WO2012144418A1 - Coated film - Google Patents

Coated film Download PDF

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Publication number
WO2012144418A1
WO2012144418A1 PCT/JP2012/060032 JP2012060032W WO2012144418A1 WO 2012144418 A1 WO2012144418 A1 WO 2012144418A1 JP 2012060032 W JP2012060032 W JP 2012060032W WO 2012144418 A1 WO2012144418 A1 WO 2012144418A1
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WO
WIPO (PCT)
Prior art keywords
film
coating
metal
coated film
particles
Prior art date
Application number
PCT/JP2012/060032
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French (fr)
Japanese (ja)
Inventor
開俊啓
神田俊宏
藤田真人
Original Assignee
三菱樹脂株式会社
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Publication of WO2012144418A1 publication Critical patent/WO2012144418A1/en

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • 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
    • C08J7/046—Forming abrasion-resistant coatings; Forming surface-hardening coatings
    • 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
    • C08J2433/18—Homopolymers or copolymers of nitriles
    • C08J2433/20—Homopolymers or copolymers of acrylonitrile

Definitions

  • the present invention relates to a coated film, and in particular, relates to a coated film having an excellent metal vapor deposition appearance and good adhesion to the vapor deposited metal.
  • Metal vapor deposition film by selecting vapor deposition metal, characteristics such as gas barrier properties, moisture impermeability, visible / ultraviolet light shielding properties, heat ray reflectivity, conductivity, transparent conductivity, magnetic recording properties, and beauty Therefore, it is used in various applications such as packaging materials, decorative materials, window glass shielding materials, gold / silver thread materials, capacitor materials, display materials, wiring board materials, magnetic recording materials and the like.
  • the metal vapor-deposited film has a drawback that the adhesion between a polyester film known as a general base film and the vapor-deposited metal is poor.
  • the present invention has been made in view of the above circumstances, and a problem to be solved thereof is to provide a coated film having an excellent appearance of metal vapor deposition and having good adhesion to the vapor deposited metal.
  • the gist of the present invention is a coating film having a coating layer stretched in at least one direction on at least one side of a polyester film, the coating layer containing an acrylonitrile as a copolymerization component, a melamine compound
  • the coating film is formed from a coating solution containing particles having an average particle size of 0.01 to 0.3 ⁇ m.
  • the present invention it is possible to provide a coated film having an excellent appearance of metal vapor deposition and good adhesion to the vapor deposited metal, and the industrial value of the present invention is high.
  • the base film of the coated film of the present invention is made of polyester.
  • polyesters include dicarboxylic acids such as terephthalic acid, isophthalic acid, 2,6-naphthalenedicarboxylic acid, adipic acid, sebacic acid, 4,4′-diphenyldicarboxylic acid, 1,4-cyclohexyldicarboxylic acid or esters thereof.
  • It is a polyester produced by melt polycondensation with glycols such as ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, 1,4-butanediol, neopentyl glycol, and 1,4-cyclohexanedimethanol.
  • Polyesters composed of these acid components and glycol components can be produced by arbitrarily using a commonly used method. For example, a transesterification reaction between a lower alkyl ester of an aromatic dicarboxylic acid and a glycol, or a direct esterification of an aromatic dicarboxylic acid and a glycol, to form a substantially bisglycol of an aromatic dicarboxylic acid A method is employed in which an ester or a low polymer thereof is formed and then polycondensed by heating under reduced pressure. Depending on the purpose, an aliphatic dicarboxylic acid may be copolymerized.
  • polyester in the present invention examples include polyethylene terephthalate, polyethylene-2,6-naphthalate, poly-1,4-cyclohexanedimethylene terephthalate, and the like. It may be a polymerized polyester and may contain other components and additives as necessary.
  • particles can be contained for the purpose of ensuring the running property of the film and preventing scratches.
  • examples of such particles include inorganic particles such as silica, calcium carbonate, magnesium carbonate, calcium phosphate, kaolin, talc, aluminum oxide, titanium oxide, alumina, barium sulfate, calcium fluoride, lithium fluoride, zeolite, and molybdenum sulfide.
  • organic particles such as crosslinked polymer particles and calcium oxalate, and precipitated particles during the polyester production process can be used.
  • the particle size and content of the particles are selected according to the use and purpose of the film, but the average particle size (d50) is usually 0.01 to 3 ⁇ m, preferably 0.02 to 2.5 ⁇ m, more preferably It is in the range of 0.03 to 2 ⁇ m. If the average particle size exceeds 3.0 ⁇ m, the surface roughness of the film becomes too rough, or the particles are likely to fall off from the film surface. When the average particle size is less than 0.01 ⁇ m, the surface roughness is too small and sufficient slipperiness may not be obtained.
  • the particle content is usually in the range of 0.0003 to 1.0% by weight, preferably 0.0005 to 0.5% by weight, based on the polyester.
  • the particle content is less than 0.0003 wt%, the slipperiness of the film may be insufficient.
  • the content exceeds 1.0 wt%, the transparency of the film is insufficient. There are cases.
  • the thickness of the polyester film is not particularly limited, but is usually in the range of 3 to 500 ⁇ m, preferably in the range of 5 to 200 ⁇ m from the viewpoint of mechanical strength and flexibility.
  • the coating layer in the present invention is formed from an aqueous acrylic resin containing acrylonitrile as a copolymerization component, a melamine compound, and a coating solution containing particles having an average particle size of 0.01 to 0.3 ⁇ m.
  • the coating layer contains both unreacted components and reaction products of the component.
  • the coating solution in the present invention contains a water-based acrylic resin containing acrylonitrile as a copolymerization component from the viewpoint of developing strong adhesiveness with the deposited metal.
  • the content of the aqueous acrylic resin is usually 50 to 95% by weight, preferably 65 to 90% by weight, as a ratio in the nonvolatile content in the coating solution.
  • the content of the aqueous acrylic resin is out of the above ratio, the adhesion with the deposited metal may be lowered.
  • the coating solution in the present invention contains a melamine compound as a crosslinking agent.
  • a melamine compound for example, an alkylolated melamine derivative, a compound obtained by reacting an alcohol with an alkylolated melamine derivative or partially etherified, or the like can be used.
  • a copolymer of a melamine compound and another compound can be used, and in the present invention, a copolymer of urea is particularly preferable because it improves the adhesion to the deposited metal.
  • the melamine compound may be either a monomer or a dimer or higher multimer, or a mixture thereof. It is also possible to use a catalyst to increase the reactivity of the melamine compound.
  • the content of the melamine compound is usually 7 to 40% by weight, preferably 10 to 30% by weight as a ratio in the nonvolatile content in the coating solution.
  • the content of the melamine compound is out of the above ratio, the effect of improving the adhesion with the deposited metal due to the synergistic action with the aqueous acrylic resin containing acrylonitrile as the copolymerization component is not sufficiently exhibited, and the deposited metal Adhesiveness may decrease.
  • the coating liquid in the present invention preferably contains an epoxy compound in combination.
  • the epoxy compound include sorbitol polyglycidyl ether, polyglycerol polyglycidyl ether, pentaerythritol polyglycidyl ether, diglycerol polyglycidyl ether, triglycidyl tris (2-hydroxyethyl) isocyanate, glycerol polyglycidyl ether, trimethylolpropane.
  • polyglycidyl ether is mentioned.
  • glycol diglycidyl ether, polytetramethylene glycol diglycidyl ether, and monoepoxy compounds include allyl glycidyl ether, 2-ethylhexyl glycidyl ether, phenyl glycidyl ether, and glycidyl amine compounds such as N, N, N ′, N ′, -Tetraglycidyl-m-xylylenediamine, 1,3-bis (N, N-diglycidylamino) cyclohexane, etc. It is below
  • the coating solution in the present invention contains particles having an average particle diameter of 0.01 to 0.3 ⁇ m.
