WO2011096493A1 - 積層ポリエステルフィルム - Google Patents
積層ポリエステルフィルム Download PDFInfo
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- WO2011096493A1 WO2011096493A1 PCT/JP2011/052291 JP2011052291W WO2011096493A1 WO 2011096493 A1 WO2011096493 A1 WO 2011096493A1 JP 2011052291 W JP2011052291 W JP 2011052291W WO 2011096493 A1 WO2011096493 A1 WO 2011096493A1
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- coating layer
- polyester film
- acid
- resin
- coating
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Classifications
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- 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
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- 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
- B32B27/30—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
- B32B27/308—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers comprising acrylic (co)polymers
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- 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
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- 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
- B32B27/40—Layered products comprising a layer of synthetic resin comprising polyurethanes
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- 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
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- 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
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- 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
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- 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
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- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
- G02B1/10—Optical coatings produced by application to, or surface treatment of, optical elements
- G02B1/14—Protective coatings, e.g. hard coatings
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- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
- G02B1/10—Optical coatings produced by application to, or surface treatment of, optical elements
- G02B1/18—Coatings for keeping optical surfaces clean, e.g. hydrophobic or photo-catalytic films
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- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B27/00—Optical systems or apparatus not provided for by any of the groups G02B1/00 - G02B26/00, G02B30/00
- G02B27/0006—Optical systems or apparatus not provided for by any of the groups G02B1/00 - G02B26/00, G02B30/00 with means to keep optical surfaces clean, e.g. by preventing or removing dirt, stains, contamination, condensation
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- 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
- B32B2369/00—Polycarbonates
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2457/00—Electrical equipment
- B32B2457/20—Displays, e.g. liquid crystal displays, plasma displays
- B32B2457/202—LCD, i.e. liquid crystal displays
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/25—Web or sheet containing structurally defined element or component and including a second component containing structurally defined particles
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/31504—Composite [nonstructural laminate]
- Y10T428/31551—Of polyamidoester [polyurethane, polyisocyanate, polycarbamate, etc.]
- Y10T428/31565—Next to polyester [polyethylene terephthalate, etc.]
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/31504—Composite [nonstructural laminate]
- Y10T428/31786—Of polyester [e.g., alkyd, etc.]
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/31504—Composite [nonstructural laminate]
- Y10T428/31786—Of polyester [e.g., alkyd, etc.]
- Y10T428/31797—Next to addition polymer from unsaturated monomers
Definitions
- the present invention relates to a laminated polyester film, and is particularly suitably used as a microlens sheet, a prism sheet, a light diffusion sheet, a touch panel member, etc. used in a backlight unit of a liquid crystal display, etc.
- the present invention relates to a laminated polyester film having good prevention properties.
- liquid crystal displays have been widely used as display devices for televisions, personal computers, digital cameras, mobile phones and the like. Since these liquid crystal displays do not have a light emitting function by a liquid crystal display unit alone, a method of displaying by irradiating light using a backlight from the back side is widespread.
- various optical sheets such as a microlens sheet, a prism sheet, and a light diffusion sheet are used.
- these optical sheets are provided with a backcoat layer in order to impart easy slipping and anti-sticking properties to the surface opposite to the optical functional layer such as a microlens layer, a prism layer, and a light diffusion layer.
- the backcoat layer generally has a thickness of about 1 to 15 ⁇ m, and is formed by offline coating as a coating liquid in which particles of about 1 to 30 ⁇ m and a resin binder are mixed with a large amount of an organic solvent (Patent Document 1, 2).
- the present invention has been made in view of the above circumstances, and a solution to the problem is that it is formed by water-based in-line coating, and has slipperiness, anti-sticking property, and antistatic property.
- the backlight of a liquid crystal display An object of the present invention is to provide a laminated polyester film that can be suitably used as a member for a microlens sheet, a prism sheet, or a light diffusion sheet used in a unit or the like.
- the gist of the present invention is to have a coating layer containing a resin, particles and an antistatic agent on one side of the polyester film, and a coating layer containing a resin on the other side of the polyester film.
- the feature resides in a laminated polyester film.
- a laminated polyester film having excellent slipperiness, anti-sticking property and antistatic property can be provided, and its industrial value is high.
- the polyester film constituting the laminated polyester film in the present invention may have a single layer structure or a multilayer structure, and may have four or more layers as long as it does not exceed the gist of the present invention other than a two-layer or three-layer structure. It may be a multilayer, and is not particularly limited.
- the polyester used in the present invention 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 polyester layer of the film of the present invention it is preferable to blend particles for the main purpose of imparting slipperiness and preventing 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 of the particles include magnesium, kaolin, aluminum oxide, and titanium oxide. Further, the heat-resistant organic particles described in JP-B-59-5216, JP-A-59-217755 and the like may be used.
- thermosetting urea resins examples include thermosetting urea resins, thermosetting phenol resins, thermosetting epoxy resins, benzoguanamine resins, and the like.
- 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 size of the particles used is usually in the range of 0.01 to 3 ⁇ m, preferably 0.1 to 2 ⁇ 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 the thickness exceeds 3 ⁇ m, the surface roughness of the film becomes too rough, and a problem may occur when a functional layer such as a prism layer or a light diffusion layer is formed in a later step.
- the content of particles in the polyester layer is usually in the range of 0.001 to 5% by weight, preferably 0.005 to 3% by weight.
- the particle content is less than 0.001% by weight, the slipperiness of the film may be insufficient.
- the content exceeds 5% by weight, the transparency of the film is insufficient. There is a case.
- 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, ultraviolet absorbers, heat stabilizers, lubricants, dyes, pigments, etc. may be added to the polyester film in the present invention as necessary. Can do.
- the thickness of the polyester film in the present invention is not particularly limited as long as it can be formed as a film, but is usually in the range of 10 to 350 ⁇ m, preferably 50 to 250 ⁇ m.
- a production example of the polyester film in the present invention will be specifically described, but is not limited to the following production examples. 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 and / 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 constituting the laminated 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 is provided by in-line coating that treats the film surface during the stretching process of the polyester film. Since the coating can be performed simultaneously with the film formation, the manufacturing cost can be kept low. Moreover, a coating layer can be processed at high temperature and a film suitable as a polyester film can be manufactured.
