WO2015152193A1 - Film de polyester antistatique et son procédé de production - Google Patents

Film de polyester antistatique et son procédé de production Download PDF

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Publication number
WO2015152193A1
WO2015152193A1 PCT/JP2015/060037 JP2015060037W WO2015152193A1 WO 2015152193 A1 WO2015152193 A1 WO 2015152193A1 JP 2015060037 W JP2015060037 W JP 2015060037W WO 2015152193 A1 WO2015152193 A1 WO 2015152193A1
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WIPO (PCT)
Prior art keywords
polyester film
antistatic
film
antistatic layer
polymer
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PCT/JP2015/060037
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English (en)
Japanese (ja)
Inventor
嘉己 上野
康平 田中
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ユニチカ株式会社
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Priority to JP2016511906A priority Critical patent/JP6625048B2/ja
Publication of WO2015152193A1 publication Critical patent/WO2015152193A1/fr

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Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/36—Layered products comprising a layer of synthetic resin comprising polyesters
    • 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
    • C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
    • C08J7/04—Coating
    • C08J7/044—Forming conductive coatings; Forming coatings having anti-static properties
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D201/00—Coating compositions based on unspecified macromolecular compounds
    • C09D201/02—Coating compositions based on unspecified macromolecular compounds characterised by the presence of specified groups, e.g. terminal or pendant functional groups
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D201/00—Coating compositions based on unspecified macromolecular compounds
    • C09D201/02—Coating compositions based on unspecified macromolecular compounds characterised by the presence of specified groups, e.g. terminal or pendant functional groups
    • C09D201/06—Coating compositions based on unspecified macromolecular compounds characterised by the presence of specified groups, e.g. terminal or pendant functional groups containing oxygen atoms
    • C09D201/08—Carboxyl groups
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/24—Electrically-conducting paints
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives
    • C09D7/65—Additives macromolecular
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/20—Properties of the layers or laminate having particular electrical or magnetic properties, e.g. piezoelectric
    • B32B2307/21—Anti-static
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2419/00—Buildings or parts thereof
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2439/00—Containers; Receptacles
    • B32B2439/70—Food packaging
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2439/00—Containers; Receptacles
    • B32B2439/80—Medical packaging
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2457/00—Electrical equipment
    • 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
    • C08J2433/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers
    • C08J2433/02—Homopolymers or copolymers of acids; Metal or ammonium salts thereof

Definitions

  • the present invention relates to a polyester film having excellent antistatic properties.
  • Polyester film is excellent in mechanical properties, heat resistance and transparency, and widely used in packaged food applications, and in base films and process films for industrial materials such as packaging materials, information storage materials, building materials, electronic materials, and printing materials. in use.
  • plastic films and their laminated films are prone to static electricity due to contact friction and peeling during processing and product use, so dust and small dust are likely to adhere.
  • a film used as a packaging material for foods and pharmaceuticals mixing of these deposits is not preferable.
  • the occurrence of static electricity may reduce the paper feed suitability and paper discharge suitability during printing. Accordingly, it is preferable to impart antistatic performance to the film.
  • Patent Documents 1 to 3 propose the use of a polymeric antistatic agent having a quaternary ammonium group and a carboxyl group in the side chain as an antistatic agent.
  • an object of the present invention is to provide an antistatic polyester film which is excellent in antistatic properties, suppresses a decrease in transparency due to heat treatment, and has higher quality coating film uniformity.
  • the present inventors have found that the above problem can be solved by forming an antistatic layer on a polyester film using a coating liquid in a specific dispersion state, and have reached the present invention.
  • the gist of the present invention is as follows.
  • the average value of the streak-like defects is 1.0 or less per 1 m of the film width.
  • the antistatic polyester film as described in (1). (3) The antistatic polyester film according to (1) or (2), wherein the surface specific resistance value at 23 ° C. and 50% RH is less than 1 ⁇ 10 12 ⁇ / ⁇ . (4) The antistatic polyester film as described in any one of (1) to (3), wherein the antistatic layer has a thickness of 0.05 to 0.5 ⁇ m. (5) The antistatic layer further contains a crosslinking agent (B), and the mass ratio (A / B) of the polymer (A) to the crosslinking agent (B) is 95/5 to 70/30.
  • the antistatic polyester film as described in any one of (1) to (4).
  • a method for producing the antistatic polyester film described in (1) above comprising as a main component a polymer (A) having a quaternary ammonium group and a carboxyl group in the side chain as a main component.