  • Such fine particles may be inorganic or organic fine particles. Specific examples thereof include calcium carbonate, calcium oxide, aluminum oxide, kaolin, silicon oxide, zinc oxide, crosslinked acrylic resin particles, crosslinked polystyrene resin particles, melamine. Resin particles and crosslinked silicone resin particles can be mentioned, and colloidal silica and colloidal alumina can be preferably mentioned.
  • colloidal silica As the particles in the coating solution, it is particularly preferable to use colloidal silica from the viewpoint of effectively improving the slipperiness of the film. Two or more kinds of the above fine particles may be used.
  • the content of the above particles is usually 1 to 12% by weight, preferably 1 to 6% by weight as a ratio in the nonvolatile content in the coating solution.
  • the content of the particles is too small, the slippery effect on the film surface cannot be obtained sufficiently, and there is a possibility that the film surface is damaged during film production or the film cannot be wound on a roll.
  • grains when there is too much content of particle
  • the haze of the coated film is usually 10% or less, preferably 5% or less, more preferably 2% or less, from the viewpoint of metal vapor deposition appearance.
  • the coating layer can be provided on one side or both sides, and when provided on both sides, the type of the coating layer may be the same or different.
  • the coating amount of the coating layer is usually 0.002 to 1 g / m 2 , preferably 0.005 to 0.5 g / m 2 , more preferably 0.01 to 0.2 g / m 2 as a final coating. It is. When the coating amount is less than 0.002 g / m 2 , it tends to be difficult to obtain a uniform resin layer. Therefore, uneven coating may occur on the product, and the coating layer exceeding 1 g / m 2 deteriorates the appearance of metal deposition. In addition, the slipperiness of the film may be reduced, making it difficult to handle the film.
  • the thickness of the coating layer at the above coating amount varies depending on the specific gravity of the coating layer. If the specific gravity of the coating layer is 1.2 g / cm 3 , the coating amount of 0.002 to 1 g / m 2 is applied. The thickness corresponds to 0.0017 to 0.83 ⁇ m.
  • the actual coating thickness is determined by dyeing the coated film with a heavy metal such as a ruthenium compound or an osmium compound, adjusting the section of the coated film by an ultrathin section method, and then measuring the section of the coated film with a transmission electron microscope. This can be confirmed by observing a plurality of coating layers and averaging the measured values.
  • a heavy metal such as a ruthenium compound or an osmium compound
  • examples of the metal component to be deposited include aluminum, palladium, zinc, nickel, silver, copper, gold, indium, tin, stainless steel, chromium, titanium and the like, but the most preferable metal is aluminum.
  • the metal component includes a metal oxide.
  • the thickness of the metal film to be deposited is appropriately selected depending on the end use of the metal-coated film.
  • the method of vapor deposition is generally vacuum vapor deposition, but may be a method such as electroplating or sputtering.
  • a resin protective layer may be provided on the vapor-deposited metal surface in order to provide adhesion after metal vapor deposition, particularly water-resistant adhesion and scratch resistance.
  • the surface is preferably flat. Accordingly, the roughness Ra of the coated film surface is usually 0.001 to 0.05 ⁇ m, preferably 0.001 to 0.02 ⁇ m.
  • the surface roughness was measured as follows using a surface roughness measuring machine (SE-3F) manufactured by Kosaka Laboratory. That is, from the film cross-section curve, a portion having a reference length L (2.5 mm) is extracted in the direction of the center line, the center line of the extracted portion is the x axis, and the direction of the vertical magnification is the y axis.
  • SE-3F surface roughness measuring machine
  • f (x) the value given by the following equation is represented by [ ⁇ m].
  • the center line average roughness was represented by the average value of the center line average roughness of the extracted portion obtained from 10 cross section curves from the sample film surface.
  • the tip radius of the stylus was 2 ⁇ m, the load was 30 mg, and the cutoff value was 0.08 mm.
  • Average particle diameter (d50) of particles in the film The average particle diameter ( ⁇ m) was defined as the equivalent spherical diameter of the particles at the 50% point of all particles determined by a laser diffraction scattering method (“LA-910” manufactured by Horiba, Ltd.).
  • Adhesive evaluation with deposited metal 92.9% by weight of ethyl acetate, 15% by weight of Toyo Morton “AD-502”, 1% by weight of Toyo Morton “A solution consisting of “CAT-10L” was applied at a coating amount of 1.1 g / m 2 and dried at 90 ° C. for 1 minute to prepare a paste film.
  • a solution consisting of “CAT-10L” was applied at a coating amount of 1.1 g / m 2 and dried at 90 ° C. for 1 minute to prepare a paste film.
  • the aging treatment was performed by placing in a thermostat with a humidity of 90% RH for 3 hours.
  • the obtained laminated film was formed into a strip shape having a width of 25 mm, an end portion of the strip sample was partially peeled off, and T-type peeling was performed at a rate of 100 mm / min with a peeling tester.
  • Adhesiveness was evaluated by the degree of the obtained peel strength and the peeled area of the deposited metal after peeling.
  • the peel strength was evaluated in three stages A to C shown below. A indicates the highest class and C indicates the lowest class.
  • the evaluation of the peeled area of the deposited metal was performed in the following four stages A to D. A indicates the highest class and D indicates the lowest class.
  • Metal deposition appearance The metal vapor deposition film was visually inspected under a three-wavelength lamp in a dark room to evaluate the metal vapor deposition appearance. The evaluation was performed in the following four stages A to D. A: Black metal appearance. B: Metal appearance with a very small amount of whiteness. C: White metal appearance. D: White metal appearance that can be confirmed even under a fluorescent lamp.
  • Tg about 50 ° C.
  • acrylic resin composed mainly of methyl methacrylate and ethyl methacrylate
  • A5 Acrylonitrile-containing acrylic resin (“Nicasol PK-8012P” manufactured by Nippon Carbide Industries, Ltd.)
  • A6: Tg about 25 ° C.
  • B1 Crosslinkable resin of alkylol melamine / urea copolymer MA-S ")
  • B2 Polymer type cross-linking agent having an oxazoline group branched to an acrylic resin (“Epocross WS-500” manufactured by Nippon Shokubai Co., Ltd.)
  • B3 Polyglycerol polyglycidyl ether (“Denacol EX-521” manufactured by Nagase ChemteX Corporation)
  • B4 Hexaalkylol melamine crosslinkable resin (“Beccamin J-101” manufactured by Nippon Kayaku Co., Ltd.)
  • C Silica sol aqueous dispersion having an average particle size of 0.07 ⁇ m
  • polyester raw materials used in Examples and Comparative Examples are as follows.
  • Comparative Examples 1-7, Examples 1-5 A blend of polyester 1 and polyester 2 at a weight ratio of 93/7 was used as the raw material for layer A, and polyester 1 alone was used as the raw material for layer B.
  • This film was stretched 3.7 times in the longitudinal direction while passing through a heating roll group at 85 ° C. to obtain a uniaxially oriented film.
  • a coating composition as shown in Table 1 below was applied to one side of the uniaxially oriented film.
  • this film was guided to a tenter stretching machine, stretched 4.0 times in the width direction at 100 ° C., further heat treated at 230 ° C., and then subjected to a relaxation treatment of 2% in the width direction, and the film thickness was 23 ⁇ m.
  • a coated film having a coating layer of 0.019 g / m 2 on an axially oriented polyethylene terephthalate film was obtained.
  • the haze of these films was in the range of 0.7% to 0.8%, and the surface roughness was in the range of 0.01 to 0.015 ⁇ m.