- 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.
- the polyester film has a coating layer containing a resin, particles and an antistatic agent (hereinafter sometimes abbreviated as a first coating layer) on one side of the polyester film, and the resin on the other side. It is an essential requirement to have a coating layer (hereinafter sometimes abbreviated as “second coating layer”) containing bismuth.
- the first coating layer in the present invention is a backcoat layer for the purpose of imparting easy slipperiness, anti-sticking property, and antistatic property
- the second coating layer is a microlens layer, a prism layer, a light diffusion layer. It is possible to improve the adhesion with the optical functional layer.
- resins can be used as the resin contained in the first coating layer and the second coating layer, and examples thereof include polyester resins, acrylic resins, and urethane resins.
- the polyester resin in the present invention includes, for example, 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, phthalic 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 acrylic resin in the present invention is a polymer composed of a polymerizable monomer having a carbon-carbon double bond, as typified by an acrylic or methacrylic monomer. These may be either a homopolymer or a copolymer. Moreover, the copolymer of these polymers and other polymers (for example, polyester, polyurethane, etc.) is also included. For example, a block copolymer or a graft copolymer. Alternatively, a polymer (possibly a mixture of polymers) obtained by polymerizing a polymerizable monomer having a carbon-carbon double bond in a polyester solution or a polyester dispersion is also included.
- a polymer (in some cases, a mixture of polymers) obtained by polymerizing a polymerizable monomer having a carbon-carbon double bond in a polyurethane solution or polyurethane dispersion is also included.
- a polymer (in some cases, a polymer mixture) obtained by polymerizing a polymerizable monomer having a carbon-carbon double bond in another polymer solution or dispersion is also included.
- a functional machine such as a hydroxyl group or an amino group is contained. Is also possible.
- the polymerizable monomer having a carbon-carbon double bond is not particularly limited, but particularly representative compounds include, for example, acrylic acid, methacrylic acid, crotonic acid, itaconic acid, fumaric acid, maleic acid, citracone Various carboxyl group-containing monomers such as acids, and salts thereof; 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, monobutyl hydroxyl fumarate, Various hydroxyl group-containing monomers such as monobutylhydroxy itaconate; various monomers such as methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, lauryl (meth) acrylate ( (Meth) acrylic acid esters Various nitrogen-containing compounds such as (meth) acrylamide, diacetone acrylamide, N-methylolacrylamide or
- the urethane resin in the present invention is a polymer compound having a urethane resin in the molecule.
- urethane resin is prepared by reaction of polyol and isocyanate.
- the polyol include polycarbonate polyols, polyester polyols, polyether polyols, polyolefin polyols, and acrylic polyols. These compounds may be used alone or in combination.
- Polycarbonate polyols are obtained from a polyhydric alcohol and a carbonate compound by a dealcoholization reaction.
- Polyhydric alcohols include ethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, 1,5-pentane Diol, 1,6-hexanediol, 1,4-cyclohexanediol, 1,4-cyclohexanedimethanol, 1,7-heptanediol, 1,8-octanediol, 1,9-nonanediol, 1,10-decane Examples thereof include diol, neopentyl glycol, 3-methyl-1,5-pentanediol, and 3,3-dimethylol heptane.
- Examples of the carbonate compound include dimethyl carbonate, diethyl carbonate, diphenyl carbonate, and ethylene carbonate.
- Examples of the polycarbonate-based polyols obtained from these reactions include poly (1,6-hexylene) carbonate, poly (3- And methyl-1,5-pentylene) carbonate.
- Polyester polyols include polycarboxylic acids (malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, sebacic acid, fumaric acid, maleic acid, terephthalic acid, isophthalic acid, etc.) or their acid anhydrides.
- polycarboxylic acids malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, sebacic acid, fumaric acid, maleic acid, terephthalic acid, isophthalic acid, etc.
- polyhydric alcohol ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol, tripropylene glycol, butanediol, 1,3-butanediol, 1,4-butanediol, 2,3-butanediol, 2-methyl-1,3-propanediol, 1,5-pentanediol, neopentyl glycol, 1,6-hexanediol, 3-methyl-1,5-pentanediol, 2-methyl-2,4-pentanediol 2-methyl-2-propyl- , 3-propanediol, 1,8-octanediol, 2,2,4-trimethyl-1,3-pentanediol, 2-ethyl-1,3-hexanediol, 2,5-dimethyl-2,5-hexane Diol, 1,9-nonanediol
- polyether polyols examples include polyethylene glycol, polypropylene glycol, polyethylene propylene glycol, polytetramethylene ether glycol, polyhexamethylene ether glycol and the like.
- polyisocyanate compound used to obtain the urethane resin examples include aromatic diisocyanates such as tolylene diisocyanate, xylylene diisocyanate, methylene diphenyl diisocyanate, phenylene diisocyanate, naphthalene diisocyanate, and tolidine diisocyanate, ⁇ , ⁇ , ⁇ ′, ⁇ ′.
- aromatic diisocyanates such as tolylene diisocyanate, xylylene diisocyanate, methylene diphenyl diisocyanate, phenylene diisocyanate, naphthalene diisocyanate, and tolidine diisocyanate, ⁇ , ⁇ , ⁇ ′, ⁇ ′.
- -Aliphatic diisocyanates having aromatic rings such as tetramethylxylylene diisocyanate, aliphatic diisocyanates such as methylene diisocyanate, propylene diisocyanate, trimethylhexamethylene diisocyanate, hexamethylene diisocyanate, cyclohexane diisocyanate, methylcyclohexane diisocyanate, isophorone diisocyanate, dicyclohexyl Methanzi Isocyanate, alicyclic diisocyanates such as isopropylidene dicyclohexyl diisocyanates. These may be used alone or in combination.
- a chain extender may be used when synthesizing the urethane resin, and the chain extender is not particularly limited as long as it has two or more active groups that react with an isocyanate group. Alternatively, a chain extender having two amino groups can be mainly used.
- chain extender having two hydroxyl groups examples include aliphatic glycols such as ethylene glycol, propylene glycol and butanediol, aromatic glycols such as xylylene glycol and bishydroxyethoxybenzene, and esters such as neopentyl glycol hydroxypivalate. And glycols such as glycols.