  • a method for producing an antistatic polyester film comprising forming an antistatic layer using a coating liquid having an average particle size of less than 300 nm.
  • the antistatic polyester film by which the transparency fall after heat processing was suppressed can be provided.
  • the antistatic layer which comprises an antistatic polyester film has the streak-like defect resulting from the coating method suppressed, and is more excellent in appearance. Since the antistatic polyester film of the present invention can sufficiently exhibit the antistatic performance, it can improve the yield and stabilize the quality when the resulting laminated film is used as a product. For this reason, it can be used as a protective film.
  • the antistatic polyester film of the present invention has an antistatic layer formed on at least one side of a polyester film as a substrate.
  • the polyester resin constituting the polyester film substrate is not particularly limited, and examples thereof include polyethylene terephthalate, polyethylene isophthalate, polytetramethylene terephthalate, poly (1,4-cyclohexylenedimethylene terephthalate), and polyethylene-2,6.
  • -Naphthalate is exemplified, and polyethylene terephthalate and polyethylene-2,6-naphthalate are preferable.
  • the polyester resin may be copolymerized with other components as necessary, and examples of the other components include a carboxylic acid component, a hydroxycarboxylic acid component, and an alcohol component.
  • carboxylic acid component include isophthalic acid, phthalic acid, 2,6-naphthalenedicarboxylic acid, 5-sodium sulfoisophthalic acid, oxalic acid, succinic acid, adipic acid, sebacic acid, azelaic acid, dodecanedioic acid, dimer acid , Maleic anhydride, maleic acid, fumaric acid, itaconic acid, citraconic acid, mesaconic acid, cyclohexanedicarboxylic acid, trimellitic acid, trimesic acid, and pyromellitic acid.
  • Examples of the hydroxycarboxylic acid component include 4-hydroxybenzoic acid, ⁇ -caprolactone, and lactic acid.
  • Examples of the alcohol component include ethylene glycol, diethylene glycol, 1,3-propanediol, neopentyl glycol, 1,6-hexanediol, cyclohexanedimethanol, triethylene glycol, polyethylene glycol, polypropylene glycol, polytetramethylene glycol, and bisphenol.
  • Examples include ethylene oxide adducts of A and bisphenol S, trimethylolpropane, glycerin, and pentaerythritol. Two or more of these copolymer components may be used in combination.
  • the polymerization method of the polyester resin is not particularly limited, and examples thereof include a transesterification method and a direct polymerization method.
  • the transesterification catalyst include Mg, Mn, Zn, Ca, Li, Ti oxides, and compounds such as acetate.
  • the polycondensation catalyst include compounds such as Sb, Ti, Ge oxides and acetates. Since the polyester resin after polymerization contains a monomer, an oligomer, a by-product acetaldehyde, and the like, solid-state polymerization may be performed at a temperature of 200 ° C. or higher under reduced pressure or through an inert gas flow.
  • additives such as an antioxidant, a heat stabilizer, an ultraviolet absorber, and an antistatic agent can be added as necessary.
  • Antioxidants include hindered phenol compounds, hindered amine compounds, etc.
  • thermal stabilizers include phosphorus compounds, etc.
  • UV absorbers include benzophenone compounds, benzotriazole compounds, etc. Is mentioned.
  • the intrinsic viscosity of the polyester resin is preferably 0.55 to 0.80, and more preferably 0.60 to 0.75.
  • the intrinsic viscosity of the polyester resin is less than 0.55, cutting is likely to occur during film formation, and it is difficult to stably produce a film, and the resulting film has low strength.
  • the intrinsic viscosity of the polyester resin exceeds 0.80, shear heat generation increases during the melt extrusion of the resin in the film production process, and the pyrolyzate and gelled product increase. As a result, the resulting film has increased surface defects, foreign matter, and surface rough protrusions. Further, the load on the extruder is increased, the production speed must be sacrificed, and the thickness control of the film becomes difficult.
  • the intrinsic viscosity is too high, the polymerization time and the polymerization process are long, which increases the cost.
  • the thickness of the polyester film substrate made of the polyester resin is not particularly limited, but is preferably 12 to 250 ⁇ m, more preferably 16 to 150 ⁇ m, and still more preferably 20 to 75 ⁇ m.
  • the polyester film substrate may be a single-layer substrate composed of one kind of layer, but in the present invention, it is preferably a substrate having a multilayer structure formed by laminating two or more kinds of layers.