  • the obtained coated film had adhesiveness to metal deposition and metal deposition appearance as shown in Table 2 below in adhesion evaluation with metal deposition and metal deposition appearance.
  • the ratio in Table 1 represents the ratio in a dry coating film by weight%.
  • coated film of the present invention can be suitably used in applications where metal deposition is performed, for example.

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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)
  • Laminated Bodies (AREA)
  • Coating Of Shaped Articles Made Of Macromolecular Substances (AREA)

Abstract

Provided is a coated film which has an excellent metal deposition appearance when subjected to metal deposition, while exhibiting extremely good adhesion to a deposited metal. A coated film that has a coating layer, which is stretched in at least one direction, on at least one surface of a polyester film. The coating layer is formed from a coating liquid which contains an aqueous acrylic resin that contains acrylonitrile as a copolymerization component, a melamine compound, and particles having an average particle diameter of 0.01-0.3 μm.

Description

塗布フィルムCoating film
　本発明は、塗布フィルムに関するものであり、詳しくは、優れた金属蒸着外観を有し、かつ蒸着金属との間の接着性が良好な塗布フィルムに関するものである。 The present invention relates to a coated film, and in particular, relates to a coated film having an excellent metal vapor deposition appearance and good adhesion to the vapor deposited metal.
　金属蒸着フィルムは、蒸着金属を選択することにより、ガスバリアー性、水分不透過性、可視・紫外光の遮蔽性、熱線反射性、導電性、透明導電性、磁気記録性、美麗性などの特性を有するため、各種の用途、例えば、包装材料、装飾用材料、窓ガラスの遮蔽用材料、金・銀糸用材料、コンデンサー材料、表示材料、配線基板材料、磁気記録材料などに利用されている。しかしながら、金属蒸着フィルムは、一般的な基材フィルムとして知られているポリエステルフィルムと蒸着金属との接着性が悪いという欠点がある。 Metal vapor deposition film, by selecting vapor deposition metal, characteristics such as gas barrier properties, moisture impermeability, visible / ultraviolet light shielding properties, heat ray reflectivity, conductivity, transparent conductivity, magnetic recording properties, and beauty Therefore, it is used in various applications such as packaging materials, decorative materials, window glass shielding materials, gold / silver thread materials, capacitor materials, display materials, wiring board materials, magnetic recording materials and the like. However, the metal vapor-deposited film has a drawback that the adhesion between a polyester film known as a general base film and the vapor-deposited metal is poor.
　上記の接着性を改良するためには、ポリエステルフィルムと蒸着金属との間に下塗り層を設けるのが有効である。従来、下塗り層としては、各種ポリウレタンや各種ポリエステルを用いてコーティングすることによって設けられたものが知られている（例えば、特許文献１）。 In order to improve the above adhesiveness, it is effective to provide an undercoat layer between the polyester film and the deposited metal. Conventionally, as an undercoat layer, what was provided by coating using various polyurethanes or various polyesters is known (for example, patent document 1).
　上記の公報にしたがえば、蒸着金属との接着性および金属蒸着外観に優れたフィルムが得られるが、依然として高度な金属蒸着外観の要求や高度な蒸着金属との接着性に対する要求には対応できていない。 According to the above publication, a film with excellent adhesion to metal deposition and metal vapor deposition appearance can be obtained, but it still can meet the demand for high metal vapor deposition appearance and high adhesion to metal deposition. Not.
特開２０００－２３８１８３号公報JP 2000-238183 A
　本発明は、上記実情に鑑みなされたものであって、その解決課題は、優れた金属蒸着外観を有し、かつ蒸着金属との間の接着性が良好な塗布フィルムを提供することにある。 The present invention has been made in view of the above circumstances, and a problem to be solved thereof is to provide a coated film having an excellent appearance of metal vapor deposition and having good adhesion to the vapor deposited metal.
　本発明者らは、上記課題に鑑み鋭意検討した結果、特定の構成を採用することによれば、上記課題を容易に解決できることを見いだし、発明を完成するに至った。 As a result of intensive studies in view of the above problems, the present inventors have found that the above problems can be easily solved by adopting a specific configuration, and the present invention has been completed.
　すなわち、本発明の要旨は、ポリエステルフィルムの少なくとも片面に少なくとも１方向に延伸された塗布層を有する塗布フィルムであって、当該塗布層が、共重合成分としてアクリロニトリルを含有する水性アクリル樹脂、メラミン化合物、平均粒径０．０１～０．３μｍの粒子を含有する塗布液から形成されことを特徴とする塗布フィルムに存する。 That is, the gist of the present invention is a coating film having a coating layer stretched in at least one direction on at least one side of a polyester film, the coating layer containing an acrylonitrile as a copolymerization component, a melamine compound The coating film is formed from a coating solution containing particles having an average particle size of 0.01 to 0.3 μm.
　本発明よれば、優れた金属蒸着外観を有し、かつ蒸着金属との間の接着性が良好な塗布フィルムを提供することができ、本発明の工業的価値は高い。 According to the present invention, it is possible to provide a coated film having an excellent appearance of metal vapor deposition and good adhesion to the vapor deposited metal, and the industrial value of the present invention is high.
　本発明の塗布フィルムの基材フィルムは、ポリエステルからなるものである。かかるポリエステルとは、テレフタル酸、イソフタル酸、２，６－ナフタレンジカルボン酸、アジピン酸、セバシン酸、４，４’－ジフェニルジカルボン酸、１，４－シクロヘキシルジカルボン酸のようなジカルボン酸またはそのエステルとエチレングリコール、ジエチレングリコール、トリエチレングリコール、プロピレングリコール、１，４－ブタンジオール、ネオペンチルグリコール、１，４－シクロヘキサンジメタノールのようなグリコールとを溶融重縮合させて製造されるポリエステルである。これらの酸成分とグリコール成分とからなるポリエステルは、通常行われている方法を任意に使用して製造することができる。
　例えば、芳香族ジカルボン酸の低級アルキルエステルとグリコールとの間でエステル交換反応をさせるか、あるいは芳香族ジカルボン酸とグリコールとを直接エステル化させるかして、実質的に芳香族ジカルボン酸のビスグリコールエステル、またはその低重合体を形成させ、次いでこれを減圧下、加熱して重縮合させる方法が採用される。その目的に応じ、脂肪族ジカルボン酸を共重合しても構わない。 The base film of the coated film of the present invention is made of polyester. Such polyesters include dicarboxylic acids such as terephthalic acid, isophthalic acid, 2,6-naphthalenedicarboxylic acid, adipic acid, sebacic acid, 4,4′-diphenyldicarboxylic acid, 1,4-cyclohexyldicarboxylic acid or esters thereof. It is a polyester produced by melt polycondensation with glycols such as ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, 1,4-butanediol, neopentyl glycol, and 1,4-cyclohexanedimethanol. Polyesters composed of these acid components and glycol components can be produced by arbitrarily using a commonly used method.
For example, a transesterification reaction between a lower alkyl ester of an aromatic dicarboxylic acid and a glycol, or a direct esterification of an aromatic dicarboxylic acid and a glycol, to form a substantially bisglycol of an aromatic dicarboxylic acid A method is employed in which an ester or a low polymer thereof is formed and then polycondensed by heating under reduced pressure. Depending on the purpose, an aliphatic dicarboxylic acid may be copolymerized.
　本発明におけるポリエステルとしては、代表的には、ポリエチレンテレフタレートやポリエチレン－２，６－ナフタレート、ポリ－１，４－シクロヘキサンジメチレンテレフタレート等が挙げられるが、その他に上記の酸成分やグリコール成分を共重合したポリエステルであってもよく、必要に応じて他の成分や添加剤を含有していてもよい。 Typical examples of the polyester in the present invention include polyethylene terephthalate, polyethylene-2,6-naphthalate, poly-1,4-cyclohexanedimethylene terephthalate, and the like. It may be a polymerized polyester and may contain other components and additives as necessary.