- chain extender having two amino groups examples include aromatic diamines such as tolylenediamine, xylylenediamine, diphenylmethanediamine, ethylenediamine, propylenediamine, hexanediamine, 2,2-dimethyl-1,3- Propanediamine, 2-methyl-1,5-pentanediamine, trimethylhexanediamine, 2-butyl-2-ethyl-1,5-pentanediamine, 1,8-octanediamine, 1,9-nonanediamine, 1,10- Aliphatic diamines such as decane diamine, 1-amino-3-aminomethyl-3,5,5-trimethylcyclohexane, dicyclohexylmethanediamine, isoprobilitin cyclohexyl-4,4′-diamine, 1,4-diaminocyclohexane, 1 , 3-Bisaminomethylcyclohexane Alicyclic diamines, and the like of.
- the urethane resin in the present invention may be one using a solvent as a medium, but is preferably one containing water as a medium.
- a forced emulsification type using an emulsifier there are a forced emulsification type using an emulsifier, a self-emulsification type in which a hydrophilic group is introduced into the urethane resin, and a water-soluble type.
- a self-emulsification type in which an ionic group is introduced into the skeleton of a urethane resin to form an ionomer is preferable because of excellent storage stability of the liquid and water resistance, transparency, and adhesion of the resulting coating layer.
- Examples of the ionic group to be introduced include various groups such as a carboxyl group, sulfonic acid, phosphoric acid, phosphonic acid, quaternary ammonium salt, and the like, and a carboxyl group is preferable.
- a method for introducing a carboxyl group into a urethane resin various methods can be taken in each stage of the polymerization reaction. For example, there are a method of using a carboxyl group-containing resin as a copolymer component during prepolymer synthesis, and a method of using a component having a carboxyl group as one component such as polyol, polyisocyanate, and chain extender.
- a method in which a desired amount of carboxyl groups is introduced using a carboxyl group-containing diol depending on the amount of this component charged is preferred.
- dimethylolpropionic acid, dimethylolbutanoic acid, bis- (2-hydroxyethyl) propionic acid, bis- (2-hydroxyethyl) butanoic acid, and the like are copolymerized with a diol used for polymerization of a urethane resin.
- the carboxyl group is preferably in the form of a salt neutralized with ammonia, amine, alkali metal, inorganic alkali or the like. Particularly preferred are ammonia, trimethylamine and triethylamine.
- a carboxyl group from which the neutralizing agent has been removed in the drying step after coating can be used as a crosslinking reaction point by another crosslinking agent.
- another crosslinking agent it is possible to further improve the durability, solvent resistance, water resistance, blocking resistance, and the like of the obtained coating layer, as well as excellent stability in a liquid state before coating.
- the first coating layer in the present invention is provided in order to improve the luminance when it is used as an optical film, and preferably contains a polyester resin, an acrylic resin or a urethane resin from the viewpoint of coating appearance. Furthermore, since it is preferable to design with a high total light transmittance, the resin contained in the coating layer is preferably designed with a low refractive index, and among the above, acrylic resins and urethane resins, particularly acrylic resins are preferred. Used for.
- the second coating layer in the present invention it is provided in order to improve adhesion with optical functional layers such as a microlens layer, a prism layer, and a light diffusion layer.
- polyester resin acrylic resin
- acrylic resin it is preferable to contain a urethane resin.
- an acrylic resin or a urethane resin it is more preferable to contain an acrylic resin or a urethane resin.
- a urethane resin such as a polycarbonate polyol.
- the proportion of the resin in the first coating layer is usually 10 to 80% by weight, preferably 15 to 70% by weight, and more preferably 30 to 60% by weight.
- the proportion of the resin in the second coating layer is usually 20%. Is 90% by weight, preferably 30-80% by weight.
- the resin ratio is out of the above range, when the coating appearance is deteriorated, the total light transmittance may be low.
- the resin ratio is out of the above range. , The adhesion may deteriorate.
- the particles in the present invention are used for improving the slipperiness and the anti-sticking property, for example, inorganic particles such as silica, alumina, metal oxide, or organic particles such as crosslinked polymer particles. Can be mentioned.
- silica particles are preferred from the viewpoint of dispersibility in the coating layer and transparency of the resulting coating film.
- the average particle size of the particles contained in the first coating layer is usually from 0.03 to 5 ⁇ m, preferably from 0.05 to 0.5 ⁇ m. When the average particle size is less than 0.03 ⁇ m, the slipperiness and the anti-sticking property may not be sufficient, and when it exceeds 5 ⁇ m, the particles are likely to fall off from the coating layer.
- the content of particles in the first coating layer is usually in the range of 1 to 50% by weight, preferably in the range of 5 to 30% by weight, and more preferably in the range of 10 to 20% by weight. If the amount is less than 1% by weight, there is a possibility that sufficient slipperiness and anti-sticking property may not be obtained. If the amount exceeds 50% by weight, the particles are difficult to be fixed to the coating layer and may fall off. There is.
- the antistatic agent used in the present invention is used to lower the surface resistance of the film surface, and there is no particular limitation, and a conventionally known antistatic agent can be used, but it has good heat resistance and moist heat resistance. For this reason, a polymer type antistatic agent is preferable.
- the polymer type antistatic agent include quaternary ammonium salt compounds, polyether compounds, sulfonic acid compounds, betaine compounds, and electronically conductive compounds.
- the quaternary ammonium salt compound is a compound containing a quaternary ammonium salt in the molecule, for example, a pyrrolidinium ring, a quaternized alkylamine, and a copolymer of these with acrylic acid or methacrylic acid, Examples thereof include quaternized N-alkylaminoacrylamides, vinylbenzyltrimethylammonium salts, 2-hydroxy-3-methacryloxypropyltrimethylammonium salts, and the like. Further, these may be combined or copolymerized with other resins.
- anions that serve as counter ions of these quaternary ammonium salts include ions such as halogen ions, sulfonates, phosphates, nitrates, alkylsulfonates, and carboxylates.
- a compound having a pyrrolidinium ring is more preferable in terms of excellent antistatic ability and heat resistance stability.