  • the polyester film substrate has such a multilayer structure, the surface roughness of each surface can be controlled independently.
  • the antistatic layer formed on at least one side of the polyester film as a substrate is mainly composed of a polymer (A) having a quaternary ammonium group and a carboxyl group in the side chain.
  • the content of the polymer (A) in the antistatic layer is preferably 60 to 95% by mass, and more preferably 75 to 95% by mass.
  • the polymer (A) used in the present invention may be any polymer (ion conducting polymer) having electrostatic polarization relaxation properties, and the quaternary ammonium group in the polymer (A) has an electrostatic polarization property. Prompt electrostatic polarization relaxation due to ionic conductivity can be imparted.
  • the polymer (A) is preferably a polyacrylic copolymer having a quaternary ammonium group and a carboxyl group in the side chain.
  • the polyacrylic copolymer has significantly improved properties such as adhesion, durability, and heat resistance due to the crosslinking reaction with the crosslinking agent, and the antistatic effect that is effective for polyester film due to the electrostatic polarization relaxation performance of the polymer. Sex can be imparted.
  • examples of the monomer having a quaternary ammonium group include dimethylaminoethyl (meth) acrylate quaternized compounds having a counter ion of methyl sulfate or ethyl sulfate. It is done.
  • examples of the monomer having a carboxyl group include (meth) acrylic acid.
  • (meth) acrylic acid ester, styrene, and other vinyl derivatives are listed as other monomers.
  • the composition ratio of these monomers can be varied within a wide range, but the monomer having a quaternary ammonium group is preferably 15 to 50 mol% with respect to the total monomers of the copolymer,
  • the monomer having a carboxyl group is preferably 2 to 15 mol%, and the other monomer is preferably 35 to 83 mol%.
  • the copolymerization amount of the monomer having a quaternary ammonium group or the monomer having a carboxyl group exceeds this range, the coating liquid using the resulting polymer (A) has an increased viscosity, and the film becomes a film. The coatability of the coating may deteriorate.
  • an alkyl sulfate ion as a counter ion of a quaternary ammonium group.
  • an alkyl sulfate ion is used as a counter ion, the quaternary ammonium salt is hardly decomposed by Hoffman due to heat, and heat resistance can be imparted to the antistatic layer.
  • the antistatic polyester film is used as the surface layer film of the laminated film, the antistatic layer hardly deteriorates and can maintain heat resistance even when it is pressed at a high temperature.
  • the counter ion is methyl sulfate, the obtained antistatic polyester film has little increase in surface resistivity even when heated at 200 ° C.
  • Alkylsulfate ions are not decomposed like chlorine ions and do not generate chlorine gas, and even if an antistatic polyester film is used in contact with metal, it may have adverse effects such as corrosion of the metal. Absent. Further, in the production process of the antistatic polyester film, environmental pollution in the apparatus can be reduced, and a clean state can be maintained for a long time.
  • a copolymer of trimethylaminoethyl acrylate chloride whose counter ion is a chlorine ion as a monomer decomposes in 1 to 2 minutes when heated to 150 ° C. and generates chlorine gas, and is also antistatic. Performance may be degraded.
  • the antistatic layer mainly composed of the polymer (A) preferably contains a crosslinking agent (B).
  • the antistatic layer is improved in cohesiveness and adhesion.
  • crosslinking agent (B) an epoxy compound, a melamine compound, an isocyanate compound, a silane coupling agent, polyethyleneimine, polyvinyl alcohol, etc. are mentioned, for example, An epoxy compound and polyethyleneimine are especially preferable. In the present invention, it is more preferable to use two or more selected from these in combination.
  • a crosslinking agent (B) is water-soluble or water-dispersible so that it does not need to contain the organic solvent in the coating liquid used in order to form an antistatic layer.
  • the epoxy compound is preferably a bifunctional derivative such as diethylene glycol diglycidyl ether, glycerin diglycidyl ether or bisphenol A diglycidyl ether, or a trifunctional derivative such as trimethylolpropane triglycidyl ether.
  • a bifunctional derivative such as diethylene glycol diglycidyl ether, glycerin diglycidyl ether or bisphenol A diglycidyl ether
  • a trifunctional derivative such as trimethylolpropane triglycidyl ether.
