WO1994013481A1 - Film de copolyester oriente biaxialement revetu d'une premiere couche de polymeres d'acetate de vinyle - Google Patents

Film de copolyester oriente biaxialement revetu d'une premiere couche de polymeres d'acetate de vinyle Download PDF

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Publication number
WO1994013481A1
WO1994013481A1 PCT/US1992/010685 US9210685W WO9413481A1 WO 1994013481 A1 WO1994013481 A1 WO 1994013481A1 US 9210685 W US9210685 W US 9210685W WO 9413481 A1 WO9413481 A1 WO 9413481A1
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WO
WIPO (PCT)
Prior art keywords
film
biaxially oriented
primer
film according
coating
Prior art date
Application number
PCT/US1992/010685
Other languages
English (en)
Inventor
Cynthia Bennett
E-Won Choe
John Anthony Flint
Bodo Kuhmann
Original Assignee
Hoechst Aktiengesellschaft
Hoechst Celanese Corporation
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 Aktiengesellschaft, Hoechst Celanese Corporation filed Critical Hoechst Aktiengesellschaft
Priority to PCT/US1992/010685 priority Critical patent/WO1994013481A1/fr
Priority to EP93901009A priority patent/EP0674591A4/fr
Publication of WO1994013481A1 publication Critical patent/WO1994013481A1/fr

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Classifications

    • 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
    • B29C55/023—Shaping by stretching, e.g. drawing through a die; Apparatus therefor of plates or sheets using multilayered plates or sheets
    • B29C55/026—Shaping by stretching, e.g. drawing through a die; Apparatus therefor of plates or sheets using multilayered plates or sheets of preformed plates or sheets coated with a solution, a dispersion or a melt of thermoplastic material
    • 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
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
    • C08J7/04—Coating
    • C08J7/0427—Coating with only one layer of a composition containing a polymer binder
    • 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
    • C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
    • C08J7/04—Coating
    • C08J7/043—Improving the adhesiveness of the coatings per se, e.g. forming primers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2367/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
    • C08J2367/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2431/00—Characterised by the use of copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an acyloxy radical of a saturated carboxylic acid, or carbonic acid, or of a haloformic acid