　本発明におけるポリエステルフィルムには、フィルムの走行性を確保したり、キズが入ることを防いだりする等の目的で粒子を含有させることができる。このような粒子としては、例えば、シリカ、炭酸カルシウム、炭酸マグネシウム、リン酸カルシウム、カオリン、タルク、酸化アルミニウム、酸化チタン、アルミナ、硫酸バリウム、フッ化カルシウム、フッ化リチウム、ゼオライト、硫化モリブデン等の無機粒子、架橋高分子粒子、シュウ酸カルシウム等の有機粒子、さらに、ポリエステル製造工程時の析出粒子等を用いることができる。 In the polyester film of the present invention, particles can be contained for the purpose of ensuring the running property of the film and preventing scratches. Examples of such particles include inorganic particles such as silica, calcium carbonate, magnesium carbonate, calcium phosphate, kaolin, talc, aluminum oxide, titanium oxide, alumina, barium sulfate, calcium fluoride, lithium fluoride, zeolite, and molybdenum sulfide. Further, organic particles such as crosslinked polymer particles and calcium oxalate, and precipitated particles during the polyester production process can be used.
　粒子の粒径や含有量はフィルムの用途や目的に応じて選択されるが、平均粒径（ｄ５０）に関しては、通常０．０１～３μｍ、好ましくは０．０２～２．５μｍ、さらに好ましくは０．０３～２μｍの範囲である。平均粒径が３．０μｍを超えるとフィルムの表面粗度が粗くなりすぎたり、粒子がフィルム表面から脱落しやすくなったりする。平均粒径が０．０１μｍ未満では、表面粗度が小さすぎて、十分な易滑性が得られない場合がある。 The particle size and content of the particles are selected according to the use and purpose of the film, but the average particle size (d50) is usually 0.01 to 3 μm, preferably 0.02 to 2.5 μm, more preferably It is in the range of 0.03 to 2 μm. If the average particle size exceeds 3.0 μm, the surface roughness of the film becomes too rough, or the particles are likely to fall off from the film surface. When the average particle size is less than 0.01 μm, the surface roughness is too small and sufficient slipperiness may not be obtained.
　粒子含有量については、ポリエステルに対し、通常０．０００３～１．０重量％、好ましくは０．０００５～０．５重量％の範囲である。粒子含有量が０．０００３重量％未満の場合には、フィルムの易滑性が不十分な場合があり、一方、１．０重量％を超えて添加する場合にはフィルムの透明性が不十分な場合がある。 The particle content is usually in the range of 0.0003 to 1.0% by weight, preferably 0.0005 to 0.5% by weight, based on the polyester. When the particle content is less than 0.0003 wt%, the slipperiness of the film may be insufficient. On the other hand, when the content exceeds 1.0 wt%, the transparency of the film is insufficient. There are cases.
　本発明において、ポリエステルフィルムの厚さは、特に制限を受けるものではないが、通常３～５００μｍの範囲、機械強度と可撓性の点から好ましくは５～２００μｍの範囲である。 In the present invention, the thickness of the polyester film is not particularly limited, but is usually in the range of 3 to 500 μm, preferably in the range of 5 to 200 μm from the viewpoint of mechanical strength and flexibility.
　本発明における塗布層は、共重合成分としてアクリロニトリルを含有している水性アクリル樹脂、メラミン化合物、平均粒径０．０１～０．３μｍの粒子を含有する塗布液から形成される。 The coating layer in the present invention is formed from an aqueous acrylic resin containing acrylonitrile as a copolymerization component, a melamine compound, and a coating solution containing particles having an average particle size of 0.01 to 0.3 μm.
　かかる塗布層は、塗布液に含有されている成分が完全に反応していない場合、その成分の未反応物と反応生成物の双方が含まれることとなる。 When the component contained in the coating solution is not completely reacted, the coating layer contains both unreacted components and reaction products of the component.
　本発明における塗布液は、蒸着金属との強固な接着性を発現させる観点から、共重合成分としてアクリロニトリルを含有している水性アクリル樹脂を含有する。 The coating solution in the present invention contains a water-based acrylic resin containing acrylonitrile as a copolymerization component from the viewpoint of developing strong adhesiveness with the deposited metal.
　水性アクリル樹脂の含有量は、塗布液中の不揮発分中での比率として、通常５０～９５重量％、好ましくは６５～９０重量％である。水性アクリル樹脂の含有量が上記の比率を外れる場合は、蒸着金属との接着性が低下する場合がある。 The content of the aqueous acrylic resin is usually 50 to 95% by weight, preferably 65 to 90% by weight, as a ratio in the nonvolatile content in the coating solution. When the content of the aqueous acrylic resin is out of the above ratio, the adhesion with the deposited metal may be lowered.
　本発明における塗布液は、架橋剤としてメラミン化合物を含有する。かかるメラミン化合物としては、例えば、アルキロール化メラミン誘導体、アルキロール化メラミン誘導体にアルコールを反応させて部分的あるいは完全にエーテル化した化合物等が使用できる。また、メラミン化合物と他の化合物との共重合物を使用することもでき、本発明においては特に尿素を共重合したものが、蒸着金属との接着性を向上させ好ましい。 The coating solution in the present invention contains a melamine compound as a crosslinking agent. As such a melamine compound, for example, an alkylolated melamine derivative, a compound obtained by reacting an alcohol with an alkylolated melamine derivative or partially etherified, or the like can be used. In addition, a copolymer of a melamine compound and another compound can be used, and in the present invention, a copolymer of urea is particularly preferable because it improves the adhesion to the deposited metal.
　メラミン化合物は、単量体、あるいは２量体以上の多量体のいずれであってもよく、あるいはこれらの混合物を用いてもよい。また、メラミン化合物の反応性を上げるために触媒を使用することも可能である。 The melamine compound may be either a monomer or a dimer or higher multimer, or a mixture thereof. It is also possible to use a catalyst to increase the reactivity of the melamine compound.
　メラミン化合物の含有量は、塗布液中の不揮発分中での比率しとして、通常７～４０重量％、好ましくは１０～３０重量％である。メラミン化合物の含有量が上記の比率を外れる場合は、共重合成分としてアクリロニトリルを含有している水性アクリル樹脂との相乗作用による蒸着金属との接着性の向上効果が十分に発揮されず、蒸着金属との接着性が低下する場合がある。 The content of the melamine compound is usually 7 to 40% by weight, preferably 10 to 30% by weight as a ratio in the nonvolatile content in the coating solution. When the content of the melamine compound is out of the above ratio, the effect of improving the adhesion with the deposited metal due to the synergistic action with the aqueous acrylic resin containing acrylonitrile as the copolymerization component is not sufficiently exhibited, and the deposited metal Adhesiveness may decrease.
