WO1996006125A1 - Film en polyester thermofixe a etirage biaxial presentant une resistance accrue au retrait thermique - Google Patents

Film en polyester thermofixe a etirage biaxial presentant une resistance accrue au retrait thermique Download PDF

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Publication number
WO1996006125A1
WO1996006125A1 PCT/US1995/010206 US9510206W WO9606125A1 WO 1996006125 A1 WO1996006125 A1 WO 1996006125A1 US 9510206 W US9510206 W US 9510206W WO 9606125 A1 WO9606125 A1 WO 9606125A1
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WO
WIPO (PCT)
Prior art keywords
film
heat
stretching
pct
mol
Prior art date
Application number
PCT/US1995/010206
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English (en)
Inventor
David Earl Mills
Original Assignee
Eastman Chemical Company
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 Chemical Company filed Critical Eastman Chemical Company
Publication of WO1996006125A1 publication Critical patent/WO1996006125A1/fr

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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
    • C08G63/199—Acids or hydroxy compounds containing cycloaliphatic rings
    • 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
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K1/00—Printed circuits
    • H05K1/02—Details
    • H05K1/03—Use of materials for the substrate
    • H05K1/0313—Organic insulating material
    • H05K1/032—Organic insulating material consisting of one material
    • H05K1/0326—Organic insulating material consisting of one material containing O

