using 0.50 g of polymer per 100 mL of a solvent consisting of 60% by weight phenol and 40% by weight tetrachloroethane.
  • the tests used herein for determination of mechanical properties are described as follows:
  • oxygen permeability is determined according to ASTM D 3985, in cubic centimeters permeating a 1 mil thick sample, 100 inches square, for a 24-hour period under oxygen partial pressure difference of one atmosphere at 30°C using a MOCON Oxtran 10-50 instrument.
  • ester forming derivatives of the acids may be used rather than the acids themselves as in conventional practice.
  • weight of reinforcing glass fibers and nucleating agent(s) are based on total composition weight.

Abstract

Le polyester poly(2,6-naphthalènedicarboxylate) modifié avec des unités monomères de 0,1 à 10 moles % d'au moins un acide dicarboxylique ou un glycol sélectionné parmi l'acide 2,7-naphthalène dicarboxylique, le diéthylène glycol, 1,4-cyclohexanediméthanol, l'acide isophthalique et l'acide térephthalique est décrit.Polyester poly (2,6-naphthalenedicarboxylate) modified with monomer units of 0.1 to 10 mole% of at least one dicarboxylic acid or a glycol selected from 2,7-naphthalene dicarboxylic acid, diethylene glycol, 1 , 4-cyclohexanedimethanol, isophthalic acid and terephthalic acid is described.