　また本発明における塗布液はエポキシ化合物を併用して含有することが好ましい。かかるエポキシ化合物としては、例えば、ソルビトールポリグリシジルエーテル、ポリグリセロールポリグリシジルエーテル、ペンタエリスリトールポリグリシジルエーテル、ジグリセロールポリグリシジルエーテル、トリグリシジルトリス（２－ヒドロキシエチル）イソシアネート、グリセロールポリグリシジルエーテル、トリメチロールプロパンポリグリシジルエーテルが挙げられる。更に、ジエポキシ化合物としては、例えば、ネオペンチルグリコールジグリシジルエーテル、１，６－ヘキサンジオールジグリシジルエーテル、レゾルシンジグリシジルエーテル、エチレングリコールジグリシジルエーテル、ポリエチレングリコールジグリシジルエーテル、プロピレングリコールジグリシジルエーテル、ポリプロピレングリコールジグリシジルエーテル、ポリテトラメチレングリコールジグリシジルエーテル、モノエポキシ化合物としては、例えば、アリルグリシジルエーテル、２－エチルヘキシルグリシジルエーテル、フェニルグリシジルエーテル、グリシジルアミン化合物としてはＮ，Ｎ，Ｎ’，Ｎ’，－テトラグリシジル－ｍ－キシリレンジアミン、１，３－ビス（Ｎ，Ｎ－ジグリシジルアミノ）シクロヘキサン等が挙げられる。本発明においては特にポリグリセロールポリグリシジルエーテルが蒸着金属との接着性を向上させ好ましい。 In addition, the coating liquid in the present invention preferably contains an epoxy compound in combination. Examples of the epoxy compound include sorbitol polyglycidyl ether, polyglycerol polyglycidyl ether, pentaerythritol polyglycidyl ether, diglycerol polyglycidyl ether, triglycidyl tris (2-hydroxyethyl) isocyanate, glycerol polyglycidyl ether, trimethylolpropane. Polyglycidyl ether is mentioned. Further, as the diepoxy compound, for example, neopentyl glycol diglycidyl ether, 1,6-hexanediol diglycidyl ether, resorcin diglycidyl ether, ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, polypropylene Examples of glycol diglycidyl ether, polytetramethylene glycol diglycidyl ether, and monoepoxy compounds include allyl glycidyl ether, 2-ethylhexyl glycidyl ether, phenyl glycidyl ether, and glycidyl amine compounds such as N, N, N ′, N ′, -Tetraglycidyl-m-xylylenediamine, 1,3-bis (N, N-diglycidylamino) cyclohexane, etc. It is below. In the present invention, polyglycerol polyglycidyl ether is particularly preferable because it improves the adhesion to the deposited metal.
　本発明における塗布液は平均粒径０．０１～０．３μｍの粒子を含有する。かかる微粒子としては、無機または有機の微粒子の何れでもよく、その具体的例としては、炭酸カルシウム、酸化カルシウム、酸化アルミニウム、カオリン、酸化珪素、酸化亜鉛、架橋アクリル樹脂粒子、架橋ポリスチレン樹脂粒子、メラミン樹脂粒子、架橋シリコーン樹脂粒子が挙げられ、コロイダルシリカ、コロイダルアルミナを好ましく挙げることができる。 The coating solution in the present invention contains particles having an average particle diameter of 0.01 to 0.3 μm. Such fine particles may be inorganic or organic fine particles. Specific examples thereof include calcium carbonate, calcium oxide, aluminum oxide, kaolin, silicon oxide, zinc oxide, crosslinked acrylic resin particles, crosslinked polystyrene resin particles, melamine. Resin particles and crosslinked silicone resin particles can be mentioned, and colloidal silica and colloidal alumina can be preferably mentioned.
　塗布液における粒子としては、フィルムの易滑性を有効に改善する効果の観点から、コロイダルシリカを用いることが特に好ましい。上記の微粒子は２種以上用いてもよい。 As the particles in the coating solution, it is particularly preferable to use colloidal silica from the viewpoint of effectively improving the slipperiness of the film. Two or more kinds of the above fine particles may be used.
　上記の粒子の含有量は、塗布液中の不揮発分中での比率として、通常１～１２重量％、好ましくは１～６重量％である。記の粒子の含有量が少なすぎる場合は、フィルム表面の易滑効果が十分に得られず、フィルムの生産時にフィルム表面に傷が入ったり、ロールにフィルムが巻けなかったりする可能性がある。また、粒子の含有量が多すぎると、金属蒸着後の金属蒸着層表面の突起が大きくなり、金属蒸着外観の美麗性を損なうことがある。 The content of the above particles is usually 1 to 12% by weight, preferably 1 to 6% by weight as a ratio in the nonvolatile content in the coating solution. When the content of the particles is too small, the slippery effect on the film surface cannot be obtained sufficiently, and there is a possibility that the film surface is damaged during film production or the film cannot be wound on a roll. Moreover, when there is too much content of particle | grains, the protrusion of the metal vapor deposition layer surface after metal vapor deposition will become large, and the beauty of the metal vapor deposition external appearance may be impaired.
　塗布フィルムのヘーズは、金属蒸着外観の観点から、通常１０％以下、好ましくは５％以下、更に好ましくは２％以下である。 The haze of the coated film is usually 10% or less, preferably 5% or less, more preferably 2% or less, from the viewpoint of metal vapor deposition appearance.
　ポリエステルフィルムまたはシートに塗布液を塗布する方法としては、原崎勇次著、槙書店、１９７９年発行、「コーティング方式」に示されるリバースロールコータ、グラビアコーター、ロッドコーター、エアドクタコーターあるいはこれら以外の塗布装置を用いてフィルム製造工程内で塗布を行う。例えば、二軸延伸フィルムに塗布層を設ける場合は、縦方向に一軸延伸したフィルムに水溶液または水分散体とされた塗布液を塗工し、乾燥または未乾燥の状態で横方向に延伸し、引続き熱処理を施す。この方法は、製膜、塗布および乾燥を同時に行えることから、製造コスト面を加味したメリットが大きいために、特に好ましく採用される方法である。 As a method of applying a coating solution to a polyester film or sheet, Yuji Harasaki, Tsuji Shoten, published in 1979, reverse roll coater, gravure coater, rod coater, air doctor coater or other coatings shown in “Coating system” Application is performed within the film manufacturing process using an apparatus. For example, when a coating layer is provided on a biaxially stretched film, a coating solution that is an aqueous solution or water dispersion is applied to a film that is uniaxially stretched in the longitudinal direction, and stretched in the transverse direction in a dry or undried state. Continue heat treatment. This method is particularly preferably employed because it can perform film formation, coating and drying at the same time, and has a great merit in consideration of manufacturing cost.
　本発明において、塗布層は片面あるいは両面に設けることができ、また、両面に設ける場合、塗布層の種類は同一でも異なっていてもよい。なお、シートまたはフィルムへの塗布性、接着性を改良するため、塗布前にシートまたはフィルムの表面に化学処理や放電処理を施してもよい。 In the present invention, the coating layer can be provided on one side or both sides, and when provided on both sides, the type of the coating layer may be the same or different. In addition, in order to improve the applicability | paintability and adhesiveness to a sheet | seat or a film, you may perform a chemical process and an electrical discharge process to the surface of a sheet | seat or a film before application | coating.
　塗布層の塗工量は、最終的な被膜として、通常０．００２～１ｇ／ｍ２、好ましくは０．００５～０．５ｇ／ｍ２、さらに好ましくは０．０１～０．２ｇ／ｍ２である。塗工量が０．００２ｇ／ｍ２未満の場合は均一な樹脂層が得難い傾向があり、そのため製品に塗布むらが生じる場合があり、１ｇ／ｍ２を超える塗布層は、金属蒸着外観の悪化やフィルムの滑り性が低下してフィルムの取扱いが困難となることがある。 The coating amount of the coating layer is usually 0.002 to 1 g / m 2 , preferably 0.005 to 0.5 g / m 2 , more preferably 0.01 to 0.2 g / m 2 as a final coating. It is. When the coating amount is less than 0.002 g / m 2 , it tends to be difficult to obtain a uniform resin layer. Therefore, uneven coating may occur on the product, and the coating layer exceeding 1 g / m 2 deteriorates the appearance of metal deposition. In addition, the slipperiness of the film may be reduced, making it difficult to handle the film.
