EP0671990A1 - Biaxially oriented copolyester film for capacitor dielectric use or thermal transfer ribbon use - Google Patents

Biaxially oriented copolyester film for capacitor dielectric use or thermal transfer ribbon use

Info

Publication number
EP0671990A1
EP0671990A1 EP93902640A EP93902640A EP0671990A1 EP 0671990 A1 EP0671990 A1 EP 0671990A1 EP 93902640 A EP93902640 A EP 93902640A EP 93902640 A EP93902640 A EP 93902640A EP 0671990 A1 EP0671990 A1 EP 0671990A1
Authority
EP
European Patent Office
Prior art keywords
film
biaxially oriented
bibenzoate
copolyester
penbb
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Withdrawn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
EP93902640A
Other languages
German (de)
English (en)
French (fr)
Other versions
EP0671990A4 (en
Inventor
Cynthia Dr. 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 EP0671990A4 publication Critical patent/EP0671990A4/en
Publication of EP0671990A1 publication Critical patent/EP0671990A1/en
Withdrawn legal-status Critical Current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
    • 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
    • B29C55/00—Shaping by stretching, e.g. drawing through a die; Apparatus therefor
    • B29C55/02—Shaping by stretching, e.g. drawing through a die; Apparatus therefor of plates or sheets
    • B29C55/10—Shaping by stretching, e.g. drawing through a die; Apparatus therefor of plates or sheets multiaxial
    • B29C55/12—Shaping by stretching, e.g. drawing through a die; Apparatus therefor of plates or sheets multiaxial biaxial
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29D—PRODUCING PARTICULAR ARTICLES FROM PLASTICS OR FROM SUBSTANCES IN A PLASTIC STATE
    • B29D7/00—Producing flat articles, e.g. films or sheets
    • B29D7/01—Films or sheets
    • 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
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/01—Use of inorganic substances as compounding ingredients characterized by their specific function
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
    • H01G4/00—Fixed capacitors; Processes of their manufacture
    • H01G4/002—Details
    • H01G4/018—Dielectrics
    • H01G4/06—Solid dielectrics
    • H01G4/14—Organic dielectrics
    • H01G4/18—Organic dielectrics of synthetic material, e.g. derivatives of cellulose
    • 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
    • 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
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K2201/00—Specific properties of additives
    • C08K2201/016—Additives defined by their aspect ratio

