EP0674589A4 - Isolation electrique fabriquee a partir d'un film de penbb oriente biaxialement. - Google Patents

Isolation electrique fabriquee a partir d'un film de penbb oriente biaxialement.

Info

Publication number
EP0674589A4
EP0674589A4 EP93900182A EP93900182A EP0674589A4 EP 0674589 A4 EP0674589 A4 EP 0674589A4 EP 93900182 A EP93900182 A EP 93900182A EP 93900182 A EP93900182 A EP 93900182A EP 0674589 A4 EP0674589 A4 EP 0674589A4
Authority
EP
European Patent Office
Prior art keywords
biaxially oriented
penbb
film
film according
inert particles
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.)
Withdrawn
Application number
EP93900182A
Other languages
German (de)
English (en)
Other versions
EP0674589A1 (fr
Inventor
Cynthia Bennett
E-Won Choe
John Anthony Flint
Bodo Kuhmann
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.)
Mitsubishi Polyester Film GmbH
Original Assignee
Hoechst AG
Hoechst Celanese Corp
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 Hoechst AG, Hoechst Celanese Corp filed Critical Hoechst AG
Publication of EP0674589A1 publication Critical patent/EP0674589A1/fr
Publication of EP0674589A4 publication Critical patent/EP0674589A4/fr
Withdrawn legal-status Critical Current

Links

Classifications

    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08JWORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/18Manufacture of films or sheets
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B29WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29DPRODUCING PARTICULAR ARTICLES FROM PLASTICS OR FROM SUBSTANCES IN A PLASTIC STATE
    • B29D7/00Producing flat articles, e.g. films or sheets
    • B29D7/01Films or sheets
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08GMACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G63/00Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
    • C08G63/02Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
    • C08G63/12Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from polycarboxylic acids and polyhydroxy compounds
    • C08G63/16Dicarboxylic acids and dihydroxy compounds
    • C08G63/18Dicarboxylic acids and dihydroxy compounds the acids or hydroxy compounds containing carbocyclic rings
    • C08G63/181Acids containing aromatic rings
    • C08G63/185Acids containing aromatic rings containing two or more aromatic rings
    • C08G63/187Acids containing aromatic rings containing two or more aromatic rings containing condensed aromatic rings
    • C08G63/189Acids containing aromatic rings containing two or more aromatic rings containing condensed aromatic rings containing a naphthalene ring
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08KUse of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00Use of inorganic substances as compounding ingredients
    • C08K3/01Use of inorganic substances as compounding ingredients characterized by their specific function
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08KUse of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K7/00Use of ingredients characterised by shape
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B29WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29CSHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C55/00Shaping by stretching, e.g. drawing through a die; Apparatus therefor
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B29WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29KINDEXING 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
    • B29K2067/00Use of polyesters or derivatives thereof, as moulding material
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B29WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29KINDEXING 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
    • B29K2105/00Condition, form or state of moulded material or of the material to be shaped
    • B29K2105/06Condition, form or state of moulded material or of the material to be shaped containing reinforcements, fillers or inserts
    • B29K2105/16Fillers
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08JWORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2367/00Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
    • C08J2367/02Polyesters derived from dicarboxylic acids and dihydroxy compounds
    • HELECTRICITY
    • H05ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05KPRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K1/00Printed circuits
    • H05K1/02Details
    • H05K1/03Use of materials for the substrate
    • H05K1/0313Organic insulating material
    • H05K1/0353Organic insulating material consisting of two or more materials, e.g. two or more polymers, polymer + filler, + reinforcement
    • H05K1/0373Organic insulating material consisting of two or more materials, e.g. two or more polymers, polymer + filler, + reinforcement containing additives, e.g. fillers