- the compound having a pyrrolidinium ring is, for example, a polymer having a structure of the following formula (1).
- each R 1, R 2 are independently an alkyl group, a phenyl group, these alkyl groups, a phenyl group may be substituted by the following groups.
- Substitutable groups are, for example, hydroxyl group, amide group, ester group, alkoxy group, phenoxy group, naphthoxy group, thioalkoxy, thiophenoxy group, cycloalkyl group, trialkylammonium alkyl group, cyano group, and halogen.
- X- in the formula represents a halogen ion, sulfonate, phosphate, nitrate, alkyl sulfonate, carboxylate or the like.
- the polymer of the above formula (1) is obtained by cyclopolymerizing a compound represented by the following formula (2) using a radical polymerization catalyst.
- the polymerization is carried out by using a polymerization initiator such as hydrogen peroxide, benzoyl peroxide, tertiary butyl peroxide in a polar solvent such as water or methanol, ethanol, isopropanol, formamide, dimethylformamide, dioxane, acetonitrile as a solvent.
- a polymerization initiator such as hydrogen peroxide, benzoyl peroxide, tertiary butyl peroxide in a polar solvent such as water or methanol, ethanol, isopropanol, formamide, dimethylformamide, dioxane, acetonitrile as a solvent.
- a compound having a polymerizable carbon-carbon unsaturated bond may be used as a copolymerization component.
- the number average molecular weight of the quaternary ammonium salt compound is usually 1000 to 500,000, preferably 2000 to 100,000, and more preferably 5000 to 50,000.
- the molecular weight is less than 1000, the strength of the coating film may be weak or the heat resistance stability may be poor.
- the molecular weight exceeds 500,000, the viscosity of the coating solution increases, and the handleability and applicability may deteriorate.
- polyether compounds include polyethylene oxide, polyether ester amide, acrylic resin having polyethylene glycol in the side chain, and the like.
- the sulfonic acid compounds are compounds containing sulfonic acid or sulfonate in the molecule, and examples thereof include polystyrene sulfonic acid.
- Examples of the electron conductive compound include aliphatic conjugated systems such as polyacetylene, aromatic conjugated systems such as polyparaphenylene, heterocyclic conjugated systems such as polypyrrole and polythiophene, and heteroatom-containing conjugated systems such as polyaniline. .
- the proportion of the antistatic agent in the first coating layer in the present invention is usually in the range of 1 to 50% by weight, preferably in the range of 10 to 40% by weight, more preferably in the range of 20 to 30% by weight.
- the amount is less than 1% by weight, the antistatic ability is not sufficient, and dust may be attached or workability may be deteriorated due to sticking of the film.
- it exceeds 50% by weight a sufficient coated surface state may not be obtained.
- the first coating layer preferably contains a release agent for improving scratch resistance and slipperiness.
- a release agent for improving scratch resistance and slipperiness.
- examples of the release agent include wax, fluorine compound, long chain alkyl compound, and silicone.
- the wax is a wax selected from natural waxes, synthetic waxes, and blended waxes.
- Natural waxes are plant waxes, animal waxes, mineral waxes, and petroleum waxes. Examples of plant waxes include candelilla wax, carnauba wax, rice wax, wood wax, and jojoba oil. Animal waxes include beeswax, lanolin, and whale wax. Examples of the mineral wax include montan wax, ozokerite, and ceresin. Examples of petroleum wax include paraffin wax, microcrystalline wax, and petrolatum.
- Synthetic waxes include synthetic hydrocarbons, modified waxes, hydrogenated waxes, fatty acids, acid amides, amines, imides, esters, and ketones.
- Fischer-Tropsch wax also known as Sazoir wax
- polyethylene wax are famous, but in addition to this, low molecular weight polymers (specifically, polymers having a viscosity number average molecular weight of 500 to 20000)
- polypropylene ethylene / acrylic acid copolymer
- polyethylene glycol polypropylene glycol
- polyethylene glycol polyethylene glycol
- polypropylene glycol polyethylene glycol
- polypropylene glycol block or graft conjugate examples of the modified wax include montan wax derivatives, paraffin wax derivatives, and microcrystalline wax derivatives.
- the derivative herein is a compound obtained by any of purification, oxidation, esterification, saponification treatment, or a combination thereof.
- Hydrogenated waxes include hardened castor oil and hardened castor oil derivatives.
- the fluorine compound a compound containing a fluorine atom in the compound is preferable.
- An organic fluorine compound is suitably used in terms of the coated surface, and examples thereof include perfluoroalkyl group-containing compounds, polymers of olefin compounds containing fluorine atoms, and aromatic fluorine compounds such as fluorobenzene.
- a polymer compound is preferable.
- the long-chain alkyl compound is a compound having a linear or branched alkyl group having 6 or more carbon atoms, particularly preferably 8 or more.
- Specific examples include, but are not limited to, long-chain alkyl group-containing polyvinyl resins, long-chain alkyl group-containing acrylic resins, long-chain alkyl group-containing polyester resins, long-chain alkyl group-containing amine compounds, long-chain alkyl groups.
- a polymer compound is preferable.
- Silicone is a compound having a silicone structure in the molecule, and examples thereof include silicone emulsion, acrylic graft silicone, silicone graft acrylic, amino-modified silicone, perfluoroalkyl-modified silicone, and alkyl-modified silicone. In consideration of heat resistance and contamination due to transfer, it is preferable to contain a curable silicone resin.
- release agents may be used alone or in combination.
- a wax is more preferably used because good slipperiness can be imparted with a small amount.
- the proportion of the release agent in the first coating layer is usually 50% by weight or less, preferably 1 to 20% by weight, more preferably 3 to 10% by weight. If it exceeds 50% by weight, the surface state of the coating layer may deteriorate.
- a crosslinking agent can be used in combination to strengthen the coating film.
- the crosslinking agent include melamine compounds, epoxy compounds, oxazoline compounds, isocyanate compounds, carbodiimide compounds, metal coupling agents, and the like.
- the melamine compound is a compound having a melamine skeleton in the compound.
- an alkylolated melamine derivative a compound partially or completely etherified by reacting an alcohol with an alkylolated melamine derivative, and 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.
