WO2013002002A1 - 塗布フィルム - Google Patents
塗布フィルム Download PDFInfo
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- WO2013002002A1 WO2013002002A1 PCT/JP2012/064651 JP2012064651W WO2013002002A1 WO 2013002002 A1 WO2013002002 A1 WO 2013002002A1 JP 2012064651 W JP2012064651 W JP 2012064651W WO 2013002002 A1 WO2013002002 A1 WO 2013002002A1
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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
- C08J7/0427—Coating with only one layer of a composition containing a polymer binder
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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
- B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
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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
- B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
- B32B27/08—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
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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
- B32B27/16—Layered products comprising a layer of synthetic resin specially treated, e.g. irradiated
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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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- 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
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
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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
- C08J7/046—Forming abrasion-resistant coatings; Forming surface-hardening coatings
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
- C09D175/04—Polyurethanes
- C09D175/14—Polyurethanes having carbon-to-carbon unsaturated bonds
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- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B5/00—Optical elements other than lenses
- G02B5/04—Prisms
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- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B5/00—Optical elements other than lenses
- G02B5/08—Mirrors
- G02B5/0891—Ultraviolet [UV] mirrors
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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
- B32B2255/00—Coating on the layer surface
- B32B2255/10—Coating on the layer surface on synthetic resin layer or on natural or synthetic rubber layer
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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
- B32B2255/00—Coating on the layer surface
- B32B2255/26—Polymeric coating
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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
- B32B2307/00—Properties of the layers or laminate
- B32B2307/40—Properties of the layers or laminate having particular optical properties
- B32B2307/418—Refractive
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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
- B32B2307/00—Properties of the layers or laminate
- B32B2307/50—Properties of the layers or laminate having particular mechanical properties
- B32B2307/514—Oriented
- B32B2307/518—Oriented bi-axially
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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
- B32B2307/00—Properties of the layers or laminate
- B32B2307/70—Other properties
- B32B2307/71—Resistive to light or to UV
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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
- B32B2307/00—Properties of the layers or laminate
- B32B2307/70—Other properties
- B32B2307/726—Permeability to liquids, absorption
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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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- 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
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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
- C08J2375/00—Characterised by the use of polyureas or polyurethanes; Derivatives of such polymers
- C08J2375/04—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
- C08J2467/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
-
- 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
- C08J2475/00—Characterised by the use of polyureas or polyurethanes; Derivatives of such polymers
- C08J2475/04—Polyurethanes
- C08J2475/14—Polyurethanes having carbon-to-carbon unsaturated bonds
Definitions
- the present invention relates to a coated film, and particularly to a coated film having an ultraviolet curable resin layer having a high refractive index, which is suitably used as a member for a backlight unit of a liquid crystal display requiring high brightness.
- 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.
- the backlight system has a structure called an edge light type or a direct type. Recently, there is a tendency to reduce the thickness of liquid crystal displays, and an edge light type is increasingly used.
- the edge light type is generally configured in the order of a reflection sheet, a light guide plate, a light diffusion sheet, and a prism sheet. As the flow of light, the light incident on the light guide plate from the backlight is reflected by the reflection sheet and emitted from the surface of the light guide plate. The light beam emitted from the light guide plate enters the light diffusion sheet, is diffused and emitted by the light diffusion sheet, and then enters the next existing prism sheet. The light beam is condensed in the normal direction by the prism sheet and emitted toward the liquid crystal layer.
- the prism sheet used in this configuration is for improving the optical efficiency of the backlight and improving the luminance. Recently, the number of backlights is being reduced and the screen is also becoming larger in order to make the backlight unit thinner and reduce power consumption. In order to maintain the screen performance even in this situation, it is desired to increase the brightness of the prism sheet.
- Various prism sheets have been proposed in the past, but may not be compatible with current high brightness (Patent Documents 1 and 2).
- the present invention has been made in view of the above circumstances, and the problem to be solved is that it has an ultraviolet curable resin layer having a high refractive index and is suitable, for example, as a member for a backlight unit of a liquid crystal display that requires high luminance. It is in providing the coating film which can be utilized for.