Definitions

  • Flexible polymeric films have proved to be of great value as insulating films in electrical equipment and machinery.
  • biaxially oriented poly ethylene terephalate films are useful in transformer insulation, motor generato insulation, wire and cable insulation and as insulating supports for flexible circuits.
  • high stiffness and strengths including resistance to cut-through are important.
  • these applications require property retention after exposure to elevated temperatures.
  • the manufacturing process requires resistance to soldering melt temperatures found in the wave soldering process.
  • Motors, generators, transformers, and wire and cable may also be used where long term (years) of exposure to high humidities (and temperatures) may be a problem. Good hydrolytic stability is necessary. Design of equipment is limited by the present property combination of current materials.
  • the resent invention provides a biaxially oriented film of PENBB co- polyester with excellent stiffness, high temperature strength, dimensional stability, and hydrolysis resistance for use as electrical insulation.
  • biaxial oriented, heat set films made from PENBB copolyester resin exhibit greater stiffness, strength and higher melting point than films made from polyethylene terephtalate.
  • this film has improved hydrolytic stability.
  • Such improvements are important to the use of film in electrical insulation applications where high temperatures or humidities may be experienced over long periods of time.
  • Such uses might include transformer insulation, motor and generator insulation, flexible circuit substrate, and the ' .ke.
  • PENBB as used herein refers to a copolyester containing acid-derived knit of which at least 25 mole % are of the formula:
  • the bibenzoate units comprise 40 - 60 mole % of the aci derived units of the copolyester, and at least 80 mole .
  • ⁇ of the diol-derived unit are -O-(CH 2 ) 2 -O- (ethylene glycol units) .
  • the remaining acid-derived units of thi copolymer are preferably of the formula:
  • U.S. Patent No. 3,008,934 discloses copolyesters containing as aci derived units 4,4'-bibenzoate and a host of other dicarboxylates including 2, naphthalic dicarboxylate. It also discloses oriented fibers and films prepared fro these copolyesters, however, biaxially oriented PENBB films are not disclosed envisioned . In particular, those films with improved stiffness (tensile modulu and tensile strength in both MD and TD as well as thermostability, UV stabilit hydrophobicity, dimensional stability and impermeability toward gases i comparison to PET film are not disclosed in U.S. Patent No. 3,008,934.
  • the copolyester is obtained by polycondensation of the correspondin diacid or lower dialkyl diester and the corresponding diol. Both component should preferably be employed in roughly equimolar ratios. It may however b advantageous to employ one of the components - especially the diol - in exces for instance in order to influence the reaction kinetics or to serve as a solven
  • the polycondensation is carried out according to known processes used e g.
  • PET polyethylene terephthalate
  • dicarboxylic acid or dialkyldicarboxylate mixture usually about 1 00 mole- % of the dicarboxylic acid or dialkyldicarboxylate mixture are mixed with > 1 0 mole-% of the corresponding d ⁇ ol(s), in the presence of a transeste ⁇ ficatio catalyst, and heated until sufficient lower alkyl alcohol or water has bee removed from the mixture via distillation
  • This reaction yields an oligomer or low molecular weight polyester, which is subsequently subjected to polyconden sation, preferably in the presence of a stabilizer and/or catalyst.
  • Useful stabilizers and catalysts can be polyphosphates, t ⁇ organyi phosphates, antimony t ⁇ oxide or tetraalkoxy titanate (IV) or mixtures of t ⁇ phenylphosphate and antimony t ⁇ oxide
  • a preferred process for the production of such copolyester is described in U S Patent Application Ser No. 07/735, 553 which is incorpora ted herein by reference
  • a further increase in molecular weight can be achieved by solid phase polycondensation at a temperature just below the melting poin under vacuum, or a stream of dry air or inert gas.
  • the IV value inherent viscosity, a measured in a 1 A weight-ratio mixture of pentafluorophenol and hexafluoroi sopropanol at a concentration of 0.2 g/dl and a temperature of 25 ° C
  • the IV value of the PENBB polymer after extrusion be > 0.5 dl/g and preferably > 0.55 dl/g.
  • the film composition In order to provide good handling and winding properties the film composition must be such that the surface is rough. This can be achieved b incorporating fine inert insoluble particles into the film
  • inert particulates in situ by reactin the metal salt transeste ⁇ fication catalyst with phosphoric acid derivatives in th course of the polycondensation step, which causes fine particulate matter t precipitate in the polymer