Definitions

  • the present invention relates to biaxially oriented copolyester film coated on one or both sides with vinyl acetate polymers which render the copolyester film surface receptive to additional reprographic or matte coatings applied thereto, and to film containing the reclamation product of such coated film.
  • Polyester films particularly biaxially oriented film composed of polyethylene terephthalate (PET) are widely used as a base for drafting film, photographic film, and reprographic film, as well as for packaging and labeling applications.
  • Polyester films, especially PET films have disadvantages which still need to be overcome, e.g., UV resistance, dimensional stability, heat stabili ⁇ ty, and hydrolysis resistance are still poor.
  • PET film is hydrophobic and is not readily receptive to coating in most applications where the film is to serve as a base or support for other coatings, and must therefore be first coated on one or both sides with a primer coating which adheres to the film and is receptive as well to other coatings applied to it.
  • 2,627,088 and 2,698,240 teach a primer coating for PET film comprising a terpolymer composition of vinylidene chloride, acrylic ester and itaconic acid.
  • This primer layer is said to have excellent adhesion to the polyester surface and to water or alcohol based photographic gelatin layers subsequently coated thereon.
  • PET film primer includes copoiymers of a vinyl haloge- noester, such as vinyl chloroacetate which may be copoiymerized with numerous different monomers such as acrylic and methacrylic acids, esters and amides, olefins and vinyl alcohols as disclosed in U.S. Patent No.
  • Such copoiymers may also be crosslinked by the inclusion of melamine or urea formaldehyde resins in the composition.
  • the primed PET film is stated to exhibit enhanced adhesion to a variety of coatings applied thereto, including reprographic coatings.
  • thermoset, acrylic or methacrylic coatings taught in U.S. Patent No. 3,819,773, which can be applied to the PET film from aqueous medium.
  • a primer layer enhances the adhesion of organic solvent based reprographic and drafting layers applied thereto and also the heat sealability.
  • British Patent No. B 1 ,127,076 teaches the application to PET film of a primer layer which may comprise an aqueous latex of non-crosslinked polyvinyl acetate. The patent indicates that such primer layers render the film heat-sealable.
  • British Patent No. 1 ,146,215 teaches the application to PET film of a primer coating comprising an aqueous dispersion of a copolymer of vinyl acetate (100 parts), alkyl methacrylate (10 parts) and itaconic acid (6 parts). The patent indicates that the primer provides enhanced adhesion to aqueous based gelatin photographic emulsions, but does not indicate that organic solvent based coatings may be successfully applied thereto.
  • 3,674,531 discloses the application to PET film of a primer layer comprising a copolymer of a vinyl halogenoester, such as vinyl chloroacetate, which may be copolymerized with numerous different monomers such as acrylic and methacrylic acids, esters and amides, olefins and vinyl alcohol.
  • This copolymer may also be crosslinked such as by the inclusion of a melami- ne or urea formaldehyde crosslinking agent.
  • the primed PET film is stated to exhibit enhanced adhesion to a variety of coatings applied thereto, including reprographic coatings.
  • 3,624,021 discloses a matte coating composition for PET film based on a mixture of a vinyl acetate/crotonic acid copolymer and an excess of a urea formaldehyde resin which presumably crosslinks upon the application of heat.
  • British Patent 1 ,497,657 discloses a similar primer coating for PET film which is based on a mixture of an unhy- drolysed polymer or copolymer of vinyl acetate and one or more synthetic resins capable of intra-molecular crosslinking, such as a melamine formalde ⁇ hyde resin.
  • the patent indicates that the primer layer may serve, inter alia, as an anchor layer for the application of further coatings, such as light-sensiti ⁇ ve layers.
  • U.S. Pat. No. 3,720,539 discloses a primer coating system for polye ⁇ ster film comprising a first undercoat based on a composition containing a polyacryiamide or polyvinyl alcohol polymer and having applied over such undercoat a coating comprising a mixture of polyvinyl acetate and a melami- ne/formaldehyde resin.
  • this system adheres well to the film, it is a complicated formulation involving two coating steps and also includes materi ⁇ als such as trichloroacetic acid which are not especially desirable in such coating formulations.
  • British Patent No. 1 , 168, 171 teaches the application to PET film of a primer layer described as a curable copolymer of an unsaturated aliphatic acid and at least one other ethylenically unsaturated monomer.
  • the patent indica ⁇ tes that such a primer coating enhances adhesion to aqueous based gelatin photographic emulsions, but does not indicate that organic solvent based coatings may be successfully applied thereto.
  • This patent also discloses that film primed with the vinyl acetate coatings described therein may be reclai ⁇ med in the film forming extruder by mixing it with 50 percent by weight or more of virgin polyester and refeeding the mixture to the film-forming ex ⁇ truder.
