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WO2013001933A1 - Film de revêtement - Google Patents

Film de revêtement Download PDF

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Publication number
WO2013001933A1
WO2013001933A1 PCT/JP2012/062671 JP2012062671W WO2013001933A1 WO 2013001933 A1 WO2013001933 A1 WO 2013001933A1 JP 2012062671 W JP2012062671 W JP 2012062671W WO 2013001933 A1 WO2013001933 A1 WO 2013001933A1
Authority
WO
WIPO (PCT)
Prior art keywords
coating
coating layer
film
polyester
weight
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/JP2012/062671
Other languages
English (en)
Japanese (ja)
Inventor
川崎泰史
木村秀孝
藤田真人
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Mitsubishi Chemical Corp
Original Assignee
Mitsubishi Plastics Inc
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Mitsubishi Plastics Inc filed Critical Mitsubishi Plastics Inc
Publication of WO2013001933A1 publication Critical patent/WO2013001933A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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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
    • B32B27/18—Layered products comprising a layer of synthetic resin characterised by the use of special additives
    • 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
    • C08J7/042—Coating with two or more layers, where at least one layer of a composition contains 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
    • 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
    • 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
    • B32B2307/40—Properties of the layers or laminate having particular optical properties
    • B32B2307/416—Reflective
    • 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
    • C08J2467/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
    • C08J2467/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds

Definitions

  • the present invention relates to a coating film, for example, a coating film suitable for applications requiring adhesion with a conductive layer and reduction of interference unevenness due to reflection of external light, such as a transparent electrode such as a touch panel and an electromagnetic shielding film. It is.
  • polyester films have been used for various optical films, and are also used as substrates for transparent electrodes such as touch panels and transparent conductive films such as electromagnetic shielding films.
  • a transparent conductive film conventionally, a technique in which ITO (indium tin oxide) or the like is formed by a dry process such as vacuum deposition or sputtering has been the mainstream.
  • the dry process needs to be evacuated, and has the disadvantages of low processing speed and low productivity.
  • the ITO film formed by these processes does not have sufficient flexibility, there is a problem that a crack or the like is generated during a post-processing step or a punching step, resulting in a defect in which the surface resistance does not sufficiently occur.
  • Patent Document 1 a method of forming a transparent conductive layer by a wet process (a method of applying a conductive material solution) has been proposed. Since the wet process does not need to be evacuated and the processing speed can be increased, productivity can be improved. Moreover, since it is excellent in a flexibility, there also exists an advantage that generation
  • wet processes include transparent conductive polymers such as polythiophene (Patent Documents 1 and 2). However, the adhesion with the polyester film may not be sufficient.
  • the side of the transparent conductive film opposite to the side on which the conductive layer is formed is often subjected to a hard coat process in order to improve performance such as scratch prevention and surface hardness.
  • a hard coat process in order to improve the adhesion between the polyester film used as a substrate and the hard coat layer, an easily adhesive coating layer is generally provided as an intermediate layer. For this reason, interference unevenness occurs unless the refractive index of the three layers of the polyester film, the easily adhesive coating layer, and the hard coat layer is taken into consideration.
  • the refractive index of the coating layer for reducing interference unevenness is considered to be around the geometric mean of the refractive index of the polyester film of the substrate and the refractive index of the hard coat layer, and is adjusted to the refractive index around this. Ideally. Since the refractive index of the polyester film is high, it is generally necessary to design the coating layer with a high refractive index.
  • An example of improving interference unevenness by increasing the refractive index of the coating layer is, for example, a method of combining a metal chelate compound having a high refractive index and a resin in the coating layer.
  • the stability of the coating solution may not be sufficient depending on the combination due to the instability of the metal chelate in the aqueous solution, which may lead to an increase in the liquid exchange work when producing for a long time.
  • the adhesiveness with a hard-coat layer may fall if it carries out moisture-proof heat processing (patent document 3).
  • a high refractive index material usually used is inferior in adhesion to a surface functional layer such as a hard coat layer, a coating layer that can effectively improve adhesion even when combined with a high refractive index material is required. Yes.
  • the present invention has been made in view of the above circumstances, and the solution is to have excellent adhesion to the conductive layer, and to reduce interference unevenness due to external light reflection and various surface functional layers such as a hard coat layer. It is in providing the coating film excellent in adhesiveness.
  • the gist of the present invention is to have a first coating layer formed from a coating solution containing a polyester resin and an oxazoline compound on one side of a polyester film, and a metal oxide and two or more types on the other side.
  • the coating layer is formed from a coating solution containing a cross-linking agent, and the absolute reflectance of the coating layer surface has one minimum value in the wavelength range of 400 to 800 nm, and the absolute reflectance at the minimum value is It exists in the coating film characterized by having the 2nd coating layer which is 4.0% or more.
  • the adhesiveness with the conductive layer is excellent, and when various surface functional layers such as a hard coat layer are laminated, there is little interference unevenness due to reflection of external light, and the adhesiveness with various surface functional layers is excellent.
  • the base film for forming the structure of surface functional layers such as a conductive layer / base film / hard coat layer, can be provided, and its industrial value is high.
  • the polyester film constituting the coated film of the present invention may have a single layer structure or a multilayer structure, and may have four or more layers as long as the gist of the present invention is not exceeded other than the two-layer or three-layer structure. It may be a multilayer and is not particularly limited.
  • the polyester may be a homopolyester or a copolyester.
  • a homopolyester those obtained by polycondensation of an aromatic dicarboxylic acid and an aliphatic glycol are preferred.
  • the aromatic dicarboxylic acid include terephthalic acid and 2,6-naphthalenedicarboxylic acid
  • examples of the aliphatic glycol include ethylene glycol, diethylene glycol, and 1,4-cyclohexanedimethanol.
  • Typical polyester includes polyethylene terephthalate and the like.