Definitions

  • This invention relates to a biaxially oriented PENBB copolyester film having low shrinkage properties and good thermal properties for use as a capacitor dielectric film or as a thermal transfer film.
  • the film of the present invention must have good winding characteristics as well as slipperiness to permit the film to slide over a previously wound section (i.e., to be non-blocking) .
  • the film of the present invention has good stiffness (tensile modulus) and mechanical strength and thus thickness reduction can be achieved to make the film of the present invention exceptionally useful as a capacitor dielectric or as a thermal transfer ribbon material.
  • a high melting point and low thermal shrinkage values are also desirable in thermal transfer ribbons, in order to allow high printing head temperatures without causing the sticking or distortion of the printing ribbon.
  • capacitor dielectric films Another desired characteristics of capacitor dielectric films is a low water pickup.
  • Low water pickup is important because this retards the degradation of the capacitor due to corrosion of the metallized layer.
  • a film water pickup at 23 ° C and 50 % r.h. of less than 0.1 weight percent and preferably less than 0.06 weight percent are possible.
  • thermoplastic polymeric film said to have usefulness as a material for capacitors and for thermal transfer ribbons.
  • the polymeric substrate can be polyester, polyphenylene sulfides, polyami- des, polysulfones, and polyvinylidene fluoride. While some of these polymers have good thermal characteristics, they are either very expensive to produce or have poor mechanical properties that limit their usefulness for capacitor films or thermal transfer ribbons.
  • U.S. Patent No. 3,008,934 discloses copolyesters containing as acid derived units 4,4'-bibenzoate and a host of other dicarboxyiates including 2,6- naphthalic dicarboxylate. It also discloses oriented fibers and films prepared from these copolyesters, however, biaxially oriented PENBB films are not disclosed or envisioned. In particular, those films with improved stiffness (tensile modulus) and tensile strength in both MD and TD as well as thermostability, UV stability, hydrophobicity, dimensional stability and impermeability toward gases in comparison to PET film are not disclosed in U .S. Patent No. 3,008,934. Japanese Patent No.
  • thermoplastic polymer having excellent thermal stability characteristics and having the requisite stiffness (tensile modulus) and mechanical strengths sufficient to permit those skilled in the art to produce a film capable of being employed as a capacitor film or as a thermal transfer film.
  • the present invention relates to a biaxially oriented PENBB copolyester film having at least about 25 mole-% of the diacid or derived content in the copolymer of 4,4'-bibenzoic acid or of 4,4'-dialkyl bibenzoate with the remainder of the copolyester being produced from a different diacid or diester.
  • the copolyester must have a melting point sufficient to permit the copolymer to withstand a solder batn such as those known in the capacitor dielectric manufacturing industry, i.e., the biaxially oriented copolyester film must not melt or shrink to a significant extent. With the present invention, shrinkages of less than 0.5 percent at 1 50 ° C are possible, preferably films having a shrinkage of less than 0.3 percent are possible.
  • a biaxially oriented PENBB copolyester film useful for capacitor dielectrics or thermal transfer printing ribbons must also have good winding characteristics, slipperiness, as well as the stiffness and mechanical strength to form an ultrathin film.
  • the reason thickness reduction of polymeric films employed for dielectric material in a capacitor is advantageous because the electrostatic capacitance of the capacitor is proportional to the dielectric constant of the dielectric material and inversely proportional to the square of the thickness of the film. If the dielectric material is constant, reducing the thickness of the film provides a very significant improvement in size reduction and capacitance increase for the manufactured capacitors.
  • the film In thermal transfer ribbon printing, the film must also be thin so that the printing head can be activated with a low energy in order to meet the needs of high speed printing. Moreover, a thickness reduction of the polymer film produces crisper letters and figures by permitting improved heat flow from the printing head to the transferred printing layer.