Description

MODIFIED POLY(ETHYLENE 2,6-NAPHTHALENEDICARBOXYLATE) HAVING IMPROVED PROCESSABILITY
BACKGROUND OF THE INVENTION
Field of the Invention
The present invention relates to a novel poly(ethylene 2,6-naphthalenedicarboxylate) , sometimes referred herein as PEN, having improved processability. More specifically, it relates to PEN having a reduced melt viscosity which is more easily processed.
Description of the Background
Poly(ethylene terephthalate) , sometimes referred to herein as PET, is well known as a packaging material.
However, gaseous diffusion rates across barriers of PET are higher than desired from materials to be used in most food packaging applications. It is known that polyesters made from naphthalene-2,6-dicarboxylic acid, sometimes referred to herein as NDA, show superior resistance to gas permeability to those made from much more commonly available, and much less costly, terephthalic acid. In particular, the polyester formed from NDA and ethylene glycol, i.e., PEN, is superior to PET in the retention of gaseous molecules in hot-filled food and beverage containers utilizing a monolayer of these polyesters or f bricated from these polyesters. That is, gaseous diffusion rates for oxygen and other gases across barriers of PEN are less than the rates 'for similar configurations of PET. Packages fabricated from PEN are, therefore, very desirable for hot filled high barrier applications. PEN may be processed by injection stretch blow molding, reheat stretch blow molding or extrusion blow molding in order to obtain useful containers of PEN having a relatively high melting point, i.e., 510°F (265°C) and high melt viscosity. The high temperature required to process PEN frequently results in excessive drops in molecular weight during processing. Typically, processing temperatures of 575°F (300°C) to more that 600°F (315°C) are required for PEN processing. In order to compensate for the drop in molecular weight, it is necessary to produce higher molecular weight materials than are actually required so that one may end up with the desired molecular weight in the PEN containers actually produced. The higher molecular weights usually result in higher melt viscosity which in turn requires higher processing temperatures. Processing of PEN is therefore cumbersome and molecular weights are difficult to control.
Accordingly, there exists a need to improve the processability of PEN, either by reducing the melting point or by reducing the melt viscosity.
Since having a high melt viscosity could be an advantage for some applications, reducing the melting point of PEN is the desired approach to improving processability.
SUMMARY OF THE INVENTION Accordingly, one object of the present invention is to provide PEN having a reduced melting point and therefore capable of being more easily processed.
This and other objects of the present invention will become apparent from the following description of the present invention. According to the present invention, there is provided poly(ethylene 2,6-naphthalenedicarboxylate) modified with monomer units from 0.1 to 10 mol % of at least one dicarboxylic acid or glycol selected from 2,7-naphthalenedicarboxylic acid, diethylene glycol, 1,4-cyclohexanedimethanol, isophthalic acid and terephthalic acid.
The invention is also directed to a method of reducing the melting point of PEN by modifying PEN with 0.1 to 10 mol % of at least one comonomer as specified herein. The invention further provides articles made from PEN.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS The melting point of PEN, as with most polyesters, can be reduced by producing copolymers. However, this sometimes also results in increases in melt viscosity and the choice of comonomers in the production of the copolymers is critical so that PEN is produced having the desired barrier, thermal and strength properties as well as the desired reduction in melting points without increasing the melt viscosity. Applicants have discovered that incorporation of up to 10 mol % of monomer units from 2,7-naphthalenedicarboxylic acid, diethylene glycol, 1,4-cyclohexanedimethanol, isophthalic acid or terephthalic acid will reduce the melting point of PEN without effecting the barrier, thermal and strength properties or causing significant increases in melt viscosity. PEN having up to 10 mol % of monomer units from 2,7-naphthalenedicarboxylic acid are preferred.
The modified PEN described herein is referred to as a polymer. Those skilled in the art will recognize that, in the strict since of the word, the modified PEN is actually a copolymer. For simplicity, however, the modified PEN will be referred to herein as a polymer.
As described herein, the polyester is produced from 100 mol % of a dicarboxylic acid component and 100 mol % of a glycol component. Either may be modified with 0.1 to 10 mol % of the acids or glycols specified. The modifier also may be a combination of at least one acid and at least one glycol as specified herein, wherein the modification would be 0.1 to 10 mol % out of the total 200 mol %.
The modified PEN of the present invention has an inherent viscosity (I.V.) of from 0.60 to 0.90 dl/g, preferably from 0.70 to 0.80 dl/g. This modified PEN has melting points which are reduced by 10° to 18°C relative to unmodified PEN and therefore can be processed at lower temperatures than the modified PEN.
The PEN of the present invention is prepared by conventional methods for condensation polymerization well known by those skilled in the art. For example, the PEN may be bulk polymerized by reacting the monomers in batches or in an extruder, to produce pellets of the PEN. Polymers which are initially produced by bulk polymerization may be further modified by solid-phase polymerization to effect a molecular weight increase. The conventional polymer processing techniques which may be used in the preparation of the present polyester are well known to those skilled in the art.
The PEN according to this invention may be used to mold (e.g., conventional injection blow molding) articles such as containers, extruded into a packaging film, and the like. Conventional additives, such as stabilizers, plasticizers, colorants,, etc., may be used. Surprisingly, the lower melting points and inherent viscosities are obtained from the copolymers, while at the same time retaining the desired barrier, strength and thermal properties. Table 1 presents the physical characteristics for PEN films containing varying amounts of 2,7-naphthalenedicarboxylic acid, diethylene glycol, 1,4-cyclohexanedimethanol, terephthalic acid and isophthalic acid monomer units as well as the control, i.e., an unmodified PEN film. It can be seen from Table 1 that the inherent viscosity of the
2,7-naphthalenedicarboxylic acid monomer unit-containing PEN is substantially below the inherent viscosity of the control PEN. The melting point of each of the modified PEN films is below the melting point of the control, as well. However, the oxygen permeability, water vapor transmission rate, tensile strength, elongation and flexural modulus properties remain substantially similar to the control. Applicants have therefore discovered modified polyesters in which the melting points and inherent viscosities are selectively lowered without causing serious decreases in the desired barrier, thermal and strength properties.
Other features of the invention will become apparent in the course of the following descriptions of exemplary embodiments which are given for illustration of the invention and are not intended to be limiting thereof.
EXAMPLES
Example 1 (Control)
2,6-Dimethyl naphthalenedicarboxylate is reacted with ethylene glycol to produce pellets of poly(ethylene 2,6-naphthalenedicarboxylate) which has an I.V. of 0.50 dl/g. The pellets are crystallized at 200°C and then solid-phase polymerized at 220°C to an inherent viscosity of 0.72 dl/g. This material is dried at 220°C in a desiccant dryer for a minimum of 16 hours and used in a 3/4 inch Brabender Extruder to produce 20 mil film having an inherent viscosity of 0.60 dl/g. A portion of this film is biaxially oriented at 140°C with a T. M. Long Film Stretcher. See Table 1 for film properties.
Example 2
Ethylene glycol is reacted with mixtures of 2,6-dimethyl naphthalenedicarboxylate/2,7-dimethyl naphthalenedicarboxylate wherein the 2,7 isomer is either 5 or 10 mol % of the reaction mixture to produce pellets of PEN which have an inherent viscosity of 0.50 dl/g. These samples are crystallized and solid-phase polymerized as described in Example 1 to obtain a material having an inherent viscosity of
0.65 dl/g. These samples are extruded into film as described in Example 1. The sample containing 5 mol % of the 2,7 isomer gives films having an I.V. = 0.61, and the sample containing 10 mol % of the 2,7 isomer gives a film having an I.V. of 0.64. Portions of these film samples are biaxially oriented as described in Example 1. See Table 1 for film properties.
Example 3 PEN is produced as described in Examples 1 and 2 but contains 10 mol % of either diethylene glycol (DEG) or 1,4-cyclohexanedimethanol (CHDM) in the reaction mix to obtain samples of copol (ethylene/diethylene 2,6-naphthalenedicarboxylate and copoly(ethylene/1,4-σyclohexanedimethanol 2,6-naphthalenedicarbox late having an inherent viscosity of 0.73 and 0.82 dl/g, respectively. Film samples are produced as described in Example 1 and properties obtained.
Example 4
PEN is produced as described in Example 1 and 2 but contains 10 mol % of either dimethyl terephthalate (DMT) or dimethyl isophthalate (DMI) in the reaction mix to obtain samples of copoly(ethylene 2,6-naphthalene dicarboxylate/terephthalate or copol (ethylene 2,6-naphthalenedicarboxylate/isophthalate) each having an inherent viscosity of 0.75 dl/g. Film samples are produced as described in Example 1 and properties obtained.
TABLE 1 - FILM PROPERTIES OF PEN
As used herein, the inherent viscosity (I.V.) is measured at 25°C using 0.50 g of polymer per 100 mL of a solvent consisting of 60% by weight phenol and 40% by weight tetrachloroethane. The tests used herein for determination of mechanical properties are described as follows:
Water Vapor Transmission Rate ASTM F372 Tensile Strength ASTM D638-80
Elongation ASTM D638-80 Flexural Modulus ASTM D790-80
In the examples, oxygen permeability is determined according to ASTM D 3985, in cubic centimeters permeating a 1 mil thick sample, 100 inches square, for a 24-hour period under oxygen partial pressure difference of one atmosphere at 30°C using a MOCON Oxtran 10-50 instrument.
Where acids are specified herein in the formation of the polyesters or copolyesters, it should be understood that ester forming derivatives of the acids may be used rather than the acids themselves as in conventional practice.
Unless otherwise specified, all parts, percentages, ratios, etc., are by weight. Weight of reinforcing glass fibers and nucleating agent(s) are based on total composition weight.
Obviously, numerous modifications and variations of the present invention are possible in light of the above teachings. It is therefore to be understood th,at within the scope of the appended claims, the invention may be practiced otherwise than as specifically described herein.