  • examples of the dicarboxylic acid component of the copolyester include isophthalic acid, phthalic acid, terephthalic acid, 2,6-naphthalenedicarboxylic acid, adipic acid, sebacic acid, and oxycarboxylic acid (for example, p-oxybenzoic acid).
  • examples of the glycol component include one or more types such as ethylene glycol, diethylene glycol, propylene glycol, butanediol, 4-cyclohexanedimethanol, neopentyl glycol and the like.
  • the polymerization catalyst for polyester is not particularly limited, and conventionally known compounds can be used. Examples thereof include antimony compounds, titanium compounds, germanium compounds, manganese compounds, aluminum compounds, magnesium compounds, calcium compounds and the like.
  • an ultraviolet absorber can be contained in order to improve the weather resistance of the film and to prevent deterioration of the liquid crystal or the like of a liquid crystal display used for a touch panel or the like.
  • the ultraviolet absorber is not particularly limited as long as it is a compound that absorbs ultraviolet rays and can withstand the heat applied in the production process of the polyester film.
  • an organic ultraviolet absorber there are an organic ultraviolet absorber and an inorganic ultraviolet absorber, and an organic ultraviolet absorber is preferable from the viewpoint of transparency.
  • an organic type ultraviolet absorber For example, a cyclic imino ester type, a benzotriazole type, a benzophenone type etc. are mentioned. From the viewpoint of durability, a cyclic imino ester type and a benzotriazole type are more preferable. It is also possible to use two or more ultraviolet absorbers in combination.
  • the polyester film it is preferable to blend particles mainly for the purpose of imparting slipperiness and preventing the occurrence of scratches in each step.
  • the kind of the particle to be blended is not particularly limited as long as it is a particle capable of imparting slipperiness.
  • Specific examples thereof include silica, calcium carbonate, magnesium carbonate, barium carbonate, calcium sulfate, calcium phosphate, and phosphoric acid.
  • examples include inorganic particles such as magnesium, kaolin, aluminum oxide, and titanium oxide, and organic particles such as acrylic resin, styrene resin, urea resin, phenol resin, epoxy resin, and benzoguanamine resin.
  • precipitated particles obtained by precipitating and finely dispersing a part of a metal compound such as a catalyst during the polyester production process can also be used.
  • the shape of the particles to be used is not particularly limited, and any of a spherical shape, a block shape, a rod shape, a flat shape, and the like may be used. Moreover, there is no restriction
  • the average particle diameter of the particles is usually 0.01 to 5 ⁇ m, preferably 0.01 to 3 ⁇ m. If the average particle size is less than 0.01 ⁇ m, the slipperiness may not be sufficiently imparted, or the particles may be aggregated to make the dispersibility insufficient, thereby reducing the transparency of the film. On the other hand, when it exceeds 5 ⁇ m, the surface roughness of the film becomes too rough, and there may be a problem when various surface functional layers and the like are applied in a subsequent process.
  • the content of particles in the polyester layer is usually less than 5% by weight, preferably 0.0003 to 3% by weight.
  • the transparency of the film becomes high and the film becomes a good film, but the slipperiness may be insufficient. There are cases where improvement is required. Further, when the particle content exceeds 5% by weight, the transparency of the film may be insufficient.
  • the method for adding particles to the polyester layer is not particularly limited, and a conventionally known method can be adopted.
  • it can be added at any stage for producing the polyester constituting each layer, but it is preferably added after completion of esterification or transesterification.
  • a method of blending a slurry of particles dispersed in ethylene glycol or water with a vented kneading extruder and a polyester raw material, or a blending of dried particles and a polyester raw material using a kneading extruder is done by methods.
  • antioxidants In addition to the above-mentioned particles, conventionally known antioxidants, antistatic agents, heat stabilizers, lubricants, dyes, pigments and the like can be added to the polyester film as necessary.
  • the thickness of the polyester film is not particularly limited as long as it can be formed into a film, but is usually 10 to 300 ⁇ m, preferably 25 to 250 ⁇ m.
  • a production example of the polyester film will be specifically described, but is not limited to the following production example. That is, a method of using the polyester raw material described above and cooling and solidifying a molten sheet extruded from a die with a cooling roll to obtain an unstretched sheet is preferable. In this case, in order to improve the flatness of the sheet, it is preferable to improve the adhesion between the sheet and the rotary cooling drum, and an electrostatic application adhesion method or a liquid application adhesion method is preferably employed. Next, the obtained unstretched sheet is stretched in the biaxial direction. In that case, first, the unstretched sheet is stretched in one direction by a roll or a tenter type stretching machine.
  • the stretching temperature is usually 70 to 120 ° C., preferably 80 to 110 ° C., and the stretching ratio is usually 2.5 to 7 times, preferably 3.0 to 6 times.
  • the film is stretched in the direction perpendicular to the first stretching direction.
  • the stretching temperature is usually 70 to 170 ° C.
  • the stretching ratio is usually 3.0 to 7 times, preferably 3.5 to 6 times. is there.
  • heat treatment is performed at a temperature of 180 to 270 ° C. under tension or relaxation within 30% to obtain a biaxially oriented film.
  • a method in which stretching in one direction is performed in two or more stages can be employed. In that case, it is preferable to carry out so that the draw ratios in the two directions finally fall within the above ranges.
  • the simultaneous biaxial stretching method can be adopted for the production of the polyester film.
  • the simultaneous biaxial stretching method is a method in which the above-mentioned unstretched sheet is stretched and oriented simultaneously in the machine direction and the width direction in a state where the temperature is usually controlled at 70 to 120 ° C., preferably 80 to 110 ° C. Is 4 to 50 times, preferably 7 to 35 times, and more preferably 10 to 25 times in terms of area magnification. Subsequently, heat treatment is performed at a temperature of 170 to 250 ° C. under tension or under relaxation within 30% to obtain a stretched oriented film.
  • a conventionally known stretching method such as a screw method, a pantograph method, or a linear driving method can be employed.