  • Examples of the isocyanate compound include aromatic polyisocyanates such as toluene diisocyanate and diphenylmethane diisocyanate, aliphatic polyisocyanates such as hexamethylene diisocyanate, cyclohexane diisocyanate, and butane diisocyanate, and derivatives thereof.
  • a blocked isocyanate compound is preferable in terms of enhancing stability.
  • Examples of the silane coupling agent include epoxy alkyl silanes and aminoalkyl silanes, and ⁇ -glycidoxypropyltrimethoxysilane, ⁇ - (2-aminoethyl) aminopropyltrimethoxysilane and the like are preferable.
  • examples of the polyethyleneimine include highly polar and high density polyamines having a branched structure composed of primary, secondary, and tertiary amines.
  • examples of the water-soluble resin include a polyvinyl alcohol resin.
  • the polyvinyl alcohol resin preferably has a saponification degree of 89% or more and a molecular weight of 100 to 1,000.
  • the antistatic layer preferably also contains a catalyst for the crosslinking agent (B).
  • Catalysts include imidazole derivatives such as 2-methylimidazole and 2-ethyl-4-methylimidazole, epoxy ring-opening reaction catalysts such as polyamines and polyethyleneimine derivatives, melamine crosslinking catalysts such as paratoluenesulfonic acid, imidazole, and organic tin Examples include urethane crosslinking catalysts such as compounds.
  • the content of the catalyst is not particularly defined, but is preferably 5 to 30 parts by mass with respect to 100 parts by mass in total of the polymer (A) and the crosslinking agent (B), and 5 to 15 parts by mass. Is more preferable.
  • the mass ratio (A / B) of the polymer (A) and the crosslinking agent (B) is preferably 95/5 to 70/30, More preferably, it is 10 to 80/20.
  • the content of the crosslinking agent (B) is less than 5% by mass, the antistatic layer may be difficult to obtain a desired adhesion improving effect on the polyester film, and the content exceeds 30% by mass. In addition, the antistatic layer may deteriorate the antistatic performance.
  • the antistatic layer in this invention contains surfactant (C).
  • the antistatic layer can draw out the antistatic performance of the polymer (A) having electrostatic polarization relaxation to a higher degree, and in particular, without depending on humidity. Preventive property becomes stable.
  • the surfactant (C) is preferably of a low molecular ion conduction type, and specifically can be selected from general anionic surfactants, cationic surfactants, and nonionic surfactants.
  • Surfactant (C) is a quaternary ammonia because of its compatibility with the coating solution for forming the antistatic layer, the suitability for coating the coating solution, and the adhesion and blocking resistance between the resulting antistatic layer and the polyester film.
  • a compound having a nium salt and a compound having a sulfonate are preferable.
  • the content of the surfactant (C) is 1 to 15 parts by mass with respect to 100 parts by mass in total of the polymer (A) and the crosslinking agent (B).
  • the amount is 1 to 10 parts by mass.
  • the haze difference ( ⁇ Hz) before and after the heat treatment needs to be less than 1.0%, and less than 0.9% It is preferable that it is less than 0.8%.
  • the haze difference ( ⁇ Hz) exceeds 1.0%, the antistatic polyester film is impaired in transparency and becomes a problem in appearance.
  • the antistatic polyester film of the present invention is provided with antistatic properties by forming an antistatic layer on the polyester film using a coating liquid in a specific dispersion state, and the antistatic layer formed
  • the haze value does not increase after heat treatment, and appearance defects such as whitening can be reduced.
  • the antistatic polyester film of the present invention has a total of 10 points including a point 1 m from one end edge in the longitudinal direction of the film, a point 1 m from the other end edge, and a point equally divided by 9 between the two points. It is preferable that the average value of the streak-like defects observed at the full film width of the point is 1.0 or less per 1 m of the film width.
  • the edge is the edge of the film.
  • streaky defects can be counted by a method in which each point of the antistatic polyester film is irradiated from the surface of the antistatic layer using a high-intensity light source and visually observed in the width direction (TD). .
  • the streak defect means a coating stripe or coating unevenness generated in the longitudinal direction of the film.
  • the antistatic polyester film of the present invention preferably has a surface resistivity of less than 1 ⁇ 10 12 ⁇ / ⁇ at 23 ° C. and a relative humidity (RH) of 50%.
  • RH relative humidity
  • the thickness of the antistatic layer of the polyester film of the present invention is preferably 0.05 to 0.5 ⁇ m. If the thickness of the antistatic layer is less than 0.05 ⁇ m, the antistatic performance may not be exhibited, and if it exceeds 0.5 ⁇ m, the antistatic performance is saturated.