Claims

CLAIMSI claim:
1. The polyester pol (ethylene naphthalene-2,6-dicarboxylate) characterized as having monomer units from 0.1 to 10 mol % of at least one dicarboxylic acid or glycol selected from 2,7-naphthalenedicarboxylic acid, diethylene glycol, 1,4-cyclohexanedimethanol, isophthalic acid and terephthalic acid.
2. The polyester of Claim 1, characterized as having 5 to 10 mol % of said comonomer units .
3. The polyester of Claim 1, characterized as having an inherent viscosity of 0.60 to 0.90 dl/g.
4. The polyester of Claim 1, wherein said comonomer units are derived only from 2,7-naphthalene- dicarboxylic acid.
5. The polyester of Claim 1, characterized as having a melting point in the range from 187° to 190°C.
6. The method of producing poly(ethylene
2,6-naphthalenedicarboxylate) having a reduced melting point without increasing the melt viscosity thereof characterized by introducing into the polymer repeat units from 0.1 to 10 mol % of a compound selected from 2,7-naphthalenedicarboxylic acid, diethylene glycol, 1,4-cyclohexanedimethanol, isophthalic acid and terephthalic acid. 7. The method according to Claim 6, wherein said compound is 2,
7-naphthalenedicarboxylic acid.
8. Film or sheet material comprising the polyester of Claim 1.
9. A food container comprising the polyester of Claim 1.
EP89911495A 1988-10-06 1989-10-03 Modified poly(ethylene 2,6-naphthalenedicarboxylate) having improved processability Pending EP0437496A1 (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US25433888A 1988-10-06 1988-10-06
US254338 1988-10-06