- the gist of the present invention is a coated film having a coating layer on at least one surface of a polyester film, and having an ultraviolet curable resin layer having a refractive index of 1.57 or more on the surface of the coating layer, Is a coating layer formed from a coating solution containing a polyurethane resin containing a carbon-carbon double bond that is reactive with the carbon-carbon double bond contained in the compound that forms the ultraviolet curable resin layer. It exists in the coating film characterized by being.
- the present invention it is possible to provide a coated film with high brightness for the backlight unit, and the industrial value of the present invention 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. Among these, a titanium compound is preferable from the viewpoint of increasing the brightness of the film.
- an ultraviolet absorber can be contained in order to improve the weather resistance of the film and prevent deterioration of the liquid crystal.
- 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.
- particles can be blended 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 as a film, but is usually 10 to 350 ⁇ m, preferably 50 to 300 ⁇ 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 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.
- the coated film of the present invention must have a coating layer formed from a coating solution containing a polyurethane resin containing a carbon-carbon double bond having specific reactivity on at least one surface of a polyester film.
- a polyurethane resin is abbreviated as a specific polyurethane resin.
- the present inventors have found out that the adhesiveness with the coating layer deteriorates when the refractive index of the ultraviolet curable resin layer formed on the coating layer is high, and a conventionally known coating layer (for example, JP-A-2-158633). And Japanese Patent Application Laid-Open No. 2010-13550) have found that sufficient adhesion cannot be obtained. Therefore, the coating layer contains a carbon-carbon double bond, and the double bond is reacted with the carbon-carbon double bond of the compound used for forming the prism layer or the microlens layer at the time of ultraviolet irradiation to form a covalent bond. It was thought that the adhesion could be improved. As a result of various investigations, it was found that the adhesion was improved by using a polyurethane resin containing a carbon-carbon double bond.
- the specific polyurethane resin used for forming the coating layer is a polyurethane resin having a carbon-carbon double bond in the polyurethane resin, and the carbon-carbon two-carbon compound contained in the compound forming the prism layer or the microlens layer.
- Any conventionally known material can be used as long as it reacts with a heavy bond.
- introduction into a polyurethane resin in the form of an acrylate group, a methacrylate group, a vinyl group, an allyl group or the like can be mentioned.
- substituents can be introduced into the carbon-carbon double bond, such as an alkyl group such as a methyl group or an ethyl group, a phenyl group, a halogen group, an ester group, an amide group, or the like, or a conjugated double bond. You may have such a structure. Further, the amount of the substituent is not particularly limited, and any of a 1-substituted product, a 2-substituted product, a 3-substituted product, or a 4-substituted product can be used. A 2-substituted product is preferable, and a 1-substituted product is more preferable.
- an acrylate group or a methacrylate group having no substituent is preferred, and in particular, substitution More preferred are acrylate groups without groups.
- the ratio of the carbon-carbon double bond portion to the whole polyurethane resin is preferably 0.5% by weight or more, more preferably 1.0% by weight or more, and further preferably 1.5% by weight or more.
- the ratio of the carbon-carbon double bond portion to the entire resin is 0.5% by weight or more, the adhesion to the prism resin or the microlens resin, particularly the adhesion to a resin having a high refractive index, is effectively improved.
- Polyurethane resin is usually prepared by reaction of polyol and isocyanate.
- examples of the polyol include polyester polyols, polycarbonate polyols, polyether polyols, polyolefin polyols, and acrylic polyols. These compounds may be used alone or in combination.
- 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
- 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.
- polyether polyols examples include polyethylene glycol, polypropylene glycol, polyethylene propylene glycol, polytetramethylene ether glycol, polyhexamethylene ether glycol and the like.
- polyester polyols and polycarbonate polyols are preferable, and polyester polyols are more preferable in order to improve adhesion to various topcoat layers.
- polyisocyanate compound used for obtaining 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.
- These polyisocyanate compounds may be a dimer, a trimer represented by an isocyanuric ring, or a higher polymer.
- 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, isopropylidine 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.
- dimethylolpropanoic 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.
- various polymers can be used in combination for improving the coating appearance, transparency and adhesion.
- polymer examples include polyurethane resin not containing a carbon-carbon double bond, polyester resin, acrylic resin, polyvinyl (polyvinyl alcohol, polyvinyl chloride, vinyl chloride vinyl acetate copolymer, etc.), polyalkylene glycol, polyalkylene.