- Examples of the epoxy compound include a compound containing an epoxy group in the molecule, a prepolymer and a cured product thereof.
- Examples include condensates of epichlorohydrin with hydroxyl groups and amino groups such as ethylene glycol, polyethylene glycol, glycerin, polyglycerin, and bisphenol A, and polyepoxy compounds, diepoxy compounds, monoepoxy compounds, glycidylamine compounds, and the like. is there.
- polyepoxy compound examples include sorbitol, polyglycidyl ether, polyglycerol polyglycidyl ether, pentaerythritol polyglycidyl ether, diglycerol polyglycidyl ether, triglycidyl tris (2-hydroxyethyl) isocyanate, glycerol polyglycidyl ether, trimethylol.
- propane 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, propylene glycol diglycidyl ether Ether, polypropylene glycol diglycidyl ether, Ritetramethylene glycol diglycidyl ether and monoepoxy compounds include, for example, 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) cyclohex
- An oxazoline compound is a compound having an oxazoline group in the molecule.
- a polymer containing an oxazoline group is preferable, and it can be prepared by polymerization of an addition polymerizable oxazoline group-containing monomer alone or with another monomer.
- 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
- the proportion of the crosslinking agent in the first coating layer is usually 30% by weight or less, preferably 20% by weight or less, and the proportion of the crosslinking agent in the second coating layer is usually 5 to 70% by weight, preferably 15 to 50% by weight. In order to give the coating film an appropriate strength, it is preferred to use within this range. Moreover, in the 2nd application layer, when the ratio of a crosslinking agent remove
- the first coating layer and the second coating layer have an antifoaming agent, a coating property improving agent, a thickening agent, an organic lubricant, an ultraviolet absorber, and an antioxidant as necessary.
- Agents, foaming agents, pigments, dyes and the like may be contained.
- Analysis of various components in the first coating layer and the second coating layer can be performed by surface analysis such as TOF-SIMS.
- the coating layer is provided by in-line coating, and the above-described series of compounds is applied as an aqueous solution or water dispersion, and the solid content concentration is adjusted to about 0.1 to 50% by weight as a guide. It is preferable to produce a laminated polyester film by applying the liquid on the polyester film. 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 coating amount of the first coating layer provided on the polyester film is usually 0.03 to 1.0 g / m 2 , more preferably 0.05 to 0.5 g / m 2 , The range is preferably 0.07 to 0.2 g / m 2 .
- the coating amount is less than 0.03 g / m 2 , there is a high possibility that the particles fall off, and when it exceeds 1.0 g / m 2 , the appearance may be deteriorated.
- the coating amount of the second coating layer is usually 0.002 to 1.0 g / m 2 , more preferably 0.005 to 0.5 g / m 2 , and still more preferably 0.01 to 0.2 g / m 2. Range. If the coating amount is less than 0.002 g / m 2, sufficient adhesion may not be obtained, and if it exceeds 1.0 g / m 2 , the appearance and transparency may be deteriorated.
- the first coating layer and the second coating layer can be provided by a conventionally known coating method such as reverse gravure coating, direct gravure coating, roll coating, die coating, bar coating, curtain coating, or the like.
- the drying and curing conditions for forming the first coating layer and the second coating layer on the polyester film are not particularly limited, and usually at 70 to 280 ° C. for 3 to 200 seconds as a guide. It is better to perform heat treatment.
- polyester film constituting the laminated polyester film in the present invention may be subjected to surface treatment such as corona treatment or plasma treatment in advance.
- the total light transmittance is preferably high from the viewpoint of improving luminance. Since there is also an influence of the second coating layer, it cannot be generally stated, but it is preferably 90.0% or more, more preferably 91.0% or more, and further preferably 91.5% or more. .
- the haze is preferably in the range of 1.0 to 10%, more preferably in the range of 1.5 to 5.0%.
- the haze is preferably in the range of 1.0 to 10%, more preferably in the range of 1.5 to 5.0%.
- the transmittance may be reduced, and the luminance may be reduced.
- a prism layer, a microlens layer, a light diffusion layer, and the like are provided on the second coating layer of the laminated polyester film of the present invention in order to improve luminance.
- various shapes have been proposed for the prism layer in order to improve the luminance efficiently.
- prism layers are formed by arranging prism rows having a triangular cross section in parallel.
- various shapes of the microlens layer have been proposed, but in general, a large number of hemispherical convex lenses are provided on the film.
- the light diffusion layer is used for uniformly diffusing transmitted light in multiple directions, and contains particles and a binder. Any layer can have a conventionally known shape.
- Examples of the shape of the prism layer include those having a triangular section with a thickness of 10 to 500 ⁇ m, a pitch of prism rows of 10 to 500 ⁇ m, and an apex angle of 40 ° to 100 °.
- conventionally known materials can be used, for example, those made of an active energy ray-curable resin, such as polyester resin, epoxy resin, polyester (meth) acrylate, epoxy Examples include (meth) acrylate resins such as (meth) acrylate and urethane (meth) acrylate.
- the shape of the microlens layer is, for example, a hemispherical shape having a thickness of 10 to 500 ⁇ m and a diameter of 10 to 500 ⁇ m, but it may be shaped like a cone or a polygonal pyramid.
- the material used for the microlens layer conventionally known materials can be used as in the prism layer, and examples thereof include an active energy ray curable resin.
- the particles to be included in the light diffusion layer may be any particles having a property of diffusing light, such as organic particles such as acrylic resin, acrylic urethane resin, urethane resin, polyester resin, and polyvinyl resin, silica, and metal oxide. And inorganic particles such as barium sulfate can be used. Of these, acrylic resins and acrylic urethane resins having good transparency are preferably used.
- the particle diameter of these particles is not particularly limited, but the average particle diameter is 1 to 50 ⁇ m, more preferably 5 to 15 ⁇ m.
- the binder contained in the light diffusing layer is used to fix particles and develop light diffusibility.
- polyester resin acrylic resin, polyurethane resin, fluororesin, silicone resin, epoxy resin, UV curable type
- resins include resins.
- a polyol compound is preferably used, and examples thereof include acrylic polyol and polyester polyol.