  • a sufficiently dried polyester resin is supplied to an extruder, fully plasticized, melted at a temperature showing fluidity, passed through a filter selected as necessary, and then passed through a T-die. Extrude into a shape. This sheet is brought into close contact with a cooling drum whose temperature is adjusted to a glass transition point (Tg) or less of the polyester resin to obtain an unstretched film.
  • Tg glass transition point
  • the obtained unstretched film is biaxially oriented by biaxial stretching.
  • the stretching method is not particularly limited, and examples thereof include a sequential biaxial stretching method and a simultaneous biaxial stretching method.
  • the antistatic polyester film of the present invention is produced by applying a coating solution for forming an antistatic layer during the production process of the polyester film, followed by drying, stretching and heat setting treatment together with the polyester film. Can do.
  • the coating solution is applied to an unstretched film, dried, and stretched about 2 to 4 times in the longitudinal and width directions within a temperature range of 50 ° C. higher than Tg to Tg of the polyester resin.
  • Biaxial stretching is performed to obtain a magnification.
  • preliminary longitudinal stretching of about 1 to 1.2 times may be performed prior to guiding to the simultaneous biaxial stretching machine.
  • an unstretched film is heated with a roll, infrared rays or the like and stretched in the longitudinal direction to obtain a longitudinally stretched film.
  • Stretching preferably uses a difference in peripheral speed of two or more rolls and is 2.5 to 4.0 times in a temperature range 40 ° C. higher than Tg to Tg of the polyester resin.
  • the longitudinally stretched film is continuously subjected to transverse stretching, heat setting, and thermal relaxation in the width direction to form a biaxially oriented film.
  • the transverse stretching starts at a temperature 40 ° C. higher than the Tg to Tg of the polyester resin, and the maximum temperature is preferably a temperature lower by (100 to 40) ° C.
  • the transverse stretching ratio is adjusted according to the required physical properties of the final polyester film, but it is preferably 3.5 times or more, more preferably 3.8 times or more, and more preferably 4.0 times or more. preferable.
  • the elastic modulus and dimensional stability of the polyester film can be increased.
  • the polyester film is cooled to Tg or less of the polyester film to obtain a polyester film having an antistatic layer formed thereon.
  • the polyester film base material which has a multilayer structure comprises each layer in the said manufacturing method, for example.
  • Polyester resin is melt-extruded separately, laminated and fused before solidification, then biaxially stretched and heat-set, or two or more layers are melt-extruded separately to form a film, either unstretched or stretched, both It is possible to manufacture by combining the methods of laminating and fusing. From the simplicity of the process, it is preferable to use a multilayer die and laminate and fuse before solidification. In addition, you may mix
  • the coating liquid used for forming the antistatic layer comprises a polymer (A), a crosslinking agent (B) or a surfactant (C) as necessary, water, etc. These media are included. You may contain well-known additives, such as an antifoamer, antioxidant, and a lubricant, as needed.
  • the coating liquid for forming the antistatic layer needs to have an average particle size of solid content of less than 300 nm, preferably less than 275 nm, and preferably less than 250 nm. More preferably, it is less than 225 nm. In addition, the lower limit of the average particle size of the solid content that can usually be achieved is 50 nm.
  • the antistatic polyester film obtained by forming an antistatic layer using a coating liquid having an average solid content particle size in the above range can be obtained by subjecting the base material to heat treatment at 150 ° C. for 1 hour. It is possible to suppress the precipitation of oligomer components from the polyester film, the haze value does not increase, the haze difference ⁇ Hz before and after the heat treatment can be made less than 1.0%, and appearance defects such as whitening are caused. Can be reduced. Moreover, by applying the coating liquid having an average particle size of the solid content within the above range, it is possible to suppress plate jam of the gravure roll and reduce streak-like defects.
  • the polymer (A) contained in the coating liquid has both a quaternary ammonium group and a carboxyl group in the side chain, a cationic group and an anionic group coexist in the molecule, and the particles associate with each other. It is easy to secondary agglomerate. Further, even when another ionic substance is added to the coating solution, the polymer (A) may be complexed and aggregated therewith.
  • the average particle size of the solid content contained in the coating liquid in the above range, it is possible to suppress plate grabbing of the gravure roll and the like, and to prevent the occurrence of coating stripes in the film longitudinal direction.