　なお、上記の塗工量における塗布層の厚みは、塗布層の比重によって変わるが、仮に塗布層の比重を１．２ｇ／cm３とすると、塗工量０．００２～１ｇ／ｍ２は塗布厚さ０．００１７～０．８３μｍに相当する。 The thickness of the coating layer at the above coating amount varies depending on the specific gravity of the coating layer. If the specific gravity of the coating layer is 1.2 g / cm 3 , the coating amount of 0.002 to 1 g / m 2 is applied. The thickness corresponds to 0.0017 to 0.83 μm.
　また、実際の塗布厚みは、塗布フィルムをルテニウム化合物やオスミウム化合物等の重金属を用いて染色を行い、超薄切片法により塗布フィルムの断面を調整した後、透過型電子顕微鏡にて塗布フィルム断面の塗布層を複数個所観測し、その実測値を平均することで確認することができる。 The actual coating thickness is determined by dyeing the coated film with a heavy metal such as a ruthenium compound or an osmium compound, adjusting the section of the coated film by an ultrathin section method, and then measuring the section of the coated film with a transmission electron microscope. This can be confirmed by observing a plurality of coating layers and averaging the measured values.
　本発明において、蒸着する金属成分としては、アルミニウム、パラジウム、亜鉛、ニッケル、銀、銅、金、インジウム、錫、ステンレス鋼、クロム、チタン等が挙げられるが、最も好ましい金属は、アルミニウムである。なお、上記の金属成分には、金属の酸化物も含まれる。蒸着する金属膜の厚さは、金属被覆フィルムの最終用途によって適宜選択される。蒸着の方法は、一般には真空蒸着によるが、エレクトロプレーティング、スパッタリング等の方法によってもよい。なお、金属蒸着後に接着性、特に、耐水接着性や耐擦傷性等を付与するために、蒸着金属面に樹脂保護層を設けてもよい。 In the present invention, examples of the metal component to be deposited include aluminum, palladium, zinc, nickel, silver, copper, gold, indium, tin, stainless steel, chromium, titanium and the like, but the most preferable metal is aluminum. The metal component includes a metal oxide. The thickness of the metal film to be deposited is appropriately selected depending on the end use of the metal-coated film. The method of vapor deposition is generally vacuum vapor deposition, but may be a method such as electroplating or sputtering. A resin protective layer may be provided on the vapor-deposited metal surface in order to provide adhesion after metal vapor deposition, particularly water-resistant adhesion and scratch resistance.
　蒸着フィルムは表裏の美麗さが要求されるので、表面が平坦であることが好ましい。従って、塗布フィルム表面の粗さＲａは、通常０．００１～０．０５μｍ、好ましくはは０．００１～０．０２μｍである。 Since the deposited film is required to have beautiful front and back surfaces, the surface is preferably flat. Accordingly, the roughness Ra of the coated film surface is usually 0.001 to 0.05 μm, preferably 0.001 to 0.02 μm.
　以下、実施例により本発明をさらに具体的に説明するが、本発明はその要旨を越えない限り、以下の例に限定されるものではない。本発明で用いる評価方法は次に示すとおりである。 Hereinafter, the present invention will be described more specifically with reference to examples. However, the present invention is not limited to the following examples unless it exceeds the gist. The evaluation method used in the present invention is as follows.
（１）表面粗さＲａ：
　小坂研究所社製表面粗さ測定機（ＳＥ－３Ｆ）を用いて次のようにして求めた。すなわち、フィルム断面曲線から、その中心線の方向に基準長さＬ（２．５ｍｍ）の部分を抜き取り、この抜き取り部分の中心線をｘ軸、縦倍率の方向をｙ軸として粗さ曲線ｙ＝ｆ（ｘ）で表したとき、次の式で与えられた値を〔μｍ〕で表す。 (1) Surface roughness Ra:
The surface roughness was measured as follows using a surface roughness measuring machine (SE-3F) manufactured by Kosaka Laboratory. That is, from the film cross-section curve, a portion having a reference length L (2.5 mm) is extracted in the direction of the center line, the center line of the extracted portion is the x axis, and the direction of the vertical magnification is the y axis. When represented by f (x), the value given by the following equation is represented by [μm].
Figure JPOXMLDOC01-appb-M000001
Figure JPOXMLDOC01-appb-M000001
　中心線平均粗さは、試料フィルム表面から１０本の断面曲線を求め、これらの断面曲線から求めた抜き取り部分の中心線平均粗さの平均値で表した。なお、触針の先端半径は２μｍ、荷重は３０ｍｇとし、カットオフ値は０．０８ｍｍとした。 The center line average roughness was represented by the average value of the center line average roughness of the extracted portion obtained from 10 cross section curves from the sample film surface. The tip radius of the stylus was 2 μm, the load was 30 mg, and the cutoff value was 0.08 mm.
（２）ポリエステルの極限粘度：
　ポリエステルに非相溶な他のポリマー成分および顔料を除去したポリエステル１ｇを精秤し、フェノール／テトラクロロエタン＝５０／５０（重量比）の混合溶媒１００ｍｌを加えて溶解させ、３０℃で測定した。 (2) Intrinsic viscosity of polyester:
1 g of polyester from which other polymer components and pigments incompatible with polyester were removed was precisely weighed, 100 ml of a mixed solvent of phenol / tetrachloroethane = 50/50 (weight ratio) was added and dissolved, and measurement was performed at 30 ° C.
（３）フィルム中の粒子の平均粒径（ｄ５０）：
　レーザー回折散乱法（堀場製作所社製「ＬＡ－９１０」）によって求められる全粒子の５０％点にある粒子の等価球形直径をもって平均粒径（μｍ）とした。 (3) Average particle diameter (d50) of particles in the film:
The average particle diameter (μm) was defined as the equivalent spherical diameter of the particles at the 50% point of all particles determined by a laser diffraction scattering method (“LA-910” manufactured by Horiba, Ltd.).
（４）金属蒸着フィルムの作製：
　塗布フィルムの塗布面に、抵抗加熱型金属蒸着装置を用い、真空室の圧力を１０-4Ｔｏｒｒにてアルミニウムを４５０Åの厚みに蒸着した。 (4) Preparation of metal vapor deposition film:
On the coated surface of the coated film, aluminum was deposited to a thickness of 450 mm using a resistance heating type metal vapor deposition apparatus at a pressure of 10 −4 Torr in a vacuum chamber.
（５）蒸着金属との接着性評価：
　塗布フィルムと同種でコロナ処理を行った同一厚さのフィルム表面に、９２．９重量％の酢酸エチル、１５重量％の東洋モートン社製「ＡＤ－５０２」、１重量％の東洋モートン社製「ＣＡＴ－１０Ｌ」からなる溶液を塗工量１．１ｇ／ｍ２で塗布し、９０℃で１分間乾燥させて、糊フィルムを作成した。金属蒸着フィルムの蒸着薄膜層表面に、上記糊フィルムを圧着温度５０℃、圧着圧２８．９Ｎ／ｃｍ２、圧着時間１分間の条件のドライラミネート法により積層した後、積層フィルムを温度６０℃、湿度９０％ＲＨの恒温槽に３時間入れてエージング処理を行った。得られた積層フィルムを幅２５ｍｍの短冊状にし、短冊状試料の端部を一部剥離して、剥離試験機により１００ｍｍ／分の速度でＴ型剥離を行った。得られた剥離強度と剥離後の蒸着金属の剥離面積の度合で接着性の評価を行った。剥離強度の評価は以下に示すＡ～Ｃの３段階で行った。Ａは最高クラス、Ｃは最低クラスを示す。一方、蒸着金属の剥離面積の評価は以下に示すＡ～Ｄの４段階で行った。Ａは最高クラス、Ｄは最低クラスを示す。 (5) Adhesive evaluation with deposited metal:
92.9% by weight of ethyl acetate, 15% by weight of Toyo Morton “AD-502”, 1% by weight of Toyo Morton “ A solution consisting of “CAT-10L” was applied at a coating amount of 1.1 g / m 2 and dried at 90 ° C. for 1 minute to prepare a paste film. After laminating the paste film on the surface of the vapor-deposited thin film layer of the metal vapor-deposited film by a dry laminating method with a pressure bonding temperature of 50 ° C., a pressure bonding pressure of 28.9 N / cm 2 and a pressure bonding time of 1 minute, the laminated film was heated to a temperature of 60 ° C. The aging treatment was performed by placing in a thermostat with a humidity of 90% RH for 3 hours. The obtained laminated film was formed into a strip shape having a width of 25 mm, an end portion of the strip sample was partially peeled off, and T-type peeling was performed at a rate of 100 mm / min with a peeling tester. Adhesiveness was evaluated by the degree of the obtained peel strength and the peeled area of the deposited metal after peeling. The peel strength was evaluated in three stages A to C shown below. A indicates the highest class and C indicates the lowest class. On the other hand, the evaluation of the peeled area of the deposited metal was performed in the following four stages A to D. A indicates the highest class and D indicates the lowest class.