  • the coating layer constituting the coating film of the present invention
  • it may be provided by in-line coating which treats the film surface during the process of forming a polyester film, or offline coating which is applied outside the system on a once produced film may be adopted. Since the coating can be performed simultaneously with the film formation, the production can be handled at a low cost, and therefore in-line coating is preferably used.
  • the in-line coating is not limited to the following, for example, in the sequential biaxial stretching, a coating treatment can be performed particularly before the lateral stretching after the longitudinal stretching is finished.
  • a coating treatment can be performed particularly before the lateral stretching after the longitudinal stretching is finished.
  • the coating layer is provided on the polyester film by in-line coating, it is possible to apply at the same time as the film formation, and the coating layer can be processed at a high temperature in the heat treatment process of the polyester film after stretching. Performances such as adhesion to various surface functional layers that can be formed on the layer and heat-and-moisture resistance can be improved.
  • the thickness of an application layer can also be changed with a draw ratio, and compared with offline coating, thin film coating can be performed more easily. That is, a film suitable as a polyester film can be produced by in-line coating, particularly coating before stretching.
  • a polyester film has a first coating layer formed from a coating solution containing a polyester resin and an oxazoline compound on one surface, and a metal oxide and two or more types of crosslinking agents on the other surface. And a second coating layer having an absolute reflectance of one minimum value in the wavelength range of 400 to 800 nm and an absolute reflectance of 4.0% or more at the minimum value. Is an essential requirement.
  • the first coating layer is a coating layer for improving the adhesion with the conductive layer, and can be used particularly for improving the adhesion with a conductive polymer such as polythiophene or polyaniline.
  • the present inventors found out that the untreated polyester film has poor adhesion to the conductive polymer, and examined various resin layers by coating for improving adhesion. Adhesion could be improved by laminating the resin layer, but it turned out that whitening that increases haze may occur due to the heating process after forming the transparent conductive layer or moisture-resistant heat treatment, and improvement is necessary. . Various studies were conducted to clear the two characteristics of improving adhesion and suppressing haze rise by heat treatment, and found that the problem could be solved by combining polyester resin and oxazoline compound.
  • the polyester resin used for forming the first coating layer includes, for example, those composed of the following polyvalent carboxylic acid and polyvalent hydroxy compound as main constituent components. That is, as the polyvalent carboxylic acid, terephthalic acid, isophthalic acid, orthophthalic acid, phthalic acid, 4,4′-diphenyldicarboxylic acid, 2,5-naphthalenedicarboxylic acid, 1,5-naphthalenedicarboxylic acid, and 2,6 -Naphthalenedicarboxylic acid, 2,7-naphthalenedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid, 2-potassium sulfoterephthalic acid, 5-sodium sulfoisophthalic acid, adipic acid, azelaic acid, sebacic acid, dodecanedicarboxylic acid, glutar Acid, succinic acid, trimellitic acid, trimesic acid, pyromellitic acid, trimellitic anhydride
  • ethylene As the polyvalent hydroxy compound, ethylene Recall, 1,2-propylene glycol, 1,3-propylene glycol, 1,3-propanediol, 1,4-butanediol, 1,6-hexanediol, 2-methyl-1,5-pentanediol , Neopentyl glycol, 1,4-cyclohexanedimethanol, p-xylylene glycol, bisphenol A-ethylene glycol adduct, diethylene glycol, triethylene glycol, polyethylene glycol, polypropylene glycol Polytetramethylene glycol, polytetramethylene oxide glycol, dimethylolpropionic acid, glycerin, trimethylolpropane, sodium dimethylolethylsulfonate, potassium dimethylolpropionate, and the like can be used. One or more compounds may be appropriately selected from these compounds, and a polyester resin may be synthesized by a conventional polycondensation reaction.
  • the oxazoline compound used for the formation of the first coating layer is a compound having an oxazoline group in the molecule, and a polymer containing an oxazoline group is particularly preferred, and the addition-polymerizable oxazoline group-containing monomer alone or with other monomers It can be obtained by polymerization.
  • Addition-polymerizable oxazoline group-containing monomers include 2-vinyl-2-oxazoline, 2-vinyl-4-methyl-2-oxazoline, 2-vinyl-5-methyl-2-oxazoline, 2-isopropenyl-2-oxazoline, Examples thereof include 2-isopropenyl-4-methyl-2-oxazoline, 2-isopropenyl-5-ethyl-2-oxazoline, and the like, and one or a mixture of two or more thereof can be used. Of these, 2-isopropenyl-2-oxazoline is preferred because it is easily available industrially.
  • the other monomer is not particularly limited as long as it is a monomer copolymerizable with an addition polymerizable oxazoline group-containing monomer.
  • alkyl (meth) acrylate (alkyl groups include methyl, ethyl, n-propyl, isopropyl, (Meth) acrylic acid esters such as n-butyl group, isobutyl group, t-butyl group, 2-ethylhexyl group, cyclohexyl group); acrylic acid, methacrylic acid, itaconic acid, maleic acid, fumaric acid, crotonic acid, styrene
  • Unsaturated carboxylic acids such as sulfonic acid and its salts (sodium salt, potassium salt, ammonium salt, tertiary amine salt, etc.); Unsaturated nitriles such as acrylonitrile, methacrylonitrile; (meth) acrylamide, N-alky
  • a polymer other than the polyester resin and a crosslinking agent other than the oxazoline compound are used in combination within the scope of the present invention. It is also possible. Specific examples of the polymer include acrylic resin, polyurethane resin, polyalkylene glycol, polyalkyleneimine, cellulose, and starches.
  • a crosslinking agent an epoxy compound, a melamine compound, an isocyanate type compound, a carbodiimide type compound, a silane coupling compound, etc. are mentioned. Among these, an epoxy compound is preferably used from the viewpoint that adhesion is further improved.