  • the coating liquid is preferably an aqueous solution or an aqueous dispersion from the viewpoint of safety and hygiene in the production process.
  • the solid concentration of the coating liquid is preferably 5 to 30% by mass, and more preferably 10 to 20% by mass from the viewpoint of coating workability.
  • the coating liquid can be prepared by mixing the polymer (A), if necessary, the crosslinking agent (B) or surfactant (C), water, etc., and uniformly dispersing the mixture.
  • the method for adjusting the average particle size of the solids present in the coating liquid to less than 300 nm is not particularly limited, but may be a predetermined average by ultrasonic treatment, high-speed dispersion treatment, high-pressure dispersion treatment, jet mill, bead mill, etc. The method of processing so that it may become a particle size is mentioned.
  • a general coating method can be used, for example, Mayer bar coat, air knife coat, reverse roll coat, reverse gravure roll coat, gravure roll. Examples of the method include coating, lip coating, and die coating.
  • the application amount of the coating liquid is preferably 1 to 10 g / m 2 .
  • the drying conditions after coating are preferably 50 to 90 ° C. and 10 to 60 seconds.
  • the antistatic polyester film of the present invention can be used as it is, but surface treatment such as corona discharge or ion blow may be performed on the surface where the antistatic layer is formed or non-formed.
  • the antistatic polyester film of the present invention has excellent antistatic properties, suppresses a decrease in transparency due to heat treatment, and is excellent in uniformity, heat resistance, and adhesion of the antistatic layer. Therefore, it can be used in various packaging and industrial applications by adhering printing ink, adhesive, photo-curing resin, binder and the like. In particular, since generation of oligomer components during heat treatment can be suppressed, it can be suitably used as information storage materials, building materials, printing materials, electronic materials, and the like. In addition, the antistatic polyester film of the present invention has excellent antistatic properties and improved appearance with few streak-like defects. Therefore, the electrical and electronic component fields have high antistatic performance requirements.
  • it can be suitably used as an antistatic polyester film for optical applications and design fields with a high degree of demand for appearance.
  • it can be suitably used as a material for various packaging and industrial applications.
  • a surface film such as a protective film can be used.
  • the haze value was measured using a haze meter (manufactured by Tokyo Denshoku) according to ASTM D1003-61. Note that there was no volatile matter from the adhesive tape itself.
  • the temperature is kept with the heavy release protective film applied to prevent contamination. Heat treatment was performed at 150 ° C. for 1 hour. Then, the haze value (T2) after heat processing was measured about the sample which peeled off the heavy peeling side protective film.
  • measurement is performed with 5 samples for each sampling location, and each sampling is performed by subtracting the average value (TM1) of the haze value (T1) before heat treatment from the average value (TM2) of the haze value (T2) after heat treatment.
  • TM1 average value of the haze value
  • T2 average value of the haze value
  • the appearance of the antistatic layer was evaluated by the following two methods.
  • the points to be evaluated are 9 points between the two points, a point 1 m from one end edge in the longitudinal direction of the film, a point 1 m from the other end edge, in the raw material of the antistatic polyester film.
  • a total of 10 spots are drawn, a straight line is drawn with a black oil-based pen in the width direction (TD) of the film at each point, and a portion showing streak-like interference intersecting the straight line or a streak-like defect with respect to the entire width of the film Observed.
  • Evaluation method B At each evaluation point of the antistatic polyester film, using a high-intensity LED flashlight (M7R type, 400 lumen manufactured by Redlenzer) from an oblique direction of about 10 to 45 ° with respect to the surface of the antistatic layer. The number of streak-like defects in the entire width of the film at each point was visually counted by applying light at a distance of 30 cm from the film. The number of streak-like defects per 1 m of film width at each point was calculated, and the average value at the 10 points was determined.
  • M7R type 400 lumen manufactured by Redlenzer
  • Crosslinking agent (B) Aqueous solution of crosslinking agent (B-1): Aqueous solution of polyethyleneimine (Nippon Shokubai P-1000, solid content concentration 30% by mass)
  • Crosslinking agent (B-2) Polyethyleneimine (Nippon Shokubai Co., Ltd.