  • a primer coated biaxially oriented self- supporting mono- or multilayer copolyester film wherein the copolyester is PENBB and wherein the primer coating contains a vinyl acetate polymer provides excellent UV resistance, good dimensional stability, heat stability and hydrolysis resistance, lower moisture absorption, improved stiffness (tensile modulus) and tensile strength, while providing excellent adhesion to many organic solvent based coatings subsequently applied thereto, and reclai- mability when reprocessed during the manufacture of the PENBB film without giving rise to hardly any appreciable degradation of the film.
  • U.S. Patent No. 3,008,934 discloses copolyesters containing as acid derived units 4,4'-bibenzoate and a host of other dicarboxylates including 2,6-naphthalic dicarboxylate. It also discloses oriented fibers and films prepa ⁇ red 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 thermo- stability, 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.
  • PENBB as mentioned hereinbefore is a copolyester containing as acid- derived unit at least 5 mole percent of a radical of the formula
  • PENBB is a copolyester wherein at least 80 mole percent of the acid derived units (NBB) consist of bibenzoate (20 to 80 mole percent, preferably 40 to 60 mole percent) and naphthalate (80 to 20 mole percent, preferably 60 to 40 mole percent). The remaining 20 or less mole percent may consist of other acid derived units, which e.g. affect the melting point or the crystallization kinetics.
  • NNBB acid derived units
  • naphthalate 80 to 20 mole percent, preferably 60 to 40 mole percent
  • the remaining 20 or less mole percent may consist of other acid derived units, which e.g. affect the melting point or the crystallization kinetics.
  • at least 80 mole percent of the diol-derived units consist of -O(CH 2 ) 2 -O-units. The remaining
  • 20 or less mole percent consist of other diol-derived units, which e.g. may also affect the melting point or the crystallization kinetics. It may also be desirable to replace minor amounts of the acid- and/or diol-derived units with hydroxycarboxylic-acid-derived units, e.g. such derived from p-hydroxyben- zoic acid.
  • the polymer melt is extruded through a die onto a chill roll where it solidifies, is then biaxially oriented, heat set, optionally post treated and wound on a roll.
  • the IV value inherent viscosity, as measured in a 1 : 1 weight-ratio mixture of pentafluorophenoi and hexafluoroisopropanol 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.
  • in-line or off-line coating can be used.
  • the solidified film as extruded on the chill roll should be obtained in a essentially amorphous state.
  • the melt film must be pinned to the chill roll by a known method such as electrostatic pinning or vacuum, air knife or the like.
  • the biaxial orientation of the film is achieved by stretching the film at elevated temperature in the machine (MD) and transverse direction (TD).
  • This stretching can be either simultaneous or sequential.
  • the first stretching step can be in either MD or TD, followed by stretching in the other direction.
  • the orientation in MD can also be achieved in several steps, either one after another prior to stretching in TD, or before and after the TD stretching.
  • Preferred temperatures for stretching lie bet ⁇ ween the glass transition temperature and about 30 "C above the cold cry ⁇ stallization temperature of the PENBB copolymer composition in use (both temperatures can easily be measured on amorphous films by DSC).
  • the total stretch ratios ( ⁇ ) in MD and TD 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 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.
  • relaxation steps can be included in the orientation and heat setting processes.
  • the heat setting takes place at a temperature between the cold crystal- lization temperature and the melt temperature of the copolymer composition.
  • a surface treatment such as corona, plasma or flame treatment should be employed before winding the film on a roll.
  • the film Prior to coating the copolyester film surface with the acetate coating composition, the film may be surface treated in a conventional manner by exposure to, e.g. an electric corona, plasma or flame treatment.
  • Electric corona discharge is a conventional surface treatment which is commonly performed on a film to enhance its surface qualities, especially its adhesive and printing properties. Electric discharge methods and apparatus are des ⁇ cribed in U.S. Patent Nos. 3,057,792 and 4,239,973. If the surface treat ⁇ ment followed by the coating occurs before stretch orientation, heating the film before stretch orientation will drive off the water.
  • the corona treatment followed by the acetate polymer coating may occur during the in-line manufacturing process, either before stretch orientation, or between the machine draw and transverse draw of biaxial stretch orientation, or after stretch orientation. If the surface treatment and coating steps occur after stretch orientation, it is necessary to completely dry the film before winding. If the surface treatment and coating occur before orientation, or between draw during orientation, the later orientation steps which require the film to be heated would drive off the excess water from the acetate polymer coating. Preferably, for biaxially oriented film the corona treatment and subsequent acetate polymer coating occur between draws during the stretch orientation step.
  • the mono- or multilayer PENBB film is coated on the corona, plasma or flame treated surface preferably with an aqueous dispersion of the acetate coating composition described below.
  • the coating composition may conven ⁇ iently be applied as an aqueous dispersion or emulsion using any of the well known coating techniques.
  • the film may be coated by roller coating, spray coating, gravure coating, or slot coating.