  • particles can be used in combination with the formation of the first coating layer for the purpose of improving the adhesion and slipping property of the coating layer.
  • the second coating layer is designed to reduce interference unevenness due to external light after the surface functional layer such as a hard coat layer is formed, and is provided to improve the adhesion to the surface functional layer.
  • the metal oxide used for forming the second coating layer is mainly used for adjusting the refractive index of the coating layer.
  • the refractive index of the resin used in the coating layer is low, it is preferable to use a metal oxide having a high refractive index, and it is preferable to use a refractive index of 1.7 or more.
  • the metal oxide include, for example, zirconium oxide, titanium oxide, tin oxide, yttrium oxide, antimony oxide, indium oxide, zinc oxide, antimontin oxide, indium tin oxide, and the like. You may use 2 or more types. Among these, zirconium oxide and titanium oxide are more preferably used. In particular, zirconium oxide is more preferably used from the viewpoint of weather resistance.
  • the metal oxide is preferably used in the form of particles because there is a concern that the adhesion may be lowered depending on the use form, and the average particle size is preferably 100 nm or less, more preferably from the viewpoint of transparency. It is 50 nm or less, more preferably 25 nm or less.
  • Two or more types of cross-linking agents are used to improve the adhesion with a surface functional layer such as a hard coat layer provided on the coating layer.
  • the present inventors have found that the adhesion can be improved even with one kind of crosslinking agent, but the adhesion can be further improved by using two or more kinds of crosslinking agents in combination, and in particular the wet heat test. It was found that the later adhesion can be improved.
  • crosslinking agent examples include oxazoline compounds, epoxy compounds, melamine compounds, isocyanate compounds, carbodiimide compounds, silane coupling compounds, and the like.
  • crosslinking agents from the viewpoint of good adhesion, it is particularly preferable to use an oxazoline compound or an epoxy compound, and it is more preferable to use an oxazoline compound and an epoxy compound in combination.
  • the same compound as that used for the first coating layer can be used.
  • epoxy compound examples include condensates of epichlorohydrin and ethylene glycol, polyethylene glycol, glycerin, polyglycerin, bisphenol A and other hydroxyl groups and amino groups, such as polyepoxy compounds, diepoxy compounds, monoepoxy compounds, Examples include glycidylamine compounds.
  • polyepoxy compound examples include sorbitol polyglycidyl ether, polyglycerol polyglycidyl ether, pentaerythritol polyglycidyl ether, diglycerol polyglycidyl ether, triglycidyl tris (2-hydroxyethyl) isocyanate, glycerol polyglycidyl ether, trimethylolpropane.
  • polyglycidyl ether and diepoxy compound examples include neopentyl glycol diglycidyl ether, 1,6-hexanediol diglycidyl ether, resorcin diglycidyl ether, ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, and propylene glycol diglycidyl ether.
  • Polypropylene glycol diglycidyl ether polypropylene glycol diglycidyl ether, poly Examples of tetramethylene 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-xylyl. Examples include range amine and 1,3-bis (N, N-diglycidylamino) cyclohexane.
  • an alkylolated melamine derivative a compound obtained by reacting an alcohol with an alkylolated melamine derivative or partially etherified, or a mixture thereof can be used.
  • alcohol used for etherification methyl alcohol, ethyl alcohol, isopropyl alcohol, n-butanol, isobutanol and the like are preferably used.
  • a melamine compound either a monomer or a multimer more than a dimer may be sufficient, or a mixture thereof may be used.
  • a product obtained by co-condensing urea or the like with a part of melamine can be used, and a catalyst can be used to increase the reactivity of the melamine compound.
  • the isocyanate compound is a compound having an isocyanate derivative structure typified by isocyanate or blocked isocyanate.
  • isocyanate include aromatic isocyanates such as tolylene diisocyanate, xylylene diisocyanate, methylene diphenyl diisocyanate, phenylene diisocyanate, and naphthalene diisocyanate, and aromatic rings such as ⁇ , ⁇ , ⁇ ′, ⁇ ′-tetramethylxylylene diisocyanate.
  • Aliphatic isocyanates such as aliphatic isocyanate, methylene diisocyanate, propylene diisocyanate, lysine diisocyanate, trimethylhexamethylene diisocyanate, hexamethylene diisocyanate, cyclohexane diisocyanate, methylcyclohexane diisocyanate, isophorone diisocyanate, methylene bis (4-cyclohexyl isocyanate), isopropylidene dicyclohexyl diisocyanate
  • Alicyclic isocyanates such as bets are exemplified.
  • polymers and derivatives such as burettes, isocyanurates, uretdiones, and carbodiimide modified products of these isocyanates are also included. These may be used alone or in combination.
  • isocyanates aliphatic isocyanates or alicyclic isocyanates are more preferable than aromatic isocyanates in order to avoid yellowing due to ultraviolet rays.
  • the blocking agent When used in the state of blocked isocyanate, the blocking agent includes, for example, bisulfites, phenolic compounds such as phenol, cresol, and ethylphenol, and alcohols such as propylene glycol monomethyl ether, ethylene glycol, benzyl alcohol, methanol, and ethanol.
  • active methylene compounds such as dimethyl malonate, diethyl malonate, methyl acetoacetate, ethyl acetoacetate and acetylacetone, mercaptan compounds such as butyl mercaptan and dodecyl mercaptan, lactam compounds such as ⁇ -caprolactam and ⁇ -valerolactam , Amine compounds such as diphenylaniline, aniline, ethyleneimine, acetanilide, acid amide compounds of acetic acid amide, formaldehyde, acetal Examples include oxime compounds such as dooxime, acetone oxime, methyl ethyl ketone oxime, and cyclohexanone oxime, and these may be used alone or in combination of two or more.
  • the isocyanate compound may be used alone, or may be used as a mixture or a combination with various polymers. In the sense of improving the dispersibility and crosslinkability of the isocyanate compound, it is preferable to use a mixture or a bond with a polyester resin or a urethane resin.