  • Another method is the addition of fine particles to th monomers before or during polycondensation or to the polymer before extrusion
  • Such inert fine particles can be kaolin, talc, silica, carbonates of magnesium calcium or barium, sulphates of calcium or barium phosphates of lithium, calciu or magnesium, titanium oxide, lithium fluoride, carbon black and the organic aci salts of calcium, barium, zinc and manganese. It is also possible to use fin particles made of cross-linked polymers.
  • the particles may be of one type o mixtures of several types.
  • the shape of the particles can be irregular, flaky spherical or elongated .
  • the hardness, density and the color of the particles i immaterial.
  • the average size of the particles should be less than 10 ⁇ preferably less than 3 ⁇ m.
  • the amount incorporated in the film should in th range of 0.01 % to 2.00 % (by weight), preferably between 0.05 % and 0.8 (by weight) .
  • common additives such as flame retarda ⁇ ts, anti-oxidants etc. may be incorpor ted in the composition.
  • the polymer melt is extruded through a die onto a chi roll where it solidifies, is then biaxially oriented, heat set, optionally post treate and wound on a roll.
  • a multi layer film known methods for coextrusion, in-lin or off-line coating can be used .
  • the solidified film as extruded on the chill ro should be obtained in an essentially amorphous state.
  • the mel film must be pinned to the chill roll by a known method such as electrostati pinning or vacuum, air knife or the like.
  • the biaxial orientation of the film is achieved by stretching the film a elevated temperature in the machine (MD) and traverse direction (TD) . Thi stretching can be either simultaneous or sequential.
  • the first stretching step can be in either MD or TD, followed b stretching in the perpendicular direction.
  • the orientation in MD can also b achieved in several steps, either one after another prior to stretching in TD, o before and after the TD stretching.
  • Preferred temperatures for stretching li between the glass transition temperature and about 30°C above the col crystallization temperature of the PENBB copolymer composition in use (bot temperatures can easily be measured on amorphous films by DSC) .
  • the tot stretch ratios (/.) in MD and TD lie between 1 : 2 and 1 : 1 0, preferably betwee 1 : 2.5 and 1 : 5.
  • the product of the total stretch ratios should be between 1 to 30 preferably between 5 to 20.
  • the heat setting takes place at a temperature between the cold crystalliza- tion temperature and the melt temperature of the copolymer composition.
  • the copolyester film for electrical insulation is preferably coated with a primer or surface treated via known methods such as corona, plasma, or flame treatment to improve adhesion to other sheet-like materials such as fiber sheet it might be laminated to or to impregnation resins in insulation applications.
  • the film contains up to 5 % inert, opaque, white or colored fillers that render the film opaque, which makes the completed insertion of the slot liner in motor or generator manufacture visually apparent.
  • Films according to the present invention used for electrical insulation application typically are about 75-350 ⁇ m thick. In flexible printed circuit applications, a film thickness of about 25-1 50 ⁇ m is typically suitable. A thickness of about 1 5-75 ⁇ m maybe preferable for cable and/or transformer applications. For membrane switches or touch panels, film 20-300 ⁇ m thick may be needed.
  • the melt is granulated.
  • the granules are white, opaque and crystalline
  • An IV value of 0.56 dl/g is determined for the granules (measured at a concen tration of 0.1 g/ml in pentafluorophenol/Heyaf luoroisopropanol [weight ratio 1 : 1 at 25 °C) .
  • the granules are further condensed for 20 hours at 240 ° C under vacuu in the solid phase. After this treatment the IV value is 1 .1 dl/g. The meltin point (TJ is 281 °C.
  • the PENBB granules are melted in a single screw extruder at temperature of 280 - 320 °C and extruded through a sheet dye onto a cooling roll temperatu re controlled at 30 °C.
  • amorphous film is obtained which is clear and transparent.
  • This PENB prefilm is then sequentially biaxially oriented (first transversely, then longitudinal ly: 3.5x3.5) at 1 30 °C on a film stretching device .
  • a strong clear film i obtained .
  • the film is finally heat treated at 260 ° C for 1 0 minutes.
  • the annealed biaxially oriented PENBB film produced as above has th following mechanical properties
  • This film has a thermal shrinkage of 0.3% in the MD and TD directio when heated for 1 5 minutes at 1 50°C.
  • EXAMPLE 2 The dielectric properties of the biaxially oriented film in Example 1 ar measured in comparison to standard commercial PET at 1 kHz, and 50% r.h. :
  • biaxially oriented PENBB films according to th invention are superior over common biaxially oriented PET films. laims