  • the heat applied to the film during the subsequent pre-heating, stretching, and heat setting stages is generally sufficient to evaporate the water and crosslink the acetate coating, if a crosslinkable monomer comprises a portion of the acetate coa- ting.
  • the coated, biaxially oriented PENBB film may then be heat treated for a period of time necessary to crystallize the film. Crystallization imparts the improved dimensional stability and excellent tensile properties to the PENBB film.
  • the so coated crystallized, biaxially oriented PENBB film is then wound onto a roll.
  • the vinyl acetate copoiymers used as primer layers consist essentially of at least about 50% by weight of polymerized vinyl acetate, which is unhydrolyzed or less than 25% hydrolyzed, and from about 1 % to 15% by weight of a copolymerizable comonomer which in its copolymerized state is then capable of inter-molecular crosslinking by the application of heat without the addition of a separate crosslinking agent.
  • crosslinking comonomers examples include N-methylol acrylamide, N-methylol metha ⁇ crylamide and their corresponding ethers; epoxy materials such as glycidyl acrylate, glycidyl methacrylate and allylglycidyl ether; carboxyl containing materials such as crotonic acid, itaconic acid or acrylic acid; anhydrides such as maleic anhydride or itaconic anhydride; hydroxy containing monomers such as allyl alcohol and hydroxy ethyl or propyl acrylate or methacrylate; amides such as acrylamide, methacrylamide or maleamide; and isocyanates such as vinylisocyanate or allylisocyanate.
  • Preferred comonomers from the above are N-methylolacrylamide and N-methyloimethacrylamide, mainly because copolymer chains containing one of these monomers are capable of condensing with one another with the ap ⁇ plication of heat to form the desired inter-molecular crosslinking.
  • copoiymers containing the other functional monomers it is necessary to form blends of two or more copoiymers containing different functional como ⁇ nomers to achieve the desired crosslinking, e.g.
  • blended vinyl acetate copoiy ⁇ mers include copoiymers containing monomers having epoxide functionality combined with copoiymers containing monomers having amine, acid anhydri ⁇ de, carboxyl, hydroxyl or N-methylol functionality; copoiymers containing monomers have N-methylol or N-methylol ether functionality combined with copoiymers containing monomers having carboxyl, hydroxyl, or amine functionality; copoiymers containing monomers having isocyanate functionali ⁇ ty combined with copoiymers containing monomers having carboxyl or hydroxyl functionality; and so forth.
  • the functional monomers present in the mixed copolymer systems are present in approximately equimo- lar amounts.
  • the vinyl acetate copoiymers also may contain up to about 49% by weight of one or more halogen-free monoethylenically unsaturated monomers interpolymerized therewith.
  • Suitable comonomers include dialkyl maleates such as dioctyl maleate, di-isooctyl maleate and dibutyl maleate; vinyl esters of versatic acid; styrene and styrene derivatives; acrylics such as ethyl acrylate and 2-ethylhexylacrylate; acrylonitrile and similar materials.
  • the preferred crosslinking mixed copolymer compositions for the purposes of this invention are approximately 50/50 blends of a vinyl acetate/- crotonic acid copolymer (99-85: 1 -1 5 monomer weight ratio) with vinyl acetate/glycidyl acrylate copolymer (99-85: 1 -1 5 monomer weight ratio); blends of a vinyl acetate/methacrylamide copolymer (99-85:1 -15 monomer weight ratio) with a vinyl acetate/N-methyiolacrylamide copolymer (99-85:1 -
  • compositions containing non-mixed copoly- mers based on copoiymers of vinyl acetate with N-methylol acrylamide such as copoiymers containing from about 50 to 99% by weight vinyl acetate, 0 to 49% by weight of the mono-ethylenically unsaturated monomer and about
  • N-methylolacrylamide 1 to 15% by weight N-methylolacrylamide. More preferred are copoiymers containing from more than about 50 up to 90% by weight vinyl acetate, about 5 to 45% by weight of the mono-ethylenically unsaturated monomer, preferably methyl methacrylate, and from about 5 to 10% by weight N- methyloiacrylamide.
  • the polymeric vinyl acetate primer composition does not require the presence of an external crosslinking agent such as a meiamine or urea/formaldehyde condensate.
  • the primer coating is applied to the base mono- or multilayer PENBB film preferably as an aqueous dispersion or latex and at a solids concentration within the range of about 0.5 to 15%, preferably about 3 to 10% by weight.
  • the preferred solids level is such as to yield a final dry coating thickness within the range of about 1 to 300 nm, which translates into a solids level on a weight basis of from 1 mg/m 2 to 300 mg/m 2 .
  • the preferred thickness range of the dried copolymer primer is from 15 to 50 nm, with 25 nm being the target thickness.
  • the thickness of the base film to which the coating is applied may range from about 10 to about 250 ⁇ m.
  • the coating may be applied to one or both sides of the mono- or multilayer PENBB film, or it may be applied to one side only, and optionally a different coating may be applied to the opposite side.
  • Additives known in the art may be present in the coating formulation such as anti-static agents, wetting agents, surfactants, pH regulating agents, anti-oxidants, dyes, pigments, slip agents such as colloidal silica, and the like. Normally, it is desirable to include an ionic surfactant to enhance the wettability of the aqueous coating to the base PENBB film thereby further improving adhesion.