  • a bimodal particle distribution of filler material is employed to provide sufficient slip and good winding characteristics.
  • These particles may also be in the form of agglomerated fine particles which, upon blending with the polymer resin and subsequent film processing, break up into finely divided particles.
  • the present invention comprises a biaxially oriented copolyesterfilm useful for capacitor dielectric or thermal transfer printing ribbons, wherein the biaxially oriented copolyester film has at least 25 mole-% of the diacid derived content of the copolyester of 4,4'-bibenzoate units, and having a melt point sufficient to withstand a thermal treatment of at least about 260 ° C or higher for about 1 0 seconds; and incorporating into the copolyester an effective amount of one or more fillers having a bimodal particle distribution sufficient to provide slip and good winding characteristics.
  • Figure 1 is a graph showing the dependence of the melting point temperature of the preferred PENBB copolyester, polyethylene 2,6-napht- halate/4,4'-bibenzoate, on its molar diacid ratio.
  • the PENBB copolyesters of the present invention are made by reacting at least two dicarboxylic acids, or their ester equivalents with suitable glycols or diols, as is well known in the art. Such a reaction produces monomers or oligomers of the copolyester. The monomers or oligomers are then subject to a polycondensation reaction, as known in the art, to produce a copolyester.
  • the PENBB copolyester of the present invention is derived primarily from dicarboxylic acids or their ester equivalents with at least 25 mole percent of the dicarboxylic acid being 4,4'-bibenzoic acid (or the ester equivalent) having the following formula:
  • the remainder of the copolyester may be formed from other dicarboxylic acids or their ester equivalents, such as terephthalic acid, isophthalic acid, phthalic acid, naphthalene-2, 6-dicarboxylic acid, 1 ,4 cyclohexane dicarboxylic acid, di-(4-phenyl)-acetylene dicarboxylic acid; 1 ,2 di-(4-phenyl)-ethylene dicarboxylic acids, sebacic acid, malonic acid, adipic acid, azelaic acid, glutaric acid, suberic acid, succinic acid, and the like, or mixtures of these can be employed in the present invention.
  • Naphthalene-2,6-dicarboxylic acid is the preferred remainder diacid.
  • Suitable diols employed in the present invention include ethylene glycol, diethylene glycol, polypropylene glycol, butanediol, 1 ,5-pentanediol, 1 ,6- hexanediol, neopentyl glycol, 1 , 10-decanediol, cyclohexane dimethanol, and the like.
  • Ethylene glycol is the preferred glycol.
  • Suitable copolyesters of the present invention can comprise, for example, polyethylene terephthalate/4,4'-bibenzoate, polybutylene terephthalate/4,4'- bibenzoate, polypropylene terephthalate/4,4'-bibenzoate, polyethylene napht- halate/4,4'-bibenzoate, polyethyleneterephthalate/isophthalate/4,4'-bibenzoate, polyethylene terephthalate/adipate/4,4'-bibenzoate, polyethylene terepthalate/- sulphoisophthalate/4,4'-bibenzoate, and the like.
  • the IV value inherent viscosity, as measured in a 1 : 1 weight-ratio mixture of pentafluorophenol and hexafluoroi- sopropanol at a concentration of 0.2 g/dl and a temperature of 25 ° C
  • PENBB polymer after extrusion be > 0.5 dl/g and preferably > 0.55 dl/g.
  • a polyethylene naphthalate bibenzoate copolyester is made from equimolar portions of the esters 2, 6-dimethyl naphthalate and 4,4'-dimethyi bibenzoate, or the acids of naphthalene-2,6- dicarboxylic acid and 4,4'-bibenzoic acid .
  • the copolyester is obtained by polycondensation of the diacids or diesters with a diol. It may be advantageous, however, to employ an excessive amount of the diol in order to influence the reaction kinetics. After the reaction of the diacids or diesters with the diol, a polycondensation reaction is carried out according to known processes.
  • a mixture of two or more dicarboxylic acids/esters are mixed with at least 1 00 mole percent of the corresponding diol.
  • the diacids or their ester equivalents and the diols are mixed uniformly and heated to approximately 200 ° C in the presence of a transesterification catalyst, as is well known in the art.
  • the reaction yields oligomeric or low molecular weight polyester which is subsequently subjected to the polycondensation reaction in the presence of polycondensation catalyst.
  • stabilizers, antioxidants, delustrants, pigments, fillers, antistatic agents, etc. may be uniformly mixed with the copolyester.
  • Suitable catalysts are antimony, manganese, cobalt, magnesium, zinc, calcium, etc., as are well known in the art.