（剥離強度）
　Ａ：４Ｎ／２５ｍｍ以上
　Ｂ：２．１Ｎ／２５ｍｍ以上、４Ｎ／２５ｍｍ未満
　Ｃ：２．０Ｎ／２５ｍｍ未満 (Peel strength)
A: 4N / 25mm or more B: 2.1N / 25mm or more, less than 4N / 25mm C: Less than 2.0N / 25mm
（蒸着金属の剥離面積）
　Ａ：金属蒸着膜の剥がれが全く無い。
　Ｂ：５～１０％の金属蒸着膜の剥がれがある。
　Ｃ：１１～５０％の金属蒸着膜の剥がれがある。
　Ｄ：５１％以上の金属蒸着膜の剥がれがある。 (Deposition area of evaporated metal)
A: There is no peeling of a metal vapor deposition film.
B: There is peeling of the metal vapor deposition film of 5 to 10%.
C: There is peeling of the metal vapor deposition film of 11 to 50%.
D: There is peeling of a metal vapor deposition film of 51% or more.
（６）金属蒸着外観：
　金属蒸着フィルムを暗室の三波長ランプ下にて目視検査し、金属蒸着外観を評価した。評価は以下に示すＡ～Ｄの４段階で行った。
　Ａ：黒く引き締まった金属外観。
　Ｂ：極微量に白みを帯びた金属外観。
　Ｃ：白みを帯びた金属外観。
　Ｄ：蛍光灯下でも確認が可能な白い金属外観。 (6) Metal deposition appearance:
The metal vapor deposition film was visually inspected under a three-wavelength lamp in a dark room to evaluate the metal vapor deposition appearance. The evaluation was performed in the following four stages A to D.
A: Black metal appearance.
B: Metal appearance with a very small amount of whiteness.
C: White metal appearance.
D: White metal appearance that can be confirmed even under a fluorescent lamp.
（７）ヘーズ：
　ＪＩＳ－Ｋ７１３６に準じて、日本電色工業社製積分球式濁度計「ＮＤＨ－２０００」により塗布フィルムのヘーズを測定した。 (7) Haze:
According to JIS-K7136, the haze of the coated film was measured with an integrating sphere turbidimeter “NDH-2000” manufactured by Nippon Denshoku Industries Co., Ltd.
　以下の実施例および比較例において、塗布液成分としては下記を用いた。
Ａ１：下記の組成で構成されたＴｇ＝６５℃のポリエステル樹脂
　酸成分：テレフタル酸／イソフタル酸／５－ソジウムスルホイソフタル酸／／ジオール成分：エチレングリコール／ネオペンチルグリコール＝４９／４８／３／／５０／５０（モル％）
Ａ２：ポリウレタン樹脂（ＤＳＭネオレジン社製「ネオレッツＲ９６０」）
Ａ３：アクリル樹脂（ロームアンドハースジャパン社製「プライマルＨＡ－１６」）
Ａ４：メタクリル酸メチル、メタクリル酸エチルを主成分として構成されているＴｇ＝約５０℃のアクリル樹脂
Ａ５：アクリロニトリル含有アクリル樹脂（日本カーバイド工業社製「ニカゾールＰＫ－８０１２Ｐ」）
Ａ６：メタクリル酸メチル、メタクリル酸エチル、アクリル酸エチル、アクリロニトリルを主成分として構成されるＴｇ＝約２５℃のアクリル樹脂
Ｂ１：アルキロールメラミン／尿素共重合の架橋性樹脂（日本資材社製「ベッカミンＭＡ－Ｓ」）
Ｂ２：オキサゾリン基がアクリル系樹脂にブランチされたポリマー型架橋剤（日本触媒社製「エポクロスＷＳ－５００」）
Ｂ３：ポリグリセロールポリグリシジルエーテル（ナガセケムテックス社製「デナコールＥＸ－５２１」）
Ｂ４：ヘキサアルキロールメラミンの架橋性樹脂（日本資材社製「ベッカミンＪ－１０１」）
Ｃ：平均粒径０．０７μｍのシリカゾル水分散体 In the following examples and comparative examples, the following were used as coating solution components.
A1: Polyester resin having the following composition and Tg = 65 ° C. Acid component: terephthalic acid / isophthalic acid / 5-sodiumsulfoisophthalic acid // diol component: ethylene glycol / neopentyl glycol = 49/48/3 / / 50/50 (mol%)
A2: Polyurethane resin (“Neolet's R960” manufactured by DSM Neoresin)
A3: Acrylic resin ("Primal HA-16" manufactured by Rohm and Haas Japan)
A4: Tg = about 50 ° C. acrylic resin composed mainly of methyl methacrylate and ethyl methacrylate A5: Acrylonitrile-containing acrylic resin (“Nicasol PK-8012P” manufactured by Nippon Carbide Industries, Ltd.)
A6: Tg = about 25 ° C. acrylic resin composed mainly of methyl methacrylate, ethyl methacrylate, ethyl acrylate, and acrylonitrile B1: Crosslinkable resin of alkylol melamine / urea copolymer MA-S ")
B2: Polymer type cross-linking agent having an oxazoline group branched to an acrylic resin (“Epocross WS-500” manufactured by Nippon Shokubai Co., Ltd.)
B3: Polyglycerol polyglycidyl ether (“Denacol EX-521” manufactured by Nagase ChemteX Corporation)
B4: Hexaalkylol melamine crosslinkable resin (“Beccamin J-101” manufactured by Nippon Kayaku Co., Ltd.)
C: Silica sol aqueous dispersion having an average particle size of 0.07 μm
　実施例、比較例中で使用したポリエステル原料は次のとおりである。
（ポリエステル１）：実質的に粒子を含有しない、極限粘度０．６６のポリエチレンテレフタレート
（ポリエステル２）：平均粒径（ｄ５０）が３．２μmの非晶質シリカを０．６重量％含有する、極限粘度０．６５のポリエチレンテレフタレート The polyester raw materials used in Examples and Comparative Examples are as follows.