- examples include imine, methylcellulose, hydroxycellulose, and starches.
- a polyester resin, an acrylic resin, and a polyurethane resin are preferable.
- a polycarbonate-type polyurethane resin is preferable.
- a crosslinking agent in combination in order to strengthen the coating film of the coating layer and improve sufficient adhesion and heat-and-moisture resistance properties with the prism layer and the microlens layer.
- crosslinking agent examples include oxazoline compounds, epoxy compounds, melamine compounds, isocyanate compounds, carbodiimide compounds, silane coupling compounds, and the like.
- an oxazoline compound and an epoxy compound are preferable from the viewpoint of improving the adhesion, and in particular, the combined use of the oxazoline compound and the epoxy compound is preferable because the adhesion is significantly improved.
- the oxazoline compound is particularly preferably a polymer containing an oxazoline group, and 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.
- 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-alkyl ( (Meth) acrylamide, N, N-dialkyl (meth) acrylamide, Examples of the alkyl group include unsaturated amides such as methyl,
- 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, 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 average particle diameter of the particles is preferably 1.0 ⁇ m or less, more preferably 0.5 ⁇ m or less, and particularly preferably 0.2 ⁇ m or less from the viewpoint of film transparency.
- the particles to be used include inorganic particles such as silica, alumina, and metal oxide, or organic particles such as crosslinked polymer particles.
- silica particles are preferred from the viewpoint of dispersibility in the coating layer and transparency of the resulting coating film.
- an antifoaming agent a coating property improver, a thickener, an organic lubricant, an antistatic agent, an ultraviolet absorber, and an antioxidant are formed as necessary for forming the coating layer.
- Foaming agents, dyes and the like may be used in combination.
- the ratio of the specific polyurethane resin to the total nonvolatile components in the coating solution is usually 20 to 90% by weight, preferably 30 to 85% by weight, more preferably 45 to 80% by weight.
- the ratio of the polyurethane resin containing a carbon-carbon double bond in that case to the total amount of the polyurethane resin and other polymers Is usually in the range of 6% by weight or more, preferably 12% by weight or more, more preferably 19% by weight or more.
- the adhesion with the prism layer or the microlens layer may not be sufficient.
- the ratio of the crosslinking agent to the total nonvolatile components in the coating liquid is usually 80% by weight or less, preferably 10 to 60% by weight, more preferably 20 to 50% by weight. When outside the above range, the heat and moisture resistance and adhesion may not be sufficient.
- the ratio of the particles to the total nonvolatile components in the coating solution cannot be generally described because the slipping property and the blocking property change depending on the particle size and the characteristics of the polyester film, but is preferably 25% or less, more preferably 3 to 15 %, More preferably 5 to 10%. When it exceeds 25%, the transparency of the coating layer may be lowered or the adhesion may be lowered.
- the coated film of the present invention it is also possible to provide a coating layer on the surface opposite to the surface on which the coating layer is provided.
- a functional layer such as an anti-sticking layer, a light diffusion layer, or a hard coat layer
- a conventionally well-known thing can be used as a component of the coating layer formed in the surface on the opposite side. Examples thereof include polymers such as polyester resins, acrylic resins and urethane resins, cross-linking agents such as oxazoline compounds, epoxy compounds, melamine compounds, isocyanate compounds and carbodiimide compounds, and these materials may be used alone. A plurality of types may be used in combination. Further, it may be a coating layer using a polyurethane resin containing a carbon-carbon double bond as described above (a coating layer having the same surface on both sides of a polyester film).
- the analysis of the components in the coating layer can be performed, for example, by analysis such as TOF-SIMS, ESCA, fluorescent X-ray, and NMR.
- 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 coating layer is usually 0.002 to 1.0 ⁇ m, preferably 0.005 to 0.5 ⁇ m, more preferably 0.01 to 0.2 ⁇ m, and particularly preferably 0.01 to 0.1 ⁇ m.
- the film thickness is out of the above range, adhesion, coating appearance, and blocking characteristics may be deteriorated.
- coating layer As a method for providing the coating layer, conventionally known coating methods such as reverse gravure coating, direct gravure coating, roll coating, die coating, bar coating, curtain coating, and 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 provided by off-line coating, usually at 80 to 200 ° C. for 3 to 40 seconds, preferably Heat treatment is preferably performed 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 coating film in the present invention may be subjected to surface treatment such as corona treatment or plasma treatment in advance.