  • the preferred transesterification catalyst, where employed, would be manganese and/or cobalt.
  • the preferred polycondensation catalyst would be antimony compounds. Such catalysts are well known and conventional in the prior art.
  • the polyester film of the present invention can be manufactured by an extrusion process.
  • the polyester resin is first heated to a molten state and then extruded through a wide slot die in the form of an amorphous sheet onto a polished, revolving casting drum.
  • the amorphous sheet is rapidly cooled or "quenched” to form a cast sheet of polyester.
  • the cast polyester sheet is removed from the casting drum and then axially stretched in one direction, either in the direction of the film travel (machine direction) or perpendicular to the machine direction (transverse direction), while being heated to a temperature between the glass transition temperature and about 30 ° C above the cold crystallization temperature (both temperatures can easily be measured on the films by differential scanning colorimeter (DSC)).
  • DSC differential scanning colorimeter
  • the copolyester film is biaxially oriented (stretched in both the machine direction and the transverse direction).
  • the total stretch ratios in the machine direction and the transverse direction lie between 1 :2 and 1 : 10, preferably between 1 :2.5 and 1 : 5.
  • the product of the total stretch ratios should be between 1 to 30, and preferably between 5 to 20.
  • Biaxial drawing is performed such that the birefringeance is ⁇ 0.2, preferably ⁇ 0.1 to ensure adequately isotropic properties.
  • Birefringeance as mentioned herein is the absolute value of the difference between the maximum and minimum refractive indices in the plane of the film, as measured on common instruments such as Abbe refractometer, optical bench or compensators.
  • a heat setting step takes place to lock in the properties of the film.
  • the heat setting occurs at a temperature between the cold-crystallization temperature and the melt temperature of the copolymer composition.
  • the film may be wound on a roll, or in some cases surface treatment of the film such as corona treatment, plasma or flame treatment may be employed before winding the film on the roll, particularly where the film will be further coated with a primer coating or a metallic coating, for example.
  • the film it is desirable for the film to have a final total thickness of between 0.1 and 1 2 ⁇ m, preferably between 0.3 and 6 ⁇ m.
  • the capacitor incorporating the film thereof must be able to withstand a solder bath which is typically in the range of about 260 ° C for about 10 seconds.
  • Copolyesters which can survive this conditioning are thermally stable for the present invention.
  • Copolyesters of the present invention typically have a melting point dependent upon the composition.
  • Figure 1 illustrates a melting point curve based on a preferred composition of PENBB. Similar curves are also expected for other copolyesters of the present invention.
  • the film composition In order to provide good handling and winding properties, the film composition must be such that the surface is rough. This is achieved by incorporating fine inert insoluble particles ("filler”) into the film.
  • the fine inert insoluble particles can be in the form of an agglomerate which disperses or breaks up upon orientation of the film to form fine inert insoluble particles. Generally, these fine particles may be added, preferably to the monomers before or during polycondensation or to the polymer before extrusion.
  • Such inert fine particles either in agglomerated form or finely dispersed powders can be kaolin, talc, silica, carbonates of magnesium, calcium, or barium; sulfates of calcium, or barium; phosphates of lithium, calcium, or magnesium; oxides of aluminum, silicon, titanium, zirconium, or mixtures thereof, lithium fluoride, carbon black, or the organic acid salts of calcium, barium, zinc, and manganese. It is also possible to use fine particles made of crosslinked polymers such as polystyrene, polyacrylate, or polymethacrylate, for example, which are inert with respect to the reactions described herein to make the copolyester.
  • crosslinked polymers such as polystyrene, polyacrylate, or polymethacrylate
  • the particles may be of one type or mixtures of several types.
  • the shapes of the particles can be irregular, flaky, spherical, or elongated .
  • spherical particles are employed particularly for the large particles.