  • PENBB film primed with the above composition has excellent utility as a film base for the production of photosensitive reprographic films.
  • Such films are prepared by forming a coating on a surface of the primed PENBB film of a photosensitive composition comprising an organic solvent solution of a resinous binder containing or impregnated with a light-sensitive diazioni- um compound, and drying said coating.
  • Resinous binders suitable for this purpose include cellulose acetate butyrate, cellulose acetate, cellulose acetate propionate as well as vinyl polymers such as polyvinyl acetate.
  • Suitable solvents include acetone, methyl ethyl ketone, methyl isobutyl ketone, ethyle- ne glycol monomethyl ether and mixtures thereof. These reprographic coa ⁇ tings and their method of application and use are well known in the art.
  • the primed PENBB film of this invention forms an excellent substrate for the application of matte coatings which render the film suitable for use as a drawing or drafting material.
  • matte coatings may be based on an organic composition comprising a resinous binder and a finely divided particulate material which serves as a "toothing agent.”
  • the resinous binder may include the resinous materials referred to above as well as acrylic or methacrylic resins.
  • the organic solvents may also include those listed above.
  • Particulate materials include finely divided (less than 10 ⁇ m particle size) clays or silica. Other ingredients such as thickeners or dispersing agents may also be present in such matte formulations. Similar matte formulations are disclosed for example in British Patent No. 1 ,072,122 and U.S. Patent No. 3,624,021 .
  • primed PENBB film of this invention is as a packaging or label material.
  • the primed films demonstrate good adhesion to organic solvent based printing inks and markedly improved UV resistance, dimensional stability, stiffness (tensile modulus) and tensile strength when compared with unprimed film, especially unprimed PET film.
  • These inks may comprise organic solvent dispersions or solutions of pigments and/or dyes in combination with acrylic resins or other resins and thickening agents.
  • the excellent UV resistance, dimensional stability, stiff ⁇ ness (tensile modulus), tensile strength and adhesive qualities of biaxially oriented PENBB film primed with the crosslinked acetate copolymer layers of this invention to organic solvent based coatings applied thereto renders such film of more universal utility to the manufacturer of finished reprographic, graphic and packaging products.
  • Reprographic adhesion is evaluated using a lacquer comprising (in parts by weight) 9 parts cellulose acetate butyrate of "20 second" grade dissolved in a mixture of 88 parts ethylene glycol monomethyl ether (methyl cellosolve) and 3 parts methyl ethyl ketone with Rhodamine B dye added for color (3 parts of a 1 percent Rhodamine B dye in n-butanol).
  • the lacquer is applied to the coated surface of the film by means of a wire-wound bar, Meyer rod No. 70, and cured in an oven for 5 minutes at 60 * C.
  • the coating is scored with a cross-hatched pattern by means of scalpel.
  • a strip of adhe ⁇ sive tape (Scotch tape 610) is adhered to the cross-hatched area, rubbed with a fingernail to insure intimate contact and then pulled rapidly from the film.
  • the mechanical properties are measured in a tensile testing machine made by Zwick (Ulm, Germany) on 15 mm wide strips of film.
  • the initial distance between the chucks is 100 mm and the crosshead speed is 100 mm/min for the strength and elongation determination and 10 m/min for the tensile modulus determination.
  • the UV resistance is tested by measuring the retention of tensile elongation after exposure to UV light in a "Suntest" apparatus manufactured by Heraeus (Hanau, Germany) for 14 days.
  • EXAMPLE A latex comprising 4.5 percent by weight solids of a copolymer of 90 weight percent of vinyl acetate, 5 weight percent methyl methacrylate, and 5 weight percent of N-methylolacrylamide, 0.5 weight percent of colloidal silica, and an anionic surfactant is applied as a primer coating to a PENBB film which is made of 289 parts by weight of dimethyl 2,6-naphthalene dicarbox- ylate, 322 parts by weight of dimethyl 4,4'-bibenzoate, 368 parts by weight of ethylene glycol.
  • Granules of this polymer having a melting point of 281 °C are melted in a single screw extruder at temperatures of 280 to 320°C and extruded through a sheet die onto a cooling roll, which is tempe ⁇ rature controlled at 30°C.
  • a 120 ⁇ m thick film is obtained which is clear and transparent. Its density is 1.31 g/cm 3 .
  • This pre-film is then sequentially biaxially oriented.
  • the longitudinally drawn film is corona treated by a corona discharge apparatus and thereinafter coated with the latex described above by reverse gravure coating.
  • the corona treated longitudinally drawn, coated film is dried at a temperature of about 100°C. Thereafter the film is stret ⁇ ched in the transverse direction.
  • the biaxially drawn film is heat set at a temperature of 230°C.
  • the thus obtained primer coated film shows the following charac ⁇ teristics compared to a similarly coated PET film.
  • stiffness tensile modulus
  • tensile strength tensile strength
  • shrinkage tensile strength
  • the film produced according to the above example is tested for re ⁇ prographic adhesion as set forth above and provides greater than 95 percent adhesion as compared with a control uncoated polyester film which exhibited 0 percent adhesion.