Definitions

  • This invention relates to biaxially stretched, heat—set polyester film of poly(1,4—cyclohexylene— dimethylene terephthalate) (PCT) with improved thermal shrinkage resistance and a process for producing the film.
  • PCT poly(1,4—cyclohexylene— dimethylene terephthalate)
  • the process conditions described herein produce a film with significantly improved high temperature dimensional stability.
  • polyester films sometimes desirably have shrink capability.
  • polyester film may be used as a shrink—wrap material.
  • the film is applied to an object and heated so that the film shrinks around the object.
  • an object is to prepare a film having shrink resistance.
  • Shrink resistant films are often used, for example, in various applications such as flexible electronic circuits, heat resistant packaging, cooking bags, and any applications requiring dimensional stability at elevated temperatures.
  • the stretch ratio is limited to 2.5X as the maximum for good shrinkage resistance at high temperatures.
  • This film is useful for applications requiring a high end use temperature. It is particularly advantageous in applications requiring a clear, thermally stable film.
  • Typical end use temperatures for biaxially oriented, heat—set poly(ethylene terephthalate) (PET) films are 160 to 180°C.
  • the PCT films of this invention can be used at temperatures as high as 250 to 260°C.
  • An additional desirable property of these films is clarity. If the film is not stretched adequately, haze will be introduced during heat—setting.
  • the lower limit for stretching to produce haze—free films is about 2X in a simultaneous biaxial stretch.
  • PCT films would be expected to be more thermally stable than PET films. This is not necessarily the case.
  • PCT behaves differently than PET in that once the film is stretched beyond 2.5X, no amount of heat—setting (time or temperature) can anneal the internal stresses generated during the stretching process.
  • PET film which is stretched almost to its maximum before breaking can be heat—set to make it thermally stable up to about 200°C.
  • PCT cannot be made thermally stable once it is overstretched.
  • the critical process step in this invention addresses this problem.
  • Oriented PCT films are known to exhibit shrinkage upon heating. Thermal shrinkage limits the end use temperature of the film. For high temperature applications it is desirable to maximize the thermal stability. Heat—setting oriented film increases the temperature at which shrinkage occurs, but if the film is stretched too far, heat—setting does not give thermally stable films. In accordance with this invention, limiting stretch ratios to 2.5X or less, clear, thermally stable films are produced.
  • Biaxially oriented, heat—set PCT film has been previously disclosed, but using low stretch ratios for improving thermal shrinkage has not been disclosed.
  • Japanese Kokai No. JP1299019 (1980) discloses biaxially stretched, heat—set PCT films with improved dimensional stability, but they did not disclose any examples with stretch ratios less than 3.IX (MD) by 2.8X (TD) .
  • U.S. Patent No. 3,284,223 (1966) discloses biaxially oriented, heat—set films of an isophthalic acid modified PCT based copolyester. Although they claimed films from PCT homopoly er, they did not disclose any PCT homopolymer films. Furthermore, their process differed from this invention in that they used a highly asymmetric stretch of 4-5X (MD) by 1-1.25X (TD) .
  • U.S. Patent No. 2,901,466 discloses in Example 55, films of polyesters from cyclohexanedimethanol, terephthalic acid and isophthalic acid which are stretched in mutually perpendicular direction and heat set. The amount of stretching is not disclosed.
  • a biaxially stretched, heat—set film having improved resistance to thermal shrinkage comprising a polyester having repeat units from at least 90 mol % terephthalic acid and at least 90 mol % 1,4—cyclohexanedimethanol (CHDM) wherein the dimensions following biaxial stretching are between 2.0 and 2.5 times (2.0 and 2.5X) the dimensions prior to stretching.
  • CHDM cyclohexanedimethanol
  • a method of rendering a polyester film resistant to thermal shrinkage wherein the polyester has repeat units from at least 90 mol % terephthalic acid and at least 90 mol % 1,4—cyclohexanedimethanol, the method comprising biaxially stretching the film to dimensions of 2.0—2.5 times its dimensions prior to stretching, followed by subjecting the film to a temperature of 200 to 280°C, preferably 250 to 280°C, for a time of between 1 and 300 seconds to heat set the film.
  • the dicarboxylic acid portion of the polyesters and copolyesters from which the repeat units are derived and which are useful in this invention consists essentially of terephthalic acid.
  • the acid portion may be modified with up to about 10 mol % of other acids which may contain 3 to 20 carbon atoms and may consist of units of aromatic, aliphatic, or alicyclic dicarboxylic acids or combinations of these dicarboxylic acids.
  • Examples of useful aliphatic dicarboxylic acids are malonic, succinic, glutaric, adipic, pimelic, suberic, azelaic, sebacic, dodecanedioic, 1,4—, 1,5—, and 2,6—decahydro— naphthalenedicarboxylic acid, and cis— or trans—1,4—cyclohexanedicarboxylic acid.
  • aromatic dicarboxylic acids examples include terephthalic acid, isophthalic acid, 4,4'—biphenyldicarboxylic, trans 3,3'— and trans—4,4—stilbenedicarboxylie acid, 4,4'-dibenzyldicarboxylic acid, 1,4-, 1,5-, 2,3-, 2,6-, and 2,7—naphthalenedicarboxylie acid.
  • the cyclohexanedimethanol portion of the copolyester useful in this invention may be replaced with up to about 10 mol % of other aliphatic glycols, containing from about 2 to about 10 carbon atoms such as 1,3—propanediol, neopentyl glycol, 1,4—butanediol, 1,5—pentanediol or 1,6—hexanediol.
  • the cyclohexane dimethanol component is a cis—/trans—mixture of 1,4—cyclohexanedimethanol.
  • polyesters and copolyesters of the present invention are prepared by conventional polycondensation processes well known in the art, such as the process described in U.S. Patent 2,901,466 dated August 25, 1959. These include direct condensation of the acid(s) with the glycol(s) or by ester interchange using lower alkyl esters.
  • the inherent viscosity of the polyesters or copolyesters, components (a)—(d) , useful in the blends of the present invention may range from 0.5 to 1.3 dL/g, a preferred range being 0.6 to 0.8 dL/g, and a more preferred range being 0.65 to 0.75 dL/g as measured at 25°C in a solvent mixture consisting of 60% by weight phenol and 40% by weight tetrachloroethane.
  • the reaction is generally begun in the presence of an excess of the glycol and initially involves heating to a temperature sufficient to cause a preliminary condensation followed by the evaporation of excess glycol.
  • the entire reaction is conducted with agitation under an inert atmosphere.
  • the temperature can then be advantageously increased with or without the immediate application of a vacuum.
  • the 1,4—cyclohexanedimethanol employed can be used in the form of either of its isomers or a mixture thereof.