- a polyol compound When a polyol compound is used as a binder, it is preferable to contain isocyanate as a curing agent. By containing isocyanate, a stronger cross-linked structure can be formed, and physical properties as a light diffusion layer are improved. Further, when an ultraviolet curable resin is used as the binder, an acrylate resin is preferable, which can be used for improving the hardness of the light diffusion layer.
- the light diffusing layer may contain a surfactant, a fine inorganic filler, a plasticizer, a curing agent, an antioxidant, an ultraviolet absorber, a rust preventive agent, etc. within a range not impairing the light diffusion performance. .
- the mixing ratio of the binder and particles in the light diffusion layer can be appropriately set depending on the light diffusibility to be obtained, and is not particularly limited.
- the binder / particles are in the range of 0.1 to 50 in terms of weight ratio, More preferably, it is in the range of 0.5-20.
- a method of preparing a coating solution containing a binder and particles, coating and drying can be mentioned.
- a coating method a conventionally known coating method such as reverse gravure coating, direct gravure coating, roll coating, die coating, bar coating, curtain coating, spray coating, spin coating or the like can be used.
- the thickness of the light diffusion layer is not particularly limited, but it is in the range of 1 to 100 ⁇ m, more preferably in the range of 3 to 30 ⁇ m in consideration of light diffusibility, film strength, and the like.
- Measurement of total light transmittance Measurement was performed according to JIS K 7361 using a haze meter HM-150 manufactured by Murakami Color Research Laboratory.
- Second coating layer side prism adhesion evaluation method To form a prism layer, a resin, KAYARAD DPHA-40H made by Nippon Kayaku, is placed on a mold member in which a large number of prism rows with a pitch of 50 ⁇ m and an apex angle of 65 ° are arranged in parallel.
- the laminated polyester film was stacked in a direction in contact with the resin, the active energy ray-curable composition was uniformly stretched by a roller, and the resin was cured by irradiating ultraviolet rays from an ultraviolet irradiation device. Subsequently, the film was peeled off from the mold member to obtain a film on which a prism layer was formed.
- the polyester used in the examples and comparative examples was prepared as follows. ⁇ Method for producing polyester (A)> Using 100 parts by weight of dimethyl terephthalate and 60 parts by weight of ethylene glycol as starting materials, adding tetrabutoxy titanate as a catalyst to the reactor, setting the reaction start temperature to 150 ° C., and gradually increasing the reaction temperature as methanol is distilled off. It was 230 degreeC after 3 hours. After 4 hours, the transesterification reaction was substantially completed, and then a polycondensation reaction was performed for 4 hours. That is, the temperature was gradually raised from 230 ° C. to 280 ° C. On the other hand, the pressure was gradually reduced from normal pressure, and finally 0.3 mmHg.
- the reaction was stopped at a time corresponding to an intrinsic viscosity of 0.63 due to a change in stirring power of the reaction tank, and the polymer was discharged under nitrogen pressure to obtain a polyester (A) having an intrinsic viscosity of 0.63.
- the pressure was gradually reduced from normal pressure, and finally 0.3 mmHg.
- the reaction was stopped at a time corresponding to an intrinsic viscosity of 0.65 due to a change in stirring power in the reaction vessel, and the polymer was discharged under nitrogen pressure to obtain a polyester (B) having an intrinsic viscosity of 0.65.
- ⁇ Method for producing polyester (C)> In the method for producing polyester (A), 0.2 part of silica particles having an average particle diameter of 2 ⁇ m dispersed in ethylene glycol was added, and the polycondensation reaction was stopped at a time corresponding to an intrinsic viscosity of 0.66. A polyester (C) having an intrinsic viscosity of 0.66 was obtained using a method similar to the method for producing polyester (A).
- Examples of compounds constituting the coating layer are as follows.
- (Compound example) ⁇ Antistatic agent: (I) Polymer polymerized with the following composition having a pyrrolidinium ring in the main chain: Diallyldimethylammonium chloride / dimethylacrylamide / N-methylolacrylamide 90/5/5 (mol%) Number average molecular weight of about 30,000
- Acrylic resin (IIA) Acrylic resin (Nippazole manufactured by Nippon Carbide Industries Co., Ltd.) copolymerized with acrylic acid alkyl ester and methacrylic acid alkyl ester and dispersed with nonionic emulsifier
- -Urethane resin 400 parts of a 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.
- Crosslinking agent (oxazoline compound) (IV) Epocross WS-500 (manufactured by Nippon Shokubai Co., Ltd.), which is a polymer type crosslinking agent in which an oxazoline group is branched to an acrylic resin.
- the coating solution 1 shown in Table 1 below was dried on one side of the longitudinally stretched film after 0.09 g / m. 2 and the coating solution 11 is applied to the opposite surface so as to be 0.03 g / m 2 after drying, led to a tenter, and stretched 4.0 times at 120 ° C. in the transverse direction. Heat treatment was performed at 0 ° C. to obtain a polyester film having a thickness of 188 ⁇ m.
- the obtained polyester film had low surface resistivity and good scratch resistance and slipperiness on the first coating layer side.
- the properties of this film are shown in Table 2 below.
- Example 2-8 In Example 1, it manufactured similarly to Example 1 except having changed the coating agent composition into the coating agent composition shown in Table 1, and obtained the polyester film. The properties of the finished polyester film are shown in Table 2.
- Comparative Example 1 A polyester film was obtained in the same manner as in Example 1 except that the first coating layer was not provided in Example 1. The finished polyester film had a low total light transmittance and poor scratch resistance and slipperiness.
- Example 1 In Example 1, it manufactured similarly to Example 1 except having changed the coating agent composition into the coating agent composition shown in Table 1, and obtained the polyester film. The completed polyester film was found to have poor dust adhesion, scratch resistance and slipperiness.
- Example 4 In Example 4, it manufactured like Example 4 except not having provided the 2nd application layer, and obtained the polyester film. The finished polyester film had poor adhesion to the prism layer.
- the film of the present invention is, for example, a microlens sheet, a prism sheet, a light diffusion sheet, a touch panel member used for a backlight unit of a liquid crystal display, etc. Can be suitably used.