  • Carbodiimide compounds are particularly used for improving adhesion and the like.
  • a polycarbodiimide compound having two or more carbodiimide or carbodiimide derivative structures in the molecule is preferable.
  • the carbodiimide compound can be synthesized by a conventionally known technique, and generally a condensation reaction of a diisocyanate compound is used.
  • the diisocyanate compound is not particularly limited, and any of aromatic and aliphatic compounds can be used.
  • tolylene diisocyanate, xylene diisocyanate, diphenylmethane diisocyanate, phenylene diisocyanate, naphthalene diisocyanate, hexa examples include methylene diisocyanate, trimethylhexamethylene diisocyanate, cyclohexane diisocyanate, methylcyclohexane diisocyanate, isophorone diisocyanate, dicyclohexyl diisocyanate, and dicyclohexylmethane diisocyanate.
  • cross-linking agents are used in a design that improves the performance of the coating layer by reacting in the drying process or film forming process. It can be inferred that unreacted products of these crosslinking agents, compounds after the reaction, or mixtures thereof exist in the finished coating layer.
  • the second coating layer in order to improve the coating appearance, reduce interference unevenness when various surface functional layers such as a hard coat layer are laminated on the coating surface, improve transparency and adhesion, etc. It is preferable to use various polymers.
  • the polymer examples include polyester resin, acrylic resin, urethane resin, polyvinyl (polyvinyl alcohol, polyvinyl chloride, vinyl chloride vinyl acetate copolymer, etc.), polyalkylene glycol, polyalkyleneimine, methylcellulose, hydroxycellulose, starches. Etc.
  • a polyester resin, an acrylic resin, or a urethane resin from the viewpoint of improving adhesion with a surface functional layer such as a hard coat layer and improving the appearance of coating.
  • a polyester resin is particularly preferable from the viewpoint that a large number of aromatic compounds such as a benzene ring can be contained in the molecule, thereby increasing the refractive index.
  • the compound having a condensed polycyclic aromatic structure is preferably a polymer compound such as a polyester resin, an acrylic resin, or a urethane resin.
  • polyester resins are more preferable because more condensed polycyclic aromatic structures can be introduced.
  • the condensed polycyclic aromatic structure into the polyester resin, for example, by introducing two or more hydroxyl groups as substituents into the condensed polycyclic aromatic structure to form a diol component or a polyvalent hydroxyl component, Alternatively, there is a method of synthesizing a dicarboxylic acid component or a polyvalent carboxylic acid component by introducing two or more carboxylic acid groups.
  • the condensed polycyclic aromatic structure contained in the coating layer is preferably a compound having a naphthalene skeleton in that it is difficult to be colored.
  • a resin in which a naphthalene skeleton is incorporated as a polyester component is suitably used in terms of good adhesion to various surface functional layers formed on the coating layer and transparency.
  • Representative examples of the naphthalene skeleton include 1,5-naphthalenedicarboxylic acid, 2,6-naphthalenedicarboxylic acid, and 2,7-naphthalenedicarboxylic acid.
  • the condensed polycyclic aromatic structure introduces a substituent containing a sulfur element, an aromatic substituent such as a phenyl group, a halogen element group, etc.
  • substituents such as alkyl groups, ester groups, amide groups, sulfonic acid groups, carboxylic acid groups, and hydroxyl groups may be introduced.
  • particles other than the above-described metal oxide may be contained for the purpose of improving the adhesion and slipperiness of the coating layer.
  • the average particle diameter is usually 1.0 ⁇ m or less, preferably 0.5 ⁇ m or less, more preferably 0.2 ⁇ m or less from the viewpoint of transparency of the film.
  • Specific examples of the particles include silica, alumina, kaolin, calcium carbonate, and organic particles.
  • the first coating layer and the second coating layer have an antifoaming agent, coating property improving agent, thickening agent, organic lubricant, antistatic agent, ultraviolet absorption as necessary. Agents, antioxidants, foaming agents, dyes, pigments and the like may be contained.
  • the ratio of the polyester resin to the total nonvolatile components in the coating solution for forming the first coating layer is usually 50 to 99% by weight, preferably 60 to 97% by weight, and more preferably 70 to 95% by weight.
  • the amount of the polyester resin is out of the above range, the haze may be increased by heat-resistant heat treatment when the adhesiveness is not sufficient, the transparency or the appearance of the coating deteriorates.
  • the ratio of the oxazoline compound to the total nonvolatile components in the coating solution for forming the first coating layer is usually 1 to 50% by weight, preferably 3 to 20% by weight, and more preferably 5 to 15% by weight.
  • the amount of the oxazoline compound is less than 1% by weight, the adhesion may not be sufficient, and when it exceeds 50% by weight, there is a concern that the haze is increased by the heat-resistant heat treatment.
  • the ratio of the metal oxide to the total nonvolatile components in the coating solution for forming the second coating layer is usually 3 to 70% by weight, preferably 5 to 50% by weight, more preferably 5 to 40% by weight, and particularly preferably 8%. ⁇ 30% by weight.
  • the amount of the metal oxide is less than 3% by weight, the refractive index of the coating layer cannot be made sufficiently high, so that interference unevenness may not be reduced.
  • it exceeds 70% by weight the coating layer is transparent. Sexuality may worsen.
  • the ratio of two or more kinds of crosslinking agents to the total nonvolatile components in the coating solution for forming the second coating layer is usually 2 to 80% by weight, preferably 4 to 60% by weight, and more preferably 10 to 40% by weight. . If it is out of these ranges, there is a concern that the adhesion with the surface functional layer such as the hard coat layer may be lowered, if the coating appearance deteriorates, interference after the formation of the surface functional layer such as the hard coat layer The visibility may not be good due to unevenness.