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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)
  • Mechanical Engineering (AREA)
  • Dispersion Chemistry (AREA)
  • Coating Of Shaped Articles Made Of Macromolecular Substances (AREA)
  • Laminated Bodies (AREA)

Abstract

L'invention concerne un film de copolyester mono- ou multicouche, autoporteur, orienté biaxialement, revêtu d'une première couche. Le copolyester est le PENBB et le revêtement de première couche contient un copolymère d'acétate de vinyle. Le PENBB est un copolyester contenant des unités de la formule (I).
PCT/US1992/010685 1992-12-09 1992-12-09 Film de copolyester oriente biaxialement revetu d'une premiere couche de polymeres d'acetate de vinyle WO1994013481A1 (fr)

Priority Applications (2)

Application Number Priority Date Filing Date Title
PCT/US1992/010685 WO1994013481A1 (fr) 1992-12-09 1992-12-09 Film de copolyester oriente biaxialement revetu d'une premiere couche de polymeres d'acetate de vinyle
EP93901009A EP0674591A4 (fr) 1992-12-09 1992-12-09 Film de copolyester oriente biaxialement revetu d'une premiere couche de polymeres d'acetate de vinyle.

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
PCT/US1992/010685 WO1994013481A1 (fr) 1992-12-09 1992-12-09 Film de copolyester oriente biaxialement revetu d'une premiere couche de polymeres d'acetate de vinyle

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WO1994013481A1 true WO1994013481A1 (fr) 1994-06-23