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Abstract
Description
本発明における積層ポリエステルフィルムを構成するポリエステルフィルムは単層構成であっても多層構成であってもよく、2層、3層構成以外にも本発明の要旨を越えない限り、4層またはそれ以上の多層であってもよく、特に限定されるものではない。
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。
電子顕微鏡(HITACHI製S-4500)を使用して塗布層の表面を観察し、粒子10個の粒子径の平均値を平均粒子径とした。
村上色彩技術研究所製ヘーズメーターHM-150を使用して、JIS K 7361で測定した。
村上色彩技術研究所製ヘーズメーターHM-150を使用して、JIS K 7136で測定した。
日本ヒューレット・パッカード社製高抵抗測定器:HP4339Bおよび測定電極:HP16008Bを使用し、23℃、50%RHの測定雰囲気下でポリエステルフィルムを充分調湿後、印可電圧100Vで1分後の塗布層の表面固有抵抗値を測定した。
23℃、50%RHの測定雰囲気下でポリエステルフィルムを充分調湿後、塗布層を綿布で10往復こする。これを、細かく砕いた煙草の灰の上に静かに近づけ、灰の付着状況を以下の基準で評価した。
○:フィルムを灰に接触させても付着しない。
△:フィルムを灰に接触させると少し付着する。
×:フィルムを灰に近づけただけで多量に付着する。
第1塗布層面上にプリズムシートを重ね、その上に200gの重りをのせて、プリズムシートを動かしたときの表面を観察した。表面にキズが確認されない場合を○、キズが確認される場合を×とした。
第1塗布層面上を爪でこすったとき、引っかかり感がなく、滑り感がある場合を○、引っかかり感がなく、滑り感がない場合を△、引っかかり感がある場合を×とした。
プリズム層形成のために、ピッチ50μm、頂角65°のプリズム列が多数並列している型部材に、樹脂、日本化薬製 KAYARAD DPHA-40Hを配置し、その上から第2塗布層が樹脂と接触する向きに積層ポリエステルフィルムを重ね、ローラーにより活性エネルギー線硬化性組成物を均一に引き伸ばし、紫外線照射装置から紫外線を照射し、樹脂を硬化させた。次いで、フィルムを型部材から剥がし、プリズム層が形成されたフィルムを得た。その直後、カッターナイフで5mm間隔にキズをつけ、24mm幅のテープ(ニチバン株式会社製セロテープ(登録商標)CT-24)を貼り付け、180度の剥離角度で急激にはがした後、剥離面を観察し、剥離面積が10%以下ならば○、10%を超え20%以下なら△、20%を超えるならば×とした。
<ポリエステル(A)の製造方法>
テレフタル酸ジメチル100重量部とエチレングリコール60重量部とを出発原料とし、触媒としてテトラブトキシチタネートを加えて反応器にとり、反応開始温度を150℃とし、メタノールの留去とともに徐々に反応温度を上昇させ、3時間後に230℃とした。4時間後、実質的にエステル交換反応を終了させた後、4時間重縮合反応を行った。
すなわち、温度を230℃から徐々に昇温し280℃とした。一方、圧力は常圧より徐々に減じ、最終的には0.3mmHgとした。反応開始後、反応槽の攪拌動力の変化により、極限粘度0.63に相当する時点で反応を停止し、窒素加圧下ポリマーを吐出させ、極限粘度0.63のポリエステル(A)を得た。
テレフタル酸ジメチル100重量部とエチレングリコール60重量部とを出発原料とし、触媒として酢酸マグネシウム・四水塩を加えて反応器にとり、反応開始温度を150℃とし、メタノールの留去とともに徐々に反応温度を上昇させ、3時間後に230℃とした。4時間後、実質的にエステル交換反応を終了させた。この反応混合物を重縮合槽に移し、正リン酸を添加した後、二酸化ゲルマニウム加えて、4時間重縮合反応を行った。すなわち、温度を230℃から徐々に昇温し280℃とした。一方、圧力は常圧より徐々に減じ、最終的には0.3mmHgとした。反応開始後、反応槽の攪拌動力の変化により、極限粘度0.65に相当する時点で反応を停止し、窒素加圧下ポリマーを吐出させ、極限粘度0.65のポリエステル(B)を得た。
ポリエステル(A)の製造方法において、エチレングリコールに分散させた平均粒子径2μmのシリカ粒子を0.2部を加えて、極限粘度0.66に相当する時点で重縮合反応を停止した以外は、ポリエステル(A)の製造方法と同様の方法を用いて、極限粘度0.66のポリエステル(C)を得た。
(化合物例)
・帯電防止剤:(I)
主鎖にピロリジニウム環を有する下記組成で重合したポリマー:
ジアリルジメチルアンモニウムクロライド/ジメチルアクリルアミド/N-メチロール
アクリルアミド=90/5/5(mol%)
数平均分子量約30000
アクリル酸アルキルエステルとメタクリル酸アルキルエステルを共重合し、ノニオン系乳化剤で分散させたアクリル樹脂(日本カーバイド工業製ニカゾール)
1,6-ヘキサンジオールとジエチルカーボネートからなる数平均分子量が2000のポリカーボネートポリオールを400部、ネオペンチルグリコールを10.4部、イソホロンジイソシアネート58.4部、ジメチロールブタン酸が74.3部からなるプレポリマーをトリエチルアミンで中和し、イソホロンジアミンで鎖延長して得られるウレタン樹脂の水分散体。
・離型剤:(III)
攪拌機、温度計、温度コントローラーを備えた内容量1.5Lの乳化設備に融点105℃、酸価16mgKOH/g、密度0.93g/mL、平均分子量5000の酸化ポリエチレンワックス300g、イオン交換水650gとデカグリセリンモノオレエート界面活性剤を50g、48%水酸化カリウム水溶液10gを加え窒素で置換後、密封し150℃で1時間高速攪拌した後130℃に冷却し、高圧ホモジナイザーを400気圧下で通過させ40℃に冷却したワックスエマルション。
・粒子:(VIB)平均粒径0.08μmの酸性シリカ粒子
・粒子:(VIC)平均粒径0.07μmのシリカ粒子
ポリエステル(A)、(B)、(C)をそれぞれ85%、5%、10%の割合で混合した混合原料を最外層(表層)の原料とし、ポリエステル(A)、(B)をそれぞれ95%、5%の割合で混合した混合原料を中間層の原料として、2台の押出機に各々を供給し、各々290℃で溶融した後、40℃に設定した冷却ロール上に、2種3層(表層/中間層/表層=1:18:1の吐出量)の層構成で共押出し冷却固化させて未延伸シートを得た。次いで、ロール周速差を利用してフィルム温度85℃で縦方向に3.4倍延伸した後、この縦延伸フィルムの片面に、下記表1に示す塗布液1を乾燥後0.09g/m2になるように塗布し、反対側の面に塗布液11を乾燥後0.03g/m2になるように塗布し、テンターに導き、横方向に120℃で4.0倍延伸し、225℃で熱処理を行い、厚さ188μmのポリエステルフィルムを得た。