Publications (1)

Publication Number Publication Date
EP0437496A1 true EP0437496A1 (en) 1991-07-24

Family

ID=22963895

Family Applications (2)

Application Number Title Priority Date Filing Date
EP89911495A Pending EP0437496A1 (en) 1988-10-06 1989-10-03 Modified poly(ethylene 2,6-naphthalenedicarboxylate) having improved processability
EP89402716A Withdrawn EP0368690A1 (en) 1988-10-06 1989-10-03 Food container made from modified poly(ethylene 2,6-naphthalenedicarboxylate)

Family Applications After (1)

Application Number Title Priority Date Filing Date
EP89402716A Withdrawn EP0368690A1 (en) 1988-10-06 1989-10-03 Food container made from modified poly(ethylene 2,6-naphthalenedicarboxylate)

Country Status (4)

Country Link
EP (2) EP0437496A1 (en)
JP (1) JPH04500982A (en)
KR (1) KR900701890A (en)
WO (1) WO1990003993A1 (en)

Families Citing this family (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1992011740A1 (en) * 1990-12-20 1992-07-09 The Pillsbury Company Temperature controlled susceptor structure
IT1260591B (en) * 1991-07-18 1996-04-16 Donegani Guido Ist LOW SPEED POLYESTERS OF CRYSTALLIZATION AND PROCEDURE FOR THEIR PREPARATION.
JPH05230349A (en) * 1992-02-25 1993-09-07 Teijin Ltd Thermoplastic resin composition
US5731071A (en) * 1992-04-16 1998-03-24 Teijin Limited Biaxially oriented polyester film
JP2783914B2 (en) * 1992-04-16 1998-08-06 帝人株式会社 Biaxially oriented polyester film
US5912307A (en) * 1996-05-03 1999-06-15 Bp Amoco Corporation Polyester compositions
CN1101831C (en) * 1996-05-03 2003-02-19 阿莫科公司 Polyester compositions
EP1518877B1 (en) * 1997-07-25 2006-12-27 Eastman Chemical Company Large polyester containers and method for making same
US6309718B1 (en) 1997-07-25 2001-10-30 Eastman Chemical Company Large polyester containers and method for making same
AU738285B2 (en) * 1997-08-18 2001-09-13 Teijin Limited A copolyester for molding a bottle
WO1999021912A1 (en) * 1997-10-29 1999-05-06 Teijin Limited Biaxially oriented film
US6124423A (en) * 1998-07-02 2000-09-26 Shell Oil Company Process for crystallizing polyethylene naphthalate copolymers in the absence of devolatilization
US8012571B2 (en) 2008-05-02 2011-09-06 3M Innovative Properties Company Optical film comprising birefringent naphthalate copolyester having branched or cyclic C4-C10 alkyl units

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Publication number Priority date Publication date Assignee Title
JPS62136013A (en) * 1985-12-09 1987-06-19 ダイアホイルヘキスト株式会社 Polyethylene-2,6-naphthalate film for capacitor

Non-Patent Citations (1)

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Title
See references of WO9003993A1 *

Also Published As

Publication number Publication date
EP0368690A1 (en) 1990-05-16
KR900701890A (en) 1990-12-04
JPH04500982A (en) 1992-02-20
WO1990003993A1 (en) 1990-04-19

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