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Cited By (41)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0674584A1 (fr) * 1992-12-09 1995-10-04 Hoechst Aktiengesellschaft Film de pennbb oriente biaxialement utilise pour le vitrage, l'optique et la fabrication d'articles resistant aux intemperies
US6149995A (en) * 1998-03-25 2000-11-21 Mitsubishi Polyester Film Gmbh Transparent polyester film with high oxygen barrier, its use and process for its production
US6200511B1 (en) 1998-03-25 2001-03-13 Mitsubishi Polyester Film Gmbh Polyester film having a high oxygen barrier and improved adhesion to metal layers its use and process for its production
US6214440B1 (en) 1998-10-29 2001-04-10 Mitsubishi Polyester Film Gmbh Coextruded, biaxially oriented polyester film for metallizing, its use and process for its production
US6238782B1 (en) 1998-09-02 2001-05-29 Mitsubishi Polyester Film Gmbh Biaxially oriented polyester film having more than one layer
US6261663B1 (en) 1998-04-22 2001-07-17 Mitsubishi Polyster Film Gmbh Single-layer, biaxially oriented polyester film, its use, and process for its production
US6280833B1 (en) 1998-07-31 2001-08-28 Mitsubishi Polyester Film Gmbh Biaxially oriented polypropylene film having more than one layer, its use, and process for its production
US6291053B1 (en) 1997-09-23 2001-09-18 Hoechst Diafoil Gmbh Multilayer biaxially oriented polyester film, and the use thereof, and process for the production thereof
US6300048B1 (en) 1999-05-07 2001-10-09 Ferrania Spa Photographic element with a layer improving the adhesion to the support
US6358604B1 (en) 1998-07-31 2002-03-19 Mitsubishi Polyester Film Gmbh Matte, coextruded polyester film, its use and process for its production
US6376042B1 (en) 1998-04-22 2002-04-23 Mitsubishi Polyester Film Gmbh Biaxially oriented polyester film having more than one layer; its use; and process for its production
US6383585B2 (en) 1998-03-25 2002-05-07 Mitsubishi Polyester Film Gmbh Sealable polyester film with high oxygen barrier, its use and process for its production
US6391410B1 (en) 1998-03-25 2002-05-21 Mitsubishi Polyester Film, Gmbh Use of a transparent polyester film as a gas/flavor barrier film
US6409862B1 (en) 1998-08-27 2002-06-25 Mitsubishi Polyester Film Gmbh Process for producing biaxially oriented PET films and use of the same for SMD-technology film capacitors
US6410132B1 (en) 1998-09-16 2002-06-25 Mitsubishi Polyester Film Gmbh Biaxially oriented polypropylene film, the use of the film and process for its production
US6528144B2 (en) 1997-09-23 2003-03-04 Hoechst Diafoil Gmbh Biaxially oriented polyester film, the use thereof, and process for the production thereof
US6534169B2 (en) 1998-03-25 2003-03-18 Mitsubishi Polyester Film Gmbh Polyester film with a high oxygen barrier, the use of the film and process for its production
US6537647B2 (en) 1998-03-25 2003-03-25 Mitsubishi Polyester Film Gmbh Polyester film with surface topography matched to the intended use, the use of the film and process for its production
US6551686B1 (en) 1998-04-01 2003-04-22 Mitsubishi Polyester Film Gmbh Biaxially oriented polyester film having more than one layer, process for its production, and its use as magnetic tape film
US6565936B1 (en) 1998-11-03 2003-05-20 Mitsubishi Polyester Film Gmbh Film laminate comprising a biaxially oriented polyester film with high oxygen barrier, its use and a process for its production
US6641924B1 (en) 1999-07-14 2003-11-04 Mitsubishi Polyester Film Gmbh White, biaxially oriented polyester film with cycloolefin copolymer (COC), process for producing the film, and its use
US6730406B2 (en) 2000-01-20 2004-05-04 Mitsubishi Polyester Film Gmbh Matt, UV stable, flame-retardant co-extruded polyester film, a method for the production thereof and the use of the same
US6872460B2 (en) 2000-01-20 2005-03-29 Mitsubishi Polyester Film Gmbh Matt, UV-stable, Thermoformable, co-extruded polyester film, a method for the production thereof and the use of the same
US6872461B2 (en) 2000-01-20 2005-03-29 Mitsubishi Polyester Film Gmbh Matt, flame-retardant, co-extruded polyester film, a method for the production thereof and the use of the same
US6946192B2 (en) 1998-03-25 2005-09-20 Mitsubishi Polyester Film Gmbh Transparent polyester film with high oxygen barrier and additional functionality, its use and process for its production
US7056573B2 (en) 2000-01-20 2006-06-06 Mitsubishi Polyester Film Gmbh Matt, UV-stable, co-extruded polyester film, a method for the production thereof and the use of the same
US7122239B2 (en) 2000-07-20 2006-10-17 Mitsubishi Polyester Film Gmbh Opaque polyester film containing a cyclic olefin copolymer (COC) with good surface attachment, method for producing the same and use thereof
US7141307B2 (en) 2004-06-26 2006-11-28 Mitsubishi Polyester Film Gmbh Extrusion-coatable polyester film comprising poly(m-xyleneadipamide)
EP1728815A1 (fr) 2005-06-01 2006-12-06 Mitsubishi Polyester Film GmbH Feuille blanche opaque qui présente une faible transparence à haute rigidité diélectrique
US7182997B2 (en) 2000-02-19 2007-02-27 Mitsubishi Polyester Film Gmbh Opaque, white film with low transparency made from a crystallizable thermoplastic and having additional functionality
US7189451B2 (en) 2004-07-06 2007-03-13 Mitsubishi Polyester Film Gmbh Multilayer, matt, thermoformable, IR-reflective polyester film
US7189452B2 (en) 2004-07-06 2007-03-13 Mitsubishi Polyester Film Gmbh Matt, thermoformable, IR-reflective polyester film
US7205040B2 (en) 2003-11-10 2007-04-17 Mitsubishi Polyester Film Gmbh Peelable polyester film having improved oxygen barrier, process for its production and its use
US7211306B2 (en) 2003-11-10 2007-05-01 Mitsubishi Polyester Film Gmbh Peelable polyester film with self-venting, process for its production and its use
US7329453B2 (en) 2003-11-10 2008-02-12 Mitsubishi Polyester Film Gmbh White, heatsealable, peelable polyester film, process for its production and its use
US7396578B2 (en) 2003-11-10 2008-07-08 Mitsubishi Polyester Film Gmbh Adhesion-promoted , heatsealable and peelable polyester film, process for its production and its use
US8158230B2 (en) 2007-11-06 2012-04-17 Mitsubishi Polyester Film, Inc. Tamper evident composite film
WO2015077192A2 (fr) 2013-11-19 2015-05-28 Mitsubishi Polyester Film, Inc. Film polymère anti-pulvérulent et antistatique pour l'impression numérique
EP3248777A1 (fr) 2016-05-27 2017-11-29 Mitsubishi Polyester Film GmbH Feuilles en polyester thermoscellables et pelables, leur procédé de fabrication et d'utilisation
EP3321083A1 (fr) 2016-11-11 2018-05-16 Mitsubishi Polyester Film GmbH Feuilles en polyester thermoscellables et pelables à orientation biaxiale, leur procédé de fabrication et d'utilisation
WO2024083485A1 (fr) 2022-10-19 2024-04-25 Agfa-Gevaert Nv Matériau d'enregistrement contenant un film de polyester revêtu