  • the hardness, density and color of the particles is generally immaterial.
  • the average size of the particle should be less than 1 0 ⁇ m, and generally preferably less than 3 ⁇ m as will be discussed later.
  • the amount of filler incorporated into the film should generally be in a range of from 0.01 % to 4 % by weight and preferably between 0.5 % and 2.0 % by weight, based on the weight of the polyester.
  • a bimodal particle dis ⁇ tribution i.e. particles of a large size distribution and particles of a small size distribution.
  • the bimodal particle distribution for the present invention comprises from about 0.01 to about 3 % by weight of inert particles based on the weight of the copolyester, and has an average particle diameter of 2 to 50 nm which optionally may be aggregates of the fine particles, said aggregates having an average particle diameter of 0.05 to 5 ⁇ m.
  • the other modal particle distribution consists of 0.005 to 1 % by weight, based on the weight of the copolyester, and has an average particle diameter of 0.05 to 4 ⁇ m and are preferably nearly spherical with an aspect ratio of from 1 .0 to 1 .2. (The aspect ratio of a particle is the ratio of the length of its longest axis to its shortest.)
  • the content of the fine inert particles should be in a range from 0.01 to 3 % by weight based on the weight of the copolyester. If the content is less than 0.01 % by weight, the excess air is trapped between the layers upon winding. On the other hand, if the fine particle mixture exceeds 3 % by weight, the film's surface is excessively roughened and the dielectric breakdown voltage of the film is decreased.
  • the larger particles are more spherical in shape and differ from the ultra fine lumpy particles. The larger particles have a particle size of about 0.5 ⁇ m and are present in a range of 0.005 to 1 % by weight, based on the weight of the copolyester.
  • the average particle diameter of the large particles is not larger than the thickness of the film.
  • the large particle diameters size is between about 0.2 and 3 ⁇ m. If the large particle size is less than 0.05 ⁇ m, the resulting film has insufficient slipperiness and suffers from processability. If it exceeds 4 ⁇ m in size, the surface of the film is excessively rough and the dielectric breakdown voltage is decreased and insulation defects increase.
  • the bimodal particle distribution described in the present invention is generally similar to that described in European Patent Application No. 423,402, as previously described . With the present invention, however, it is contemplated that a broader range (types) of inert particles can be employed for both the fine particle size and the large particle size.
  • EXAMPLE 1 289 parts by weight of dimethyl 2,6-naphthalene dicarboxylate, 322 parts by weight of dimethyl 4,4'-bibenzoate, 368 parts by weight of ethylene glycol and 0.7 parts of manganese acetate tetrahydrate are initially introduced into a conventional polycondensation reactor provided with a blanketing gas line (N 2 ), pressure equalization, a thermometer, a condenser, a vacuum connection and a stirrer. The mixture is heated at 220 ° C for 2.5 hours, during which time methanol is distilled off.
  • N 2 blanketing gas line
  • the IV value is 1 .1 dl/g.
  • T m melting point
  • Example 1 The polymer of Example 1 is heated to a molten state (about 305 ° C) in a twin screw mixing extruder ( 1000 g) and 6 g of a fine porous silica powder (0.6 percent by weight of the polymer) having an aspect ratio of 1 0 and an average particle diameter of 3 - 50 nm, is added to the molten polyester. Additionally, 3 g of a generally spherical silica powder (0.3 % by weight, based on the weight of the polymer) having an aspect ratio of 1 .1 and an average particle diameter of 0.05 to 4 ⁇ m is added to the molten polymer. After uniform mixing, the polymer is pelletized .
  • the pellets are then dried and fed into a single screw extruder and extruded on to a chilled casting drum and then biaxially oriented at 1 30 ° C by stretching 3.9 times in the MD and stretching 4.0 times in the TD.
  • the film is heatset at 260 ° C for 1 0 seconds.
  • the film has a final thickness of 3.5 ⁇ m.
  • the film produced in accordance with Example 2 has a surface roughness of about 1 1 0 nm; a shrinkage measured at 1 50 ° C in a forced air oven of about 0.3 percent in both the MD and TD; a slip of about 0.37/0.35 (static friction/- organic friction) according to ASTM D-1 894B-63; moisture absorption at 50 percent relative humidity at 23 ° C of 0.04 percent.