  • Crosslinking agent (B-3) Epoxy compound (DIC-5 CR-5L, polyhydroxyalkane polyglycidyl ether, solid content 100% by mass)
  • Crosslinking agent (B-4) Epoxy compound (KBM-403 manufactured by Shin-Etsu Chemical Co., Ltd., epoxy silane coupling agent, solid content: 100% by mass)
  • -Aqueous solution of cross-linking agent (B-5) Aqueous solution of melamine compound (M-30WT, Changchun Plastics Co., Ltd., solid content concentration 80% by mass)
  • Surfactant (C) Surfactant (C-1): Acetylene glycol type (Nisshin Chemical Industry Olfin E1004, solid content: 100% by mass)
  • Surfactant (C-2) Acetylene glycol type (Surfinol 440 manufactured by Air Products, solid content: 100% by mass)
  • Example 1 (Preparation of coating solution) A propeller stirrer was prepared by adding 1.1 kg (solid content 0.3 kg) of an aqueous solution of a crosslinking agent (B-1) polyethyleneimine to 28.3 kg (solid content 8.5 kg) of the aqueous dispersion of polymer (A-1). And stirred vigorously. Next, 0.9 kg of the epoxy compound of the second cross-linking agent (B-3) and 0.8 kg of the acetylene glycol surfactant of the surfactant (C-1) were added and stirred for 60 minutes.
  • the mass ratio of the above components (solid content) constituting the coating liquid (polymer (A-1): crosslinking agent (B-1, polyethyleneimine): crosslinking agent (B-3, epoxy compound): interface
  • the active agent (C-1)) was 87.6: 3.1: 9.3: 8.2.
  • pure water was added to adjust the total solid content concentration to 12.7% by mass, and the mixture was further stirred for 30 minutes, and then stopped and degassed. Thereafter, an ultrasonic dispersion treatment was performed using an ultrasonic disperser (UH-600SR-1 type, manufactured by SMT Co., Ltd.) at 20 kHz so that the residence time was 5 minutes, thereby obtaining a coating solution.
  • the average particle size of the solid content in the coating solution was 127 nm.
  • Polyethylene terephthalate containing 0.07% by mass of amorphous silica particles having an average particle diameter of 2.3 ⁇ m is used as a resin for forming the resin layer A, and amorphous silica is used as a resin for forming the resin layer C.
  • Polyethylene terephthalate containing no particles was used. Each of these resins was put into two independent extruders I and II (screw diameters were extruder I: 50 mm, extruder II: 65 mm) and melted at 280 ° C.
  • an unstretched film having a total thickness of 600 ⁇ m.
  • the thickness ratio of each layer of the unstretched film was adjusted to 1/8/1.
  • antimony trioxide was used as a polymerization catalyst, and an intrinsic viscosity of 0.62, a glass transition temperature of 78 ° C., and a melting point of 255 ° C. were used.
  • the obtained unstretched film was stretched 3.5 times with a roll-type longitudinal stretching machine under the condition of 85 ° C.
  • the previously prepared coating solution was applied to the surface of the resin layer A of the longitudinally stretched film with a 120 mesh gravure roll so as to be 5 g / m 2, and then passed through a hot air drying oven at 50 ° C. for 20 seconds. I let you.
  • the end of the longitudinally stretched film coated with the coating solution and dried is continuously held by a clip of a flat stretching machine, stretched 4.5 times in width at 100 ° C, and then stretched horizontally.
  • the heat treatment was performed at 230 ° C. for 3 seconds with a direction relaxation rate of 3%, and then cooled and wound up.
  • the thickness of the obtained antistatic polyester film was 38 ⁇ m, and the thickness of the antistatic layer was about 0.15 ⁇ m. This film was evaluated for total haze, haze difference ⁇ Hz, appearance, and surface resistivity. The results are shown in Table 1.
  • Example 2 to 16 Comparative Examples 1 to 8 (Preparation of coating solution)
  • a coating solution was prepared in the same manner as in Example 1 except that the composition, total solid content concentration, dispersion method, and treatment time described in Tables 1 and 2 were used.
  • the coating liquid was dispersed under the condition of 10,000 rpm using a Filmix 56-50 type (manufactured by Tokushu Kika Kogyo Co., Ltd.).
  • a polyester film substrate was produced in the same manner as in Example 1 except that the laminated configuration of the polyester film substrate was changed to the configurations shown in Tables 1 and 2.
  • a resin for forming the resin layer B polyethylene terephthalate containing 0.03% by mass of amorphous silica particles having an average particle diameter of 2.3 ⁇ m was used.
  • the laminate in which the layer configuration was two types and two layers was adjusted such that the thickness ratio of each layer (resin layer B / resin layer A) was 4/6.