  • the ratio of the oxazoline compound to the total nonvolatile components in the coating solution for forming the second coating layer is usually 1 to 50% by weight, preferably 1 to 30% by weight, and more preferably 3%. ⁇ 20% by weight. If the amount is less than 1% by weight, there is a concern that the adhesion to the surface functional layer such as a hard coat layer may be lowered. Visibility may not be good due to interference unevenness after the surface functional layer is formed.
  • the ratio of the epoxy compound to the total nonvolatile components in the coating solution for forming the second coating layer is usually 1 to 50% by weight, preferably 3 to 30% by weight, more preferably 5%. ⁇ 20% by weight. If it is out of these ranges, there is a possibility that the adhesion with the surface functional layer such as the hard coat layer may be lowered, or the coating appearance may be deteriorated.
  • the proportion of the condensed polycyclic aromatic structure in the compound having a condensed polycyclic aromatic structure is usually 5 to 80% by weight, preferably 10 to 60% by weight.
  • the ratio of the compound to the total nonvolatile components in the coating solution is usually 5 to 80% by weight, preferably 5 to 70% by weight, more preferably 10 to 50%. % By weight.
  • the ratio of the condensed polycyclic aromatic structure can be determined by, for example, dissolving and extracting the coating layer with an appropriate solvent or warm water, separating by chromatography, analyzing the structure by NMR or IR, and further pyrolyzing GC-MS ( Gas chromatographic mass spectrometry) or optical analysis.
  • GC-MS Gas chromatographic mass spectrometry
  • the analysis of the components in the coating layer can be performed, for example, by analysis of TOF-SIMS, ESCA, fluorescent X-rays and the like.
  • a coating layer When providing a coating layer by in-line coating, apply the above-mentioned series of compounds as an aqueous solution or water dispersion on a polyester film with a coating solution adjusted to a solid content concentration of about 0.1 to 50% by weight. It is preferable to produce a coated film at. Moreover, in the range which does not impair the main point of this invention, a small amount of organic solvents may be contained in the coating liquid for the purpose of improving dispersibility in water, improving film-forming properties, and the like. Only one type of organic solvent may be used, or two or more types may be used as appropriate.
  • the film thickness of the first coating layer is usually in the range of 0.002 to 1.0 ⁇ m, preferably 0.03 to 0.3 ⁇ m, more preferably 0.05 to 0.2 ⁇ m. When the film thickness is out of the above range, the adhesion and the coating appearance may be deteriorated.
  • the film thickness of the second coating layer is usually in the range of 0.04 to 0.20 ⁇ m, preferably 0.07 to 0.15 ⁇ m. When the film thickness is out of the above range, visibility may deteriorate due to interference unevenness after the surface functional layer is laminated.
  • a conventionally known coating method such as reverse gravure coating, direct gravure coating, roll coating, die coating, bar coating, curtain coating, or the like can be used.
  • the drying and curing conditions for forming the coating layer on the polyester film are not particularly limited.
  • the coating layer is usually preferably 3 to 40 seconds at 80 to 200 ° C. Is preferably heat-treated at 100 to 180 ° C. for 3 to 40 seconds as a guide.
  • the coating layer is provided by in-line coating, it is usually preferable to perform heat treatment at 70 to 280 ° C. for 3 to 200 seconds as a guide.
  • polyester film constituting the coated film of the present invention may be subjected to surface treatment such as corona treatment or plasma treatment in advance.
  • the second coating layer has a refractive index adjusted to suppress the occurrence of interference unevenness, and the refractive index (1.55-1.65) is the refractive index (1. 60 to 1.70) and near the geometric mean of the refractive indices (1.45 to 1.65) of the surface functional layer such as the hard coat layer.
  • the refractive index of the coating layer and the reflectance of the coating layer are closely related. For the absolute reflectance of the film of the present invention, a graph showing the wavelength on the horizontal axis and the reflectance on the vertical axis is drawn, and the minimum value of the reflectance needs to be one in the wavelength range of 400 to 800 nm. Is 4.0% or more.
  • the reflectance of the minimum value is a high value when the refractive index is high, and a low value when the refractive index is low.
  • it has one minimum value in the wavelength range of 500 to 700 nm.
  • the minimum value is preferably 4.0 to 6.5%, more preferably 4.5 to 6.2%.
  • the minimum value in the wavelength range of 400 to 800 nm is not one, and if the absolute reflectance of the minimum value is outside the above value, interference unevenness occurs after the surface functional layer such as the hard coat layer is formed. The visibility of the film may be reduced.
  • a conductive layer particularly a conductive polymer is generally provided on the first coated layer.
  • the conductive polymer include, but are not limited to, polythiophene, polyaniline, polypyrrole, and the like.
  • polythiophene-based polymers using poly (3,4-ethylenedioxythiophene) in combination with polystyrene sulfonic acid are used.
  • a surface functional layer such as a hard coat layer is generally provided on the second coated layer.
  • a material used for a hard-coat layer For example, hardened
  • reactive silicon compounds such as monofunctional (meth) acrylate, polyfunctional (meth) acrylate, and tetraethoxysilane.
  • a polymerization cured product of a composition containing an ultraviolet curable polyfunctional (meth) acrylate is particularly preferable.
  • composition containing an ultraviolet curable polyfunctional (meth) acrylate is not particularly limited.
  • the UV-curable polyfunctional (meth) acrylate is not particularly limited.
  • composition containing an ultraviolet curable polyfunctional (meth) acrylate are not particularly limited. Examples thereof include inorganic or organic fine particles, polymerization initiators, polymerization inhibitors, antioxidants, antistatic agents, dispersants, surfactants, light stabilizers, and leveling agents.
  • inorganic or organic fine particles include inorganic or organic fine particles, polymerization initiators, polymerization inhibitors, antioxidants, antistatic agents, dispersants, surfactants, light stabilizers, and leveling agents.
  • an arbitrary amount of solvent can be added.