実施例1において、塗布剤組成を表1に示す塗布剤組成に変更する以外は実施例1と同様にして製造し、ポリエステルフィルムを得た。でき上がったポリエステルフィルムの特性を表2に示す。
実施例1において、第1塗布層を設けなかったこと以外は実施例1と同様にして製造し、ポリエステルフィルムを得た。でき上がったポリエステルフィルムは全光線透過率が低く、耐擦傷性や滑り性が悪いものであった。
実施例1において、塗布剤組成を表1に示す塗布剤組成に変更する以外は実施例1と同様にして製造し、ポリエステルフィルムを得た。でき上がったポリエステルフィルムは、塵埃付着性や耐擦傷性や滑り性が悪い場合が見られた。
実施例4において、第2塗布層を設けなかったこと以外は実施例4と同様にして製造し、ポリエステルフィルムを得た。でき上がったポリエステルフィルムはプリズム層との密着性が弱いものであった。
Claims (9)
- ポリエステルフィルムの一方の面に、樹脂、粒子および帯電防止剤を含有する第1塗布層を有し、もう一方のポリエステルフィルム面に、樹脂を含有する第2塗布層を有することを特徴とする積層ポリエステルフィルム。
- 第1塗布層および第2塗布層に含有される樹脂が、ポリエステル樹脂、アクリル樹脂、ウレタン樹脂の群から選択される何れかである請求項1に記載の積層ポリエステルフィルム。
- 第1塗布層に含有される粒子が、平均粒子径0.03~5μmの無機粒子または架橋高分子粒子である請求項1又は2に記載の積層ポリエステルフィルム。
- 第1塗布層に占める樹脂の割合が10~80重量%であり、第2塗布層に占める樹脂の割合が20~90重量%である請求項1~3の何れかに記載の積層ポリエステルフィルム。
- 第1塗布層に占める粒子の割合が1~50重量%である請求項1~4の何れかに記載の積層ポリエステルフィルム。
- 第1塗布層が離型剤を含有する請求項1~5の何れかに記載の積層ポリエステルフィルム。
- 第1塗布層に占める離型剤の割合が50重量%以下である請求項6に記載の積層ポリエステルフィルム。
- 第1塗布層および第2塗布層が架橋剤を含有する請求項1~7の何れかに記載の積層ポリエステルフィルム。
- 第1塗布層に占める架橋剤の割合が30重量%以下であり、第2塗布層に占める架橋剤の割合が5~70重量%である請求項8に記載の積層ポリエステルフィルム。
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US20140011036A1 (en) * | 2011-02-22 | 2014-01-09 | Mitsubishi Plastics, Inc. | Laminated polyester film |
CN104802483B (zh) * | 2011-10-19 | 2016-11-09 | 三菱树脂株式会社 | 聚酯膜 |
WO2013058315A1 (ja) * | 2011-10-22 | 2013-04-25 | 三菱樹脂株式会社 | 塗布フィルム |
-
2010
- 2010-02-07 JP JP2010024915A patent/JP5553627B2/ja active Active
-
2011
- 2011-02-03 CN CN201180005427.5A patent/CN102695613B/zh active Active
- 2011-02-03 WO PCT/JP2011/052291 patent/WO2011096493A1/ja active Application Filing
- 2011-02-03 EP EP11739841.2A patent/EP2532517A4/en not_active Withdrawn
- 2011-02-03 US US13/520,629 patent/US20120315465A1/en not_active Abandoned
- 2011-02-03 KR KR1020127018290A patent/KR20120123328A/ko not_active Application Discontinuation
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Cited By (9)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP2769841A4 (en) * | 2011-10-22 | 2015-06-24 | Mitsubishi Plastics Inc | Coating Film |
JP2015003993A (ja) * | 2013-06-21 | 2015-01-08 | 三菱樹脂株式会社 | 積層ポリエステルフィルム |
JP2015139925A (ja) * | 2014-01-28 | 2015-08-03 | 三菱樹脂株式会社 | 積層ポリエステルフィルム |
WO2015114891A1 (ja) * | 2014-01-28 | 2015-08-06 | 三菱樹脂株式会社 | 塗布フィルム |
JP2016118727A (ja) * | 2014-12-24 | 2016-06-30 | 三菱樹脂株式会社 | ドライフィルムレジスト用保護フィルムおよび感光性樹脂積層体 |
JP2016074225A (ja) * | 2015-12-16 | 2016-05-12 | 三菱樹脂株式会社 | 積層ポリエステルフィルム |
JP2016102213A (ja) * | 2015-12-16 | 2016-06-02 | 三菱樹脂株式会社 | 積層ポリエステルフィルム |
JP2016128566A (ja) * | 2015-12-16 | 2016-07-14 | 三菱樹脂株式会社 | 積層ポリエステルフィルム |
CN106671546A (zh) * | 2016-12-23 | 2017-05-17 | 合肥乐凯科技产业有限公司 | 一种高硬度光学聚酯薄膜 |
Also Published As
Publication number | Publication date |
---|---|
EP2532517A1 (en) | 2012-12-12 |
JP2011161697A (ja) | 2011-08-25 |
EP2532517A4 (en) | 2014-03-05 |
KR20120123328A (ko) | 2012-11-08 |
CN102695613B (zh) | 2015-01-21 |
CN102695613A (zh) | 2012-09-26 |
US20120315465A1 (en) | 2012-12-13 |
JP5553627B2 (ja) | 2014-07-16 |
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