  • an antistatic layer was formed in the same manner as in Example 1 except that the polyester film layer surfaces shown in Tables 1 and 2 were made to have the thicknesses shown in Tables 1 and 2.
  • Tables 1 and 2 show the average particle size of the solid content in the prepared coating liquid and various performance evaluation results of the obtained antistatic polyester film.
  • the antistatic polyester films of the examples had a haze difference ⁇ Hz of less than 1.0% before and after the heat treatment when heat-treated at a temperature of 150 ° C. for 1 hour, and suppressed a decrease in transparency due to the heat treatment. It was what was done.
  • the antistatic layer was excellent in appearance with no streak-like defects even when a high-intensity light source was used.
  • the antistatic polyester film of the comparative example in which the antistatic layer is formed using the coating liquid having a large average particle size of the solid content has a haze difference ⁇ Hz of 1.0% or more before and after the heat treatment.
  • a high-intensity light source was used, streaky defects were generated in the antistatic layer and the appearance was poor.
  • Comparative Example 5 using a coating liquid with a low solid content concentration the surface resistivity was high and the antistatic performance was inferior compared to Example 5 using a coating liquid with the same solid content concentration. .

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Health & Medical Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Wood Science & Technology (AREA)
  • Laminated Bodies (AREA)
  • Coating Of Shaped Articles Made Of Macromolecular Substances (AREA)
  • Paints Or Removers (AREA)

Abstract

La présente invention concerne un film de polyester antistatique obtenu par formation d'une couche antistatique sur au moins une surface d'un film de polyester, le film de polyester antistatique étant caractérisé en ce que la couche antistatique contient principalement un polymère (A) ayant un groupe ammonium quaternaire et un groupe carboxy dans une chaîne latérale et en ce que, lorsque le film de polyester antistatique est soumis à un traitement thermique pendant une heure à une température de 150 °C, la différence de trouble (ΔHz) avant et après le traitement thermique est inférieure à 1,0 %.
PCT/JP2015/060037 2014-03-31 2015-03-31 Film de polyester antistatique et son procédé de production WO2015152193A1 (fr)

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JP2017179023A (ja) * 2016-03-29 2017-10-05 三菱ケミカル株式会社 積層ポリエステルフィルム
JP2018051921A (ja) * 2016-09-29 2018-04-05 ユニチカ株式会社 帯電防止性ポリエステルフィルム

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US20220379589A1 (en) * 2019-11-20 2022-12-01 Toyobo Co., Ltd. Laminated film

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JPH11300918A (ja) * 1998-04-24 1999-11-02 Toray Ind Inc 易接着性ポリエステルフィルム
JP2004195775A (ja) * 2002-12-18 2004-07-15 Toray Ind Inc ポリエステルフィルム
JP2005178313A (ja) * 2003-12-24 2005-07-07 Toyobo Co Ltd 積層ポリエステルフィルムおよびその製造方法
JP2006160883A (ja) * 2004-12-07 2006-06-22 Unitika Ltd 易接着ポリエステルフィルム
JP2013006299A (ja) * 2011-06-23 2013-01-10 Unitika Ltd 帯電防止フィルム
JP2013006300A (ja) * 2011-06-23 2013-01-10 Unitika Ltd 帯電防止フィルム
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JPH11300918A (ja) * 1998-04-24 1999-11-02 Toray Ind Inc 易接着性ポリエステルフィルム
JP2004195775A (ja) * 2002-12-18 2004-07-15 Toray Ind Inc ポリエステルフィルム
JP2005178313A (ja) * 2003-12-24 2005-07-07 Toyobo Co Ltd 積層ポリエステルフィルムおよびその製造方法
JP2006160883A (ja) * 2004-12-07 2006-06-22 Unitika Ltd 易接着ポリエステルフィルム
JP2013006299A (ja) * 2011-06-23 2013-01-10 Unitika Ltd 帯電防止フィルム
JP2013006300A (ja) * 2011-06-23 2013-01-10 Unitika Ltd 帯電防止フィルム
JP2013071445A (ja) * 2011-09-29 2013-04-22 Unitika Ltd 帯電防止性ポリエステルフィルム

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2017179023A (ja) * 2016-03-29 2017-10-05 三菱ケミカル株式会社 積層ポリエステルフィルム
JP2018051921A (ja) * 2016-09-29 2018-04-05 ユニチカ株式会社 帯電防止性ポリエステルフィルム

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