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Cited By (47)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0674584A1 (fr) * 1992-12-09 1995-10-04 Hoechst Aktiengesellschaft Film de pennbb oriente biaxialement utilise pour le vitrage, l'optique et la fabrication d'articles resistant aux intemperies
EP0674584A4 (fr) * 1992-12-09 1995-11-22 Hoechst Ag Film de pennbb oriente biaxialement utilise pour le vitrage, l'optique et la fabrication d'articles resistant aux intemperies.
US6291053B1 (en) 1997-09-23 2001-09-18 Hoechst Diafoil Gmbh Multilayer biaxially oriented polyester film, and the use thereof, and process for the production thereof
US6528144B2 (en) 1997-09-23 2003-03-04 Hoechst Diafoil Gmbh Biaxially oriented polyester film, the use thereof, and process for the production thereof
US6383585B2 (en) 1998-03-25 2002-05-07 Mitsubishi Polyester Film Gmbh Sealable polyester film with high oxygen barrier, its use and process for its production
US6149995A (en) * 1998-03-25 2000-11-21 Mitsubishi Polyester Film Gmbh Transparent polyester film with high oxygen barrier, its use and process for its production
US6946192B2 (en) 1998-03-25 2005-09-20 Mitsubishi Polyester Film Gmbh Transparent polyester film with high oxygen barrier and additional functionality, its use and process for its production
US6537647B2 (en) 1998-03-25 2003-03-25 Mitsubishi Polyester Film Gmbh Polyester film with surface topography matched to the intended use, the use of the film and process for its production
US6534169B2 (en) 1998-03-25 2003-03-18 Mitsubishi Polyester Film Gmbh Polyester film with a high oxygen barrier, the use of the film and process for its production
US6200511B1 (en) 1998-03-25 2001-03-13 Mitsubishi Polyester Film Gmbh Polyester film having a high oxygen barrier and improved adhesion to metal layers its use and process for its production
US6391410B1 (en) 1998-03-25 2002-05-21 Mitsubishi Polyester Film, Gmbh Use of a transparent polyester film as a gas/flavor barrier film
US6551686B1 (en) 1998-04-01 2003-04-22 Mitsubishi Polyester Film Gmbh Biaxially oriented polyester film having more than one layer, process for its production, and its use as magnetic tape film
US6376042B1 (en) 1998-04-22 2002-04-23 Mitsubishi Polyester Film Gmbh Biaxially oriented polyester film having more than one layer; its use; and process for its production
US6261663B1 (en) 1998-04-22 2001-07-17 Mitsubishi Polyster Film Gmbh Single-layer, biaxially oriented polyester film, its use, and process for its production
US6358604B1 (en) 1998-07-31 2002-03-19 Mitsubishi Polyester Film Gmbh Matte, coextruded polyester film, its use and process for its production
US6280833B1 (en) 1998-07-31 2001-08-28 Mitsubishi Polyester Film Gmbh Biaxially oriented polypropylene film having more than one layer, its use, and process for its production
US6409862B1 (en) 1998-08-27 2002-06-25 Mitsubishi Polyester Film Gmbh Process for producing biaxially oriented PET films and use of the same for SMD-technology film capacitors
US6238782B1 (en) 1998-09-02 2001-05-29 Mitsubishi Polyester Film Gmbh Biaxially oriented polyester film having more than one layer
US6410132B1 (en) 1998-09-16 2002-06-25 Mitsubishi Polyester Film Gmbh Biaxially oriented polypropylene film, the use of the film and process for its production
US6214440B1 (en) 1998-10-29 2001-04-10 Mitsubishi Polyester Film Gmbh Coextruded, biaxially oriented polyester film for metallizing, its use and process for its production
US6565936B1 (en) 1998-11-03 2003-05-20 Mitsubishi Polyester Film Gmbh Film laminate comprising a biaxially oriented polyester film with high oxygen barrier, its use and a process for its production
US6300048B1 (en) 1999-05-07 2001-10-09 Ferrania Spa Photographic element with a layer improving the adhesion to the support
US6641924B1 (en) 1999-07-14 2003-11-04 Mitsubishi Polyester Film Gmbh White, biaxially oriented polyester film with cycloolefin copolymer (COC), process for producing the film, and its use
US6730406B2 (en) 2000-01-20 2004-05-04 Mitsubishi Polyester Film Gmbh Matt, UV stable, flame-retardant co-extruded polyester film, a method for the production thereof and the use of the same
US6872460B2 (en) 2000-01-20 2005-03-29 Mitsubishi Polyester Film Gmbh Matt, UV-stable, Thermoformable, co-extruded polyester film, a method for the production thereof and the use of the same
US7056573B2 (en) 2000-01-20 2006-06-06 Mitsubishi Polyester Film Gmbh Matt, UV-stable, co-extruded polyester film, a method for the production thereof and the use of the same
US6872461B2 (en) 2000-01-20 2005-03-29 Mitsubishi Polyester Film Gmbh Matt, flame-retardant, co-extruded polyester film, a method for the production thereof and the use of the same
US7182997B2 (en) 2000-02-19 2007-02-27 Mitsubishi Polyester Film Gmbh Opaque, white film with low transparency made from a crystallizable thermoplastic and having additional functionality
US7122239B2 (en) 2000-07-20 2006-10-17 Mitsubishi Polyester Film Gmbh Opaque polyester film containing a cyclic olefin copolymer (COC) with good surface attachment, method for producing the same and use thereof
US7329453B2 (en) 2003-11-10 2008-02-12 Mitsubishi Polyester Film Gmbh White, heatsealable, peelable polyester film, process for its production and its use
US7205040B2 (en) 2003-11-10 2007-04-17 Mitsubishi Polyester Film Gmbh Peelable polyester film having improved oxygen barrier, process for its production and its use
US7211306B2 (en) 2003-11-10 2007-05-01 Mitsubishi Polyester Film Gmbh Peelable polyester film with self-venting, process for its production and its use
US7396578B2 (en) 2003-11-10 2008-07-08 Mitsubishi Polyester Film Gmbh Adhesion-promoted , heatsealable and peelable polyester film, process for its production and its use
US7141307B2 (en) 2004-06-26 2006-11-28 Mitsubishi Polyester Film Gmbh Extrusion-coatable polyester film comprising poly(m-xyleneadipamide)
US7189451B2 (en) 2004-07-06 2007-03-13 Mitsubishi Polyester Film Gmbh Multilayer, matt, thermoformable, IR-reflective polyester film
US7189452B2 (en) 2004-07-06 2007-03-13 Mitsubishi Polyester Film Gmbh Matt, thermoformable, IR-reflective polyester film
EP1728815A1 (fr) 2005-06-01 2006-12-06 Mitsubishi Polyester Film GmbH Feuille blanche opaque qui présente une faible transparence à haute rigidité diélectrique
US7238419B2 (en) 2005-06-01 2007-07-03 Mitsubishi Polyester Film Gmbh White opaque film having low transparency and improved dielectric strength
US8158230B2 (en) 2007-11-06 2012-04-17 Mitsubishi Polyester Film, Inc. Tamper evident composite film
WO2015077192A2 (fr) 2013-11-19 2015-05-28 Mitsubishi Polyester Film, Inc. Film polymère anti-pulvérulent et antistatique pour l'impression numérique
EP3248777A1 (fr) 2016-05-27 2017-11-29 Mitsubishi Polyester Film GmbH Feuilles en polyester thermoscellables et pelables, leur procédé de fabrication et d'utilisation
DE102016209214A1 (de) 2016-05-27 2017-11-30 Mitsubishi Polyester Film Gmbh Heißsiegelbare und peelfähige Polyesterfolie, Verfahren zu ihrer Herstellung und ihre Verwendung
US10843447B2 (en) 2016-05-27 2020-11-24 Mitsubishi Polyester Film Gmbh Heat-sealable and peelable polyester film, use thereof and process for production thereof
EP3321083A1 (fr) 2016-11-11 2018-05-16 Mitsubishi Polyester Film GmbH Feuilles en polyester thermoscellables et pelables à orientation biaxiale, leur procédé de fabrication et d'utilisation
DE102016222146A1 (de) 2016-11-11 2018-05-17 Mitsubishi Polyester Film Gmbh Biaxial orientierte, heißsiegelbare und peelfähige Polyesterfolie, Verfahren zu ihrer Herstellung und ihre Verwendung
US11465396B2 (en) 2016-11-11 2022-10-11 Mitsubishi Polyester Film Gmbh Biaxially oriented, heat-sealable and peelable polyester film, process for production thereof and use thereof
WO2024083485A1 (fr) 2022-10-19 2024-04-25 Agfa-Gevaert Nv Matériau d'enregistrement contenant un film de polyester revêtu

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