  • the hard coat layer when an organic material is used, a general wet coat method such as a roll coat method or a die coat method is employed.
  • the formed hard coat layer can be subjected to a curing reaction by heating, irradiation with active energy rays such as ultraviolet rays and electron beams as necessary.
  • the refractive index of the surface functional layer formed on the coating layer is generally 1.45 to 1.65 as described above.
  • Coating layer thickness measurement method The surface of the coating layer was dyed with RuO 4 and embedded in an epoxy resin. Thereafter, the section prepared by the ultrathin section method was stained with RuO 4 , and the cross section of the coating layer was measured using TEM (“H-7650” acceleration voltage 100 V manufactured by Hitachi High-Technologies Corporation).
  • first coating layer A mixture of poly (3,4-ethylenedioxythiophene) and polystyrene sulfonic acid (“CELVIOS PH500” manufactured by HC Starck Co., Ltd.), which is a conductive polymer, is applied to the first coating layer side of the polyester film at 100 ° C. A conductive layer was formed by drying. The obtained film was treated for 10 days in an environment of 85 ° C. and 85% RH, and an 18 mm width tape (Cello Tape (registered trademark) “CT-18” manufactured by Nichiban Co., Ltd.) was attached to the film at 180 degrees. When the peeled area was less than 10%, the peeled surface after abrupt peeling was observed as A, and when the peeled area was less than 10%, it was B, and when it was 50% or more, C.
  • CELVIOS PH500 polystyrene sulfonic acid
  • Evaluation method of haze increase value of first coating layer The polyester film was treated for 10 days in an environment of 85 ° C. and 85% RH. Thereafter, on the second coating layer side, 80 parts by weight of dipentaerythritol hexaacrylate, 20 parts by weight of 2-hydroxy-3-phenoxypropyl acrylate, a photopolymerization initiator (trade name “Irgacure 184” manufactured by Ciba Specialty Chemicals Co., Ltd.) 5 A mixed coating solution of 200 parts by weight of methyl ethyl ketone is applied so that the dry film thickness is 5 ⁇ m, and a hard coat layer cured by irradiating with ultraviolet rays is provided, and similarly on the second coating layer side of the film before processing The haze value when the hard coat layer was provided was compared, and the haze increase value after the treatment was evaluated.
  • the haze was measured according to JIS K 7136 using a haze meter “HM-150” manufactured by Murakami Color Research Laboratory.
  • the haze increase value is preferably 1.5% or less, more preferably 1.0% or less, and particularly preferably 0.5% or less.
  • the heating step after the formation of the conductive layer or wet heat treatment may be used. , Whitening is suppressed, and the film has good visibility.
  • a conductive layer was formed on the first coating layer side of the polyester film in the same manner as in the evaluation of (4) above, and the treatment was performed in an environment of 85 ° C. and 85% RH for 10 days.
  • the surface of the conductive layer was observed with the naked eye, and the case where whitening was not confirmed was designated as A, and the case where whitening was confirmed was designated as B.
  • Interference unevenness evaluation method On the second coating layer side of the polyester film, 72 parts by weight of dipentaerythritol hexaacrylate, 18 parts by weight of 2-hydroxy-3-phenoxypropyl acrylate, 10 parts by weight of antimony pentoxide, a photopolymerization initiator (trade name “Irgacure 184”) A mixed coating solution of 1 part by weight of Ciba Specialty Chemicals Co., Ltd. and 200 parts by weight of methyl ethyl ketone was applied so that the dry film thickness was 5 ⁇ m and cured by irradiating with ultraviolet rays to form a hard coat layer.
  • the obtained film is visually observed under a three-wavelength light area type fluorescent lamp, and interference unevenness is observed.
  • a when interference unevenness cannot be confirmed is A
  • B is thin but linear.
  • the case where the interference unevenness was confirmed was C
  • the case where the clear interference unevenness was confirmed was D.
  • the obtained film was subjected to 10 ⁇ 10 cross cut after 100 hours in an environment of 80 ° C. and 90% RH, and a 18 mm wide tape (Cello Tape (registered trademark) “Nichiban Co., Ltd.” “ CT-18 ”) is applied, and the peeled surface is observed after abrupt peeling at a 180 degree peel angle. If the peel area is less than 3%, A is 3% or more and less than 10% B, 10% or more. If less than 50%, C, and if more than 50%, D.
  • polyester (A) 100 parts by weight of dimethyl terephthalate, 60 parts by weight of ethylene glycol, 30 ppm of ethyl acid phosphate with respect to the produced polyester, and 100 ppm with respect to the produced polyester of magnesium acetate tetrahydrate as the catalyst at 260 ° C. in a nitrogen atmosphere. The reaction was allowed to proceed. Subsequently, 50 ppm of tetrabutyl titanate was added to the resulting polyester, the temperature was raised to 280 ° C. over 2 hours and 30 minutes, the pressure was reduced to an absolute pressure of 0.3 kPa, and melt polycondensation was further carried out for 80 minutes. 0.63 polyester (A) was obtained.
  • polyester (C) is obtained using the same method as the production method of polyester (A), except that 0.3 part by weight of silica particles having an average particle diameter of 2 ⁇ m is added before melt polymerization. It was.
  • Examples of compounds constituting the coating layer are as follows.
  • Oxazoline compound (IIA) Acrylic polymer “Epocross WS-500” having an oxazoline group and a polyalkylene oxide chain (manufactured by Nippon Shokubai Co., Ltd., containing about 38% by weight of 1-methoxy-2-propanol solvent)
  • Oxazoline compound (IIB) Acrylic polymer “Epocross WS-700” having an oxazoline group and a polyalkylene oxide chain (manufactured by Nippon Shokubai Co., Ltd., VOC free type)
  • Epoxy compound (IIIA) “Denacol EX-521” (manufactured by Nagase ChemteX Corporation), which is polyglycerol polyglycidyl ether.