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  • Engineering & Computer Science (AREA)
  • Chemical & Material Sciences (AREA)
  • Manufacturing & Machinery (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Mechanical Engineering (AREA)
  • Power Engineering (AREA)
  • Materials Engineering (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Manufacture Of Macromolecular Shaped Articles (AREA)
EP93902640A 1992-12-09 1992-12-09 Biaxially oriented copolyester film for capacitor dielectric use or thermal transfer ribbon use Withdrawn EP0671990A1 (en)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
PCT/US1992/010710 WO1994013464A1 (en) 1992-12-09 1992-12-09 Biaxially oriented copolyester film for capacitor dielectric use or thermal transfer ribbon use

Publications (2)

Publication Number Publication Date
EP0671990A4 EP0671990A4 (en) 1995-08-01
EP0671990A1 true EP0671990A1 (en) 1995-09-20

Family

ID=22231624

Family Applications (1)

Application Number Title Priority Date Filing Date
EP93902640A Withdrawn EP0671990A1 (en) 1992-12-09 1992-12-09 Biaxially oriented copolyester film for capacitor dielectric use or thermal transfer ribbon use

Country Status (3)

Country Link
EP (1) EP0671990A1 (ja)
JP (1) JP2931850B2 (ja)
WO (1) WO1994013464A1 (ja)

Families Citing this family (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0770473B1 (de) * 1995-10-25 2001-04-11 Mitsubishi Polyester Film GmbH Polyesterfolie
KR101137214B1 (ko) 2003-08-19 2012-04-19 토요 보세키 가부시기가이샤 폴리에스테르 필름
EP1698664B1 (en) * 2003-12-22 2007-12-12 Denki Kagaku Kogyo Kabushiki Kaisha Curable resin composition
CN107108923B (zh) * 2014-12-24 2020-11-20 京瓷株式会社 介电膜、以及使用了其的薄膜电容器和连结型电容器、以及逆变器、电动车辆
JP6904809B2 (ja) * 2016-06-27 2021-07-21 京セラ株式会社 複合樹脂材料、誘電体フィルムと、これを用いたフィルムコンデンサおよび連結型コンデンサ、ならびにインバータ、電動車輌
CN109313959B (zh) * 2016-06-29 2021-05-25 京瓷株式会社 绝缘材料和布线部件

Citations (3)

* 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
EP0389385A1 (en) * 1989-02-27 1990-09-26 Eastman Chemical Company Copolyesters of 4,4'-biphenyldicarboxylic acid, 1,4-butanediol and ethylene glycol
EP0423402A1 (en) * 1988-04-19 1991-04-24 Teijin Limited Thermoplastic polymeric film

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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
US3714772A (en) * 1971-03-22 1973-02-06 Goodyear Tire & Rubber Polyamide in combination with polycarbonate, metal complex, polyisocyanating agent for polyester modification and rubber tire structures made therefrom
US3793132A (en) * 1972-02-23 1974-02-19 Goodyear Tire & Rubber Modified polyester and rubber structures made therefrom
JPS50135333A (ja) 1974-04-16 1975-10-27
US3991013A (en) * 1974-05-10 1976-11-09 E. I. Du Pont De Nemours And Company Copolyesters of derivatives of hydroquinone
JPS62245520A (ja) * 1986-04-16 1987-10-26 Diafoil Co Ltd 磁気記録媒体
JP2519300B2 (ja) * 1988-08-09 1996-07-31 ダイアホイルヘキスト株式会社 コンデンサ用二軸配向ポリエステルフィルム
US5069942A (en) * 1990-04-30 1991-12-03 E. I. Du Pont De Nemours And Company Process for improving adhesion of polysiloxane coatings to polymeric substrates via reduced alkali metal cation content

Patent Citations (3)

* 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
EP0423402A1 (en) * 1988-04-19 1991-04-24 Teijin Limited Thermoplastic polymeric film
EP0389385A1 (en) * 1989-02-27 1990-09-26 Eastman Chemical Company Copolyesters of 4,4'-biphenyldicarboxylic acid, 1,4-butanediol and ethylene glycol

Non-Patent Citations (3)

* Cited by examiner, † Cited by third party
Title
DATABASE WPI Section Ch, Week 9013 Derwent Publications Ltd., London, GB; Class A85, AN 90-096312 & JP-A-02 049 309 ( DIA FOIL KK) , 19 February 1990 *
PATENT ABSTRACTS OF JAPAN vol. 007 no. 037 (M-193) ,15 February 1983 & JP-A-57 189823 (TORAY KK) 22 November 1982, *
See also references of WO9413464A1 *

Also Published As

Publication number Publication date
WO1994013464A1 (en) 1994-06-23
JPH08505165A (ja) 1996-06-04
JP2931850B2 (ja) 1999-08-09
EP0671990A4 (en) 1995-08-01

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