  • the 1,4—cyclohexanedimethanol or any of the other glycols can be employed as esters thereof (such as esters of a lower alkanoic acid) . However, it is generally advantageous to employ the free glycol.
  • the condensation reaction can be advantageously facilitated by the employment of a catalyst.
  • the best catalyst for each reaction is determined by the nature of the reactants. Generally, when an alkyl ester of the acidic compound is being employed, an ester interchange type of catalyst is to be preferred. Various techniques as to the use of the catalyst are well known in the art. For example, if the free acid is being reacted with the free glycol, a catalyst is generally not added until after the preliminary condensation is under way.
  • polyester It is sometimes desirable to include any various additives with the polyester mentioned above.
  • additives for example, titanium dioxide, granulated silica, kaolin, calcium carbonate, and other lubricants; antistatic agents; ultraviolet—light absorbants; pigments; dyes; plasticizers; stabilizers; etc.
  • compositions are formed into a film by any well-known method (such as extrusion, the calendar method, etc.)
  • shape of the film is not restricted in any way; for example, it can be a flat sheet or a tube.
  • the stretching method can be by any usual method.
  • this method for example, there are the roll stretching method, the long— ap stretching method, the tenter—stretching method, and the tubular stretching method.
  • biaxial stretching it is possible to do stretching in the machine direction and transverse direction at the same time; or the stretching can be done first in one direction and then in the other direction to result in effective biaxial stretching; stretching can be done first in either direction.
  • the film mentioned above is preliminarily heated at a temperature in the range of a mean glass transition temperature (T g ) of the polymer composition constituting the film to T g + 5°C to T g + 80°, preferably T g + 10°C to T g + 20°C.
  • T g mean glass transition temperature
  • the stretch rate is 5—20 in./sec.
  • Stretch ratio is defined as the draw ratio in the x—axis direction x the draw ratio in the y—axis direction.
  • the draw ratio is the final length of the film divided by the original length of the film.
  • This process restriction results in film that when subsequently heat—set is shrinkage resistant up to 260°C, depending on heat—setting conditions.
  • this invention comprises a similar process to that practiced in the art with the provision that the stretch ratio is limited to a maximum of 2.5X in either direction.
  • the process used to make the PCT films of this invention comprises 1) extruding the polymer into essentially amorphous sheet, 2) stretching the film at a temperature above the polymer glass transition, and
  • the polymer is extruded into amorphous sheet using methods generally known in the art.
  • the melt temperature is 300 to 340°C, preferably 305 to 315°C.
  • the roll temperature is 75 to 125°C, preferably 80 to 100°C.
  • the extruded sheet thickness can be in the range of 3 to 60 mil with the actual thickness dependent on the desired end use.
  • the essentially amorphous sheet is biaxially stretched.
  • the film may be either simultaneously or sequentially stretched in both machine (MD) and transverse (TD) directions.
  • MD machine
  • TD transverse
  • the preferred stretch ratio is 2.5X in both directions.
  • either MD or TD may be stretched first with the preferred ratio being 2 to 2.5X for the first stretch and 1.5 to 2.5X for the second stretch.
  • the film is maintained at a temperature of 105 to 150°C, preferably 110 to 140°C.
  • the film After stretching, the film is annealed or heat—set by heating it to a temperature of 180 to 285°C, preferably 240 to 280°C for up to 120 seconds, preferably 2 to 30 seconds. During the heat—setting process, the film dimensions can be held constant or allowed to shrink up to 5 percent.
  • polyester used has repeat units from 100 mol % terephthalic acid and 100 mol % CHDM.
  • the PCT resin had a crystalline melting point of 293°C, a glass transition of 92°C, and an inherent viscosity of 0.80 dl/g.
  • the extrusion die temperature is 300°C and the extrusion roll temperature is 80°C.
  • This amorphous sheet is subjected to various stretching and heat—setting conditions as described in the following examples.
  • the stretching step is carried out on a T. M. Long machine. Stretching is simultaneous in both machine and transverse directions at a rate of 13 in./sec. Stretched films are clamped in a frame and placed in a forced—air oven for heat—setting.
  • Thermal shrinkage resistance is measured as tensile heat deflection temperature (HDT) according to ASTM D1637. The test measures the temperature at which 2% deflection occurs under 50 psi stress and does not specify elongation or shrinkage. Except as noted, all deflections reported in these examples as HDT were shrinkage. All HDT measurements are reported as the average of machine direction and transverse direction. Clarity is measured either as transparency according to ASTM D1746 or as haze according to ASTM D1003.
  • HDT tensile heat deflection temperature
  • PCT film is stretched 2X by 2X at 130°C using a preheat time of 45 sec. After heat—setting at 250°C for 2 min, the biaxially oriented, heat—set PCT film has an HDT of 234°C.
  • PCT film is stretched 2.5X by 2.5X at 130°C using a preheat time of 45 sec. After heat—setting at 280°C for 2 min, the biaxially oriented, heat-set PCT film has an HDT of 265°C.
  • PCT film is stretched 2.5X by 2.5X at 130°C using a preheat time of 45 sec. After heat—setting at 250°C for 2 min, the biaxially oriented, heat-set PCT film has an HDT of 235°C and 1.3% haze. - 10 -
  • PET film is stretched 3X by 3X at 100°C using a preheat time of 45 sec. After heat—setting at 240°C for 2 min, the biaxially oriented, heat—set PET film has an HDT of 217°C and 0.7% haze.
  • PCT film is stretched 3X by 3X at 110°C using a preheat time of 45 sec. After heat—setting in two stages at 150°C for 2 min, followed by 200°C for 2 min the biaxially oriented, heat—set PCT film has an HDT of 140°C and 88% transparency.
  • PCT film is stretched 3X by 3X at 110°C using a preheat time of 45 sec. After heat—setting in two stages at 150°C for 2 min, followed by 250°C for 2 min the biaxially oriented, heat—set PCT film has an HDT of 168°C and 87% transparency.
  • PCT film is stretched 3X by 3X at 130°C using a preheat time of 45 sec. After heat—setting at 250°C for 2 min, the biaxially oriented, heat—set PCT film has an HDT of 175°C and 85% transparency.
  • PET film is stretched 2X by 2X at 100°C using a preheat time of 45 sec. After heat—setting at 220°C for 2 min, the biaxially oriented, heat—set PET film has a HDT of 195°C.
  • X as used herein, such as 2X and 2.5X, means the film is stretched that many times its dimensions prior to stretching.
  • 2X means that the film is stretched to a final elongation of 100%.
  • the film dimension in the stretching direction doubles in a 2X stretch.