(Polyester 1): Polyethylene terephthalate having an intrinsic viscosity of 0.66 substantially free of particles (Polyester 2): containing 0.6% by weight of amorphous silica having an average particle diameter (d50) of 3.2 μm, Polyethylene terephthalate with intrinsic viscosity of 0.65
　比較例１～７、実施例１～５：
　ポリエステル１とポリエステル２とを重量比で９３／７でブレンドしたものをＡ層、ポリエステル１のみのものをＢ層の原料として、二台のベント式二軸押出機にそれぞれを供給し、２８５℃に加熱溶融し、Ａ層を二分配して再外層（表層）、Ｂ層を中間層とする二種三層（Ａ／Ｂ／Ａ）の層構成で共押出し、静電密着法を用いて表面温度４０℃～５０℃の鏡面冷却ドラムに密着させながら冷却固化させて、厚み構成比がＡ／Ｂ／Ａ＝１／８／１となる未延伸ポリエチレンテレフタレートフィルムを作成した。このフィルムを８５℃の加熱ロール群を通過させながら長手方向に３．７倍延伸し、一軸配向フィルムとした。この一軸配向フィルムの片面に、下記表１に示すとおりの塗布組成物を塗布した。次いでこのフィルムをテンター延伸機に導き、１００℃で幅方向に４．０倍延伸し、さらに２３０℃で熱処理を施した後、幅方向に２％の弛緩処理を行い、フィルム厚みが２３μｍの二軸配向ポリエチレンテレフタレートフィルムの上に０．０１９ｇ／ｍ２の量の塗布層を設けた塗布フィルムを得た。これらのフィルムのヘーズは０．７％～０．８％の範囲にあり、表面粗さは０．０１～０．０１５μｍの範囲にあった。得られた塗布フィルムは、蒸着金属との接着性評価および金属蒸着外観において、下記表２に示すとおりの蒸着金属との接着性と金属蒸着外観を有していた。なお、表１中の比率は乾燥塗膜中での比率を重量％で表している。 Comparative Examples 1-7, Examples 1-5:
A blend of polyester 1 and polyester 2 at a weight ratio of 93/7 was used as the raw material for layer A, and polyester 1 alone was used as the raw material for layer B. To the outer layer (surface layer) and the B layer as an intermediate layer, and coextruded in a layer configuration of two types and three layers (A / B / A) using an electrostatic adhesion method. The film was cooled and solidified while closely contacting a mirror surface cooling drum having a surface temperature of 40 ° C. to 50 ° C. to prepare an unstretched polyethylene terephthalate film having a thickness composition ratio of A / B / A = 1/8/1. This film was stretched 3.7 times in the longitudinal direction while passing through a heating roll group at 85 ° C. to obtain a uniaxially oriented film. A coating composition as shown in Table 1 below was applied to one side of the uniaxially oriented film. Next, this film was guided to a tenter stretching machine, stretched 4.0 times in the width direction at 100 ° C., further heat treated at 230 ° C., and then subjected to a relaxation treatment of 2% in the width direction, and the film thickness was 23 μm. A coated film having a coating layer of 0.019 g / m 2 on an axially oriented polyethylene terephthalate film was obtained. The haze of these films was in the range of 0.7% to 0.8%, and the surface roughness was in the range of 0.01 to 0.015 μm. The obtained coated film had adhesiveness to metal deposition and metal deposition appearance as shown in Table 2 below in adhesion evaluation with metal deposition and metal deposition appearance. In addition, the ratio in Table 1 represents the ratio in a dry coating film by weight%.
Figure JPOXMLDOC01-appb-T000002
Figure JPOXMLDOC01-appb-T000002
Figure JPOXMLDOC01-appb-T000003
Figure JPOXMLDOC01-appb-T000003
　本発明の塗布フィルムは、例えば、金属蒸着が施される用途において好適に利用することができる。 The coated film of the present invention can be suitably used in applications where metal deposition is performed, for example.

Claims (5)

  1. 　ポリエステルフィルムの少なくとも片面に少なくとも１方向に延伸された塗布層を有する塗布フィルムであって、当該塗布層が、共重合成分としてアクリロニトリルを含有する水性アクリル樹脂、メラミン化合物、平均粒径０．０１～０．３μｍの粒子を含有する塗布液から形成されことを特徴とする塗布フィルム。 A coating film having a coating layer stretched in at least one direction on at least one side of a polyester film, the coating layer comprising an aqueous acrylic resin containing acrylonitrile as a copolymerization component, a melamine compound, an average particle size of 0.01 to A coated film formed from a coating solution containing 0.3 μm particles.
  2. 　塗布液中の不揮発分中での比率として、水性アクリル樹脂の含有量が５０～９５重量％、メラミン化合物の含有量が７～４０重量％、平均粒径０．０１～０．３μｍの粒子の含有量が１～１２重量％である請求項１に記載の塗布フィルム。 The ratio of the non-volatile content in the coating solution is 50 to 95% by weight of the aqueous acrylic resin, 7 to 40% by weight of the melamine compound, and an average particle size of 0.01 to 0.3 μm. The coated film according to claim 1, wherein the content is 1 to 12% by weight.
  3. 　メラミン化合物が尿素を共重合成分として含有する請求項１又は２に記載の塗布フィルム。 The coated film according to claim 1 or 2, wherein the melamine compound contains urea as a copolymerization component.
  4. 　塗布層の塗工量が０．００２～１ｇ／ｍ２である請求項１～３の何れかに記載の塗布フィルム。 The coated film according to any one of claims 1 to 3, wherein the coating amount of the coating layer is 0.002 to 1 g / m 2 .
  5. 　塗布層の表面に金属蒸着層を有する請求項１～４の何れかに記載の塗布フィルム。 The coated film according to any one of claims 1 to 4, further comprising a metal vapor-deposited layer on the surface of the coated layer.
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Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH07195640A (en) * 1993-12-28 1995-08-01 Teijin Ltd Laminated polyester film and vapor deposition film
JPH1158652A (en) * 1997-08-28 1999-03-02 Teijin Ltd Packaging polyester film
JP2000141566A (en) * 1998-11-10 2000-05-23 Mitsubishi Polyester Film Copp Coated film
JP2004315563A (en) * 2003-04-11 2004-11-11 Mitsubishi Polyester Film Copp Biaxially oriented polyester film
JP2006249210A (en) * 2005-03-10 2006-09-21 Mitsubishi Polyester Film Copp Light scattering biaxially stretched polyester film
WO2008053756A1 (en) * 2006-10-30 2008-05-08 Toyo Boseki Kabushiki Kaisha Polyester coating film for use in rubber laminate, rubber-polyester film laminate, process for production of the laminate, and composite material
JP2008208223A (en) * 2007-02-27 2008-09-11 Mitsubishi Plastics Ind Ltd Laminated polyester film for antireflection film
JP2009154543A (en) * 2009-04-06 2009-07-16 Mitsubishi Plastics Inc Coating film
WO2012020722A1 (en) * 2010-08-10 2012-02-16 東レ株式会社 Laminated polyester film and optical laminated film using same

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH07195640A (en) * 1993-12-28 1995-08-01 Teijin Ltd Laminated polyester film and vapor deposition film
JPH1158652A (en) * 1997-08-28 1999-03-02 Teijin Ltd Packaging polyester film
JP2000141566A (en) * 1998-11-10 2000-05-23 Mitsubishi Polyester Film Copp Coated film
JP2004315563A (en) * 2003-04-11 2004-11-11 Mitsubishi Polyester Film Copp Biaxially oriented polyester film
JP2006249210A (en) * 2005-03-10 2006-09-21 Mitsubishi Polyester Film Copp Light scattering biaxially stretched polyester film
WO2008053756A1 (en) * 2006-10-30 2008-05-08 Toyo Boseki Kabushiki Kaisha Polyester coating film for use in rubber laminate, rubber-polyester film laminate, process for production of the laminate, and composite material
JP2008208223A (en) * 2007-02-27 2008-09-11 Mitsubishi Plastics Ind Ltd Laminated polyester film for antireflection film
JP2009154543A (en) * 2009-04-06 2009-07-16 Mitsubishi Plastics Inc Coating film
WO2012020722A1 (en) * 2010-08-10 2012-02-16 東レ株式会社 Laminated polyester film and optical laminated film using same

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