Landscapes

  • 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)
  • Mechanical Engineering (AREA)
  • Insulating Bodies (AREA)
  • Organic Insulating Materials (AREA)
  • Manufacture Of Macromolecular Shaped Articles (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

L'invention concerne un film de copolyester orienté biaxialement contenant des particules inertes, ledit copolyester étant du PENBB et les particules inertes étant soit produites in situ et ajoutées aux monomères avant ou après la polycondensation, soit ajoutées au PENBB avant le procédé de formage du film. Selon les applications, ce film peut présenter différentes épaisseurs, contenir une substance pigmentaire et/ou peut être enduit ou traité en surface. Le PENBB selon l'invention est un copolyester contenant des unités représentées par la formule (I).
EP93900182A 1992-12-09 1992-12-09 Isolation electrique fabriquee a partir d'un film de penbb oriente biaxialement. Withdrawn EP0674589A4 (fr)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
PCT/US1992/010713 WO1994013485A1 (fr) 1992-12-09 1992-12-09 Isolation electrique fabriquee a partir d'un film de penbb oriente biaxialement

Publications (2)

Publication Number Publication Date
EP0674589A1 EP0674589A1 (fr) 1995-10-04
EP0674589A4 true EP0674589A4 (fr) 1996-02-28

Family

ID=22231627

Family Applications (1)

Application Number Title Priority Date Filing Date
EP93900182A Withdrawn EP0674589A4 (fr) 1992-12-09 1992-12-09 Isolation electrique fabriquee a partir d'un film de penbb oriente biaxialement.

Country Status (3)

Country Link
EP (1) EP0674589A4 (fr)
JP (1) JPH08504469A (fr)
WO (1) WO1994013485A1 (fr)

Families Citing this family (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE10110432A1 (de) * 2001-03-05 2002-09-19 Mitsubishi Polyester Film Gmbh Amorphe, gedeckt eingefärbte Folie aus einem bibenzolmodifizierten Thermoplasten, Verfahren zu ihrer Herstellung und ihre Verwendung
CN103753920B (zh) * 2013-12-27 2015-11-25 四川东方绝缘材料股份有限公司 多层共挤双向拉伸光反射聚酯薄膜及其制造方法
US20180044507A1 (en) * 2015-03-05 2018-02-15 Toray Industries, Inc. Polyester film and electrical insulation sheet manufactured using same, wind power generator, and adhesive tape
JP6699659B2 (ja) * 2016-03-31 2020-05-27 東レ株式会社 フィルムおよびそれを用いた電気絶縁シート、粘着テープ、回転機
CN109834960A (zh) * 2019-02-15 2019-06-04 柔电(武汉)科技有限公司 一种碳纳米管膜及其制备方法

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3008934A (en) * 1958-07-28 1961-11-14 American Viscose Corp Filament and film forming interpolyesters of bibenzoic acid, certain aromatic acids and a dihydric alcohol
EP0580093A1 (fr) * 1992-07-22 1994-01-26 Hoechst Aktiengesellschaft Feuille mince selon un double axe contenant des couches de polyéthylènenaphtalatebibenzoate (PENBB), procédé de préparation de ces feuilles et utilisation de celles-ci

Family Cites Families (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS57189823A (en) * 1981-05-20 1982-11-22 Toray Ind Inc Production of polyester film
EP0088635B1 (fr) * 1982-03-10 1986-12-30 Toray Industries, Inc. Film laminé et milieu d'enregistrement magnétique fabriqué avec ce film
US4539389A (en) * 1983-03-30 1985-09-03 Teijin Limited Biaxially oriented polyester film
US4833024A (en) * 1987-04-03 1989-05-23 W. R. Grace & Co. Low shrink energy films
JP2856283B2 (ja) * 1989-06-02 1999-02-10 三菱化学ポリエステルフィルム株式会社 二軸配向ポリエステルフィルム

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3008934A (en) * 1958-07-28 1961-11-14 American Viscose Corp Filament and film forming interpolyesters of bibenzoic acid, certain aromatic acids and a dihydric alcohol
EP0580093A1 (fr) * 1992-07-22 1994-01-26 Hoechst Aktiengesellschaft Feuille mince selon un double axe contenant des couches de polyéthylènenaphtalatebibenzoate (PENBB), procédé de préparation de ces feuilles et utilisation de celles-ci

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See also references of WO9413485A1 *

Also Published As

Publication number Publication date
EP0674589A1 (fr) 1995-10-04
WO1994013485A1 (fr) 1994-06-23
JPH08504469A (ja) 1996-05-14

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