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Materials Engineering (AREA)
  • Manufacture Of Macromolecular Shaped Articles (AREA)
  • Shaping By String And By Release Of Stress In Plastics And The Like (AREA)

Abstract

Film thermofixé à étirage biaxial présentant une résistance accrue au retrait thermique et son procédé de fabrication. Le film consiste en un polyester présentant des unités répétitives d'acide téréphtalique d'au moins 90 moles % et de 1,4-cyclohexanedimétanol d'au moins 90 moles % dont les dimensions après étirage sont de 2 à 2,5 fois celles avant étirage.
PCT/US1995/010206 1994-08-22 1995-08-11 Film en polyester thermofixe a etirage biaxial presentant une resistance accrue au retrait thermique WO1996006125A1 (fr)

Applications Claiming Priority (2)

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US29362794A 1994-08-22 1994-08-22
US08/293,627 1994-08-22

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WO1996006125A1 true WO1996006125A1 (fr) 1996-02-29

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Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2000038917A1 (fr) * 1998-12-23 2000-07-06 Polimoon As Recipient en plastique a double couche
WO2004003055A1 (fr) * 2002-06-26 2004-01-08 Eastman Chemical Company Film polyester oriente biaxialement et stratifies de celui-ci comprenant du cuivre
US7524920B2 (en) 2004-12-16 2009-04-28 Eastman Chemical Company Biaxially oriented copolyester film and laminates thereof
US9284108B2 (en) 2009-02-23 2016-03-15 Graphic Packaging International, Inc. Plasma treated susceptor films
US20170190903A1 (en) * 2015-11-24 2017-07-06 Eastman Chemical Company Polymer compositions and substrates for high temperature transparent conductive film applications
EP3800970A3 (fr) * 2019-09-24 2021-07-07 Jin Young Global Co., Ltd. Carte de circuit imprimé flexible (fpcb) utilisant un film pct en tant que couche isolante et son procédé de fabrication