  • Polyester resin (IVB) A water dispersion of a polyester resin copolymerized with the composition described below.
  • -Urethane resin 400 parts of polycarbonate polyol composed of 1,6-hexanediol and diethyl carbonate having a number average molecular weight of 2000, 10.4 parts of neopentyl glycol, 58.4 parts of isophorone diisocyanate, and 74.3 parts of dimethylolbutanoic acid.
  • An aqueous dispersion of urethane resin obtained by neutralizing a prepolymer with triethylamine and extending the chain with isophoronediamine.
  • -Urethane resin “Hydran AP-40”, a carboxylic acid water-dispersed polyester polyurethane resin (manufactured by DIC Corporation)
  • VIA silica particles having an average particle size of 0.07 ⁇ m
  • VIB silica particles having an average particle size of 0.15 ⁇ m
  • Example 1 A mixed raw material in which polyesters (A) and (B) are mixed at a ratio of 95% and 5%, respectively, is used as a raw material for the outermost layer (surface layer), and polyesters (A), (B), and (C) are 89% and 5%, respectively.
  • the coating liquid A1 shown in Table 1 below was applied to one side of the longitudinally stretched film (first coating layer).
  • the coating liquid B3 shown in Table 2 below is applied to the opposite surface (formation of the second coating layer), led to a tenter, stretched 4.0 times at 120 ° C in the transverse direction, and heat-treated at 225 ° C. Thereafter, the film is relaxed by 2% in the lateral direction, and the thickness of the first coating layer (after drying) is 0.05 ⁇ m, and the thickness of the second coating layer (after drying) is 0.10 ⁇ m.
  • a polyester film was obtained.
  • Example 2-33 In Example 1, it manufactured like Example 1 except having changed the coating composition into the coating composition shown in Table 1 and Table 2, and obtained the polyester film. As shown in Tables 3 and 4, the obtained polyester film has good adhesion between the first coating layer and the second coating layer, the second coating layer has high reflectance, and the interference unevenness level is also good. there were.
  • Example 1 In Example 1, it manufactured like Example 1 except having changed the coating composition into the coating composition shown in Table 1 and Table 2, and obtained the polyester film. When the obtained coated film was evaluated, as shown in Tables 5 and 6 below, when the adhesion was inferior, when the haze increase value was high, clear interference unevenness could be observed.
  • the coated film of the present invention is suitably used for applications that place importance on adhesion with a conductive layer, adhesion with a surface functional layer such as a hard coat layer, and visibility, such as a transparent electrode such as a touch panel and an electromagnetic shielding film. can do.

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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

La présente invention concerne un film de revêtement caractérisé par une remarquable adhérence à une couche conductrice et pouvant tout à fait être utilisé chaque fois qu'une très bonne visibilité et une forte adhérence à une couche de revêtement rigide, et équivalent, s'avèrent nécessaires. Comme exemples de ces utilisations, on peut citer les films conducteurs transparents pour électrodes transparentes ou les films de protection contre les ondes électromagnétiques des écrans tactiles et équivalent. La présente invention concerne, donc, un film de revêtement comportant une première couche de revêtement déposée sur une surface d'un film polyester et à base d'un liquide de revêtement contenant une résine polyester et un composé oxazoline ; et une seconde couche de revêtement déposée sur l'autre surface du film polyester et à base d'un liquide de revêtement contenant un oxyde métallique et au moins deux types de durcisseurs. La réflectance absolue de la surface de la seconde couche de revêtement présente une valeur minimale dans l'intervalle des longueurs d'onde allant de 400 à 800 nm et ladite valeur minimale est supérieure ou égale à 4,0 %.
PCT/JP2012/062671 2011-06-27 2012-05-17 Film de revêtement Ceased WO2013001933A1 (fr)

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JP2004054161A (ja) * 2002-07-24 2004-02-19 Teijin Dupont Films Japan Ltd 光学用易接着性ポリエステルフィルム
JP2008183882A (ja) * 2007-01-31 2008-08-14 Fujifilm Corp 光学用積層フィルム及びその製造方法、反射防止フィルム並びに画像表示装置
WO2010143551A1 (fr) * 2009-06-12 2010-12-16 三菱樹脂株式会社 Film polyester stratifié
WO2011037032A1 (fr) * 2009-09-23 2011-03-31 三菱樹脂株式会社 Film de polyester stratifié
WO2011135994A1 (fr) * 2010-04-29 2011-11-03 三菱樹脂株式会社 Film polyester stratifié

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JPH11286092A (ja) * 1998-04-02 1999-10-19 Toray Ind Inc 積層ポリエステルフィルムおよびその製造方法
JP4838972B2 (ja) * 2003-03-25 2011-12-14 帝人デュポンフィルム株式会社 光学用易接着性ポリエステルフィルム
JP4661946B2 (ja) * 2007-11-22 2011-03-30 東洋紡績株式会社 光学用易接着性ポリエステルフィルム及び光学用積層ポリエステルフィルム
JP2009234009A (ja) * 2008-03-27 2009-10-15 Toray Ind Inc 積層フィルム
JP2010176357A (ja) * 2009-01-29 2010-08-12 Nof Corp 透明導電性フィルム及びタッチパネル

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JP2004054161A (ja) * 2002-07-24 2004-02-19 Teijin Dupont Films Japan Ltd 光学用易接着性ポリエステルフィルム
JP2008183882A (ja) * 2007-01-31 2008-08-14 Fujifilm Corp 光学用積層フィルム及びその製造方法、反射防止フィルム並びに画像表示装置
WO2010143551A1 (fr) * 2009-06-12 2010-12-16 三菱樹脂株式会社 Film polyester stratifié
WO2011037032A1 (fr) * 2009-09-23 2011-03-31 三菱樹脂株式会社 Film de polyester stratifié
WO2011135994A1 (fr) * 2010-04-29 2011-11-03 三菱樹脂株式会社 Film polyester stratifié

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