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS57135118A (en) * 1981-02-16 1982-08-20 Teijin Ltd Manufacture of biaxially oriented polyester film
JPH02191638A (ja) * 1989-01-19 1990-07-27 Unitika Ltd ポリエステル２軸配向フイルム
EP0402861A2 (fr) * 1989-06-13 1990-12-19 Diafoil Hoechst Co., Ltd Film en polyester à basse rétraction
EP0483757A2 (fr) * 1990-10-29 1992-05-06 Diafoil Company, Limited Film de polyester pour condensateur
WO1992014771A1 (fr) * 1991-02-20 1992-09-03 Eastman Kodak Company Base de support en polyester pour films de projection cinematographique

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS57135118A (en) * 1981-02-16 1982-08-20 Teijin Ltd Manufacture of biaxially oriented polyester film
JPH02191638A (ja) * 1989-01-19 1990-07-27 Unitika Ltd ポリエステル２軸配向フイルム
EP0402861A2 (fr) * 1989-06-13 1990-12-19 Diafoil Hoechst Co., Ltd Film en polyester à basse rétraction
EP0483757A2 (fr) * 1990-10-29 1992-05-06 Diafoil Company, Limited Film de polyester pour condensateur
WO1992014771A1 (fr) * 1991-02-20 1992-09-03 Eastman Kodak Company Base de support en polyester pour films de projection cinematographique

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
DATABASE WPI Derwent World Patents Index; AN 82-82365E(39) *
DATABASE WPI Derwent World Patents Index; AN 90-271569(36) *

Cited By (15)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2000038917A1 (fr) * 1998-12-23 2000-07-06 Polimoon As Recipient en plastique a double couche
KR100980518B1 (ko) * 2002-06-26 2010-09-06 이스트만 케미칼 컴파니 이축 배향 폴리에스터 필름 및 구리를 갖는 이것의 적층물
JP2015178623A (ja) * 2002-06-26 2015-10-08 イーストマン ケミカル カンパニー 二軸配向ポリエステルフィルム及びそれらの銅との積層板
US7147927B2 (en) 2002-06-26 2006-12-12 Eastman Chemical Company Biaxially oriented polyester film and laminates thereof with copper
CN100357338C (zh) * 2002-06-26 2007-12-26 伊斯曼化学公司 双轴取向的聚酯薄膜和它与铜形成的层压板
JP2005530908A (ja) * 2002-06-26 2005-10-13 イーストマン ケミカル カンパニー 二軸配向ポリエステルフィルム及びそれらの銅との積層板
WO2004003055A1 (fr) * 2002-06-26 2004-01-08 Eastman Chemical Company Film polyester oriente biaxialement et stratifies de celui-ci comprenant du cuivre
JP2012246485A (ja) * 2002-06-26 2012-12-13 Eastman Chemical Co 二軸配向ポリエステルフィルム及びそれらの銅との積層板
US7524920B2 (en) 2004-12-16 2009-04-28 Eastman Chemical Company Biaxially oriented copolyester film and laminates thereof
US9284108B2 (en) 2009-02-23 2016-03-15 Graphic Packaging International, Inc. Plasma treated susceptor films
US20170190903A1 (en) * 2015-11-24 2017-07-06 Eastman Chemical Company Polymer compositions and substrates for high temperature transparent conductive film applications
CN108350257A (zh) * 2015-11-24 2018-07-31 伊士曼化工公司 用于高温透明导电膜应用的聚合物组合物和基板
US10767041B2 (en) 2015-11-24 2020-09-08 Eastman Chemical Company Polymer compositions and substrates for high temperature transparent conductive film applications
CN108350257B (zh) * 2015-11-24 2021-06-15 伊士曼化工公司 用于高温透明导电膜应用的聚合物组合物和基板
EP3800970A3 (fr) * 2019-09-24 2021-07-07 Jin Young Global Co., Ltd. Carte de circuit imprimé flexible (fpcb) utilisant un film pct en tant que couche isolante et son procédé de fabrication

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