- the coated film of the present invention is required to have an ultraviolet curable resin layer having a refractive index of 1.57 or more on the coated layer.
- the refractive index of the polyester film is 1.65. Therefore, the refractive index of the ultraviolet curable resin layer is usually 1.57 to 1.65, preferably 1.58 to 1.64, more preferably 1.59. ⁇ 1.63. If it is out of the above range, the luminance may not be sufficiently increased.
- the ultraviolet curable resin layer is, for example, a prism layer or a microlens layer.
- 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. 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 °.
- Examples of the material used for the prism layer include conventionally known ultraviolet curable resins, and (meth) acrylate resins are typical examples.
- As a constituent compound of the resin generally, for example, it has a polyhydric alcohol component such as ethylene glycol, propylene glycol, tetramethylene glycol, hexamethylene glycol, bisphenol A structure, urethane structure, polyester structure, epoxy structure, etc. ( Examples include meth) acrylate compounds.
- the prescription for increasing the refractive index for increasing the brightness includes a method using a compound having a large aromatic structure, a sulfur atom, a halogen atom, and a metal compound in addition to the above general compound.
- a method using a compound having a large aromatic structure or a sulfur atom is particularly preferable from the viewpoint of the environment because the refractive index of the prism layer and the microlens layer can be made uniform.
- Examples of the compound having a large aromatic structure include condensed polycyclic aromatic structures such as naphthalene, anthracene, phenanthrene, naphthacene, benzo [a] anthracene, benzo [a] phenanthrene, pyrene, benzo [c] phenanthrene, and perylene. , A compound having a biphenyl structure, a compound having a fluorene structure, and the like.
- substituents may be introduced into the condensed polycyclic aromatic structure, biphenyl structure, and fluorene structure.
- those having a benzene ring-containing substituent such as a phenyl group have a refractive index. Since it can be made higher, it is preferable. It is also possible to introduce atoms that increase the refractive index, such as sulfur atoms and halogen atoms.
- various functional groups such as an ester group, an amide group, a hydroxyl group, an amino group, and an ether group can be introduced in order to improve the adhesion with the coating layer.
- the condensed polycyclic aromatic structure, biphenyl structure, and fluorene structure can be incorporated into the aforementioned ultraviolet curable resin.
- the total number of condensed polycyclic aromatic structures, biphenyl structures, fluorene structures, and aromatic compounds substituted for these structures in the UV curable resin layer also depends on the type and amount of other structures or the curing conditions. Therefore, although it cannot be generally stated, it is preferably 20 to 80% by weight, more preferably 25 to 70% by weight, and further preferably 30 to 60% by weight with respect to the entire ultraviolet curable resin layer. If it is out of the above range, the luminance may decrease or the formation of the ultraviolet curable resin layer may not be successful.
- the ratio of the compound having a condensed polycyclic aromatic structure, biphenyl structure, and fluorene structure that forms the ultraviolet curable resin layer is usually 10% as a ratio to the total nonvolatile components of the compound composition that forms the ultraviolet curable resin layer. % Or more, preferably 20 to 90% by weight, more preferably 25 to 80% by weight. If it is less than 10% by weight, the refractive index may be low, and the luminance may not be sufficient.
- 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.
- a material used for the microlens layer a conventionally known material can be used as in the prism layer.
- an optical functional layer that scatters or condenses transmitted light on a transparent film that is, a microlens sheet or a prism sheet formed with a microlens layer or a prism layer is generally referred to as an optical functional film.
- the analysis of the components of the ultraviolet curable resin layer can be performed by analysis such as TOF-SIMS, ESCA, fluorescent X-ray, and NMR.
- Refractive index measurement method An ultraviolet curable resin compound was placed flat on the coating layer side with a film thickness of 10 ⁇ m and cured with ultraviolet rays to form a flat ultraviolet curable resin layer.
- the refractive index of the ultraviolet curable resin layer side was measured using a refractometer (“SL-NA-B” manufactured by Atago Co., Ltd.).
- Adhesion evaluation method The coated film was treated in an environment of 60 ° C. and 90% RH for 24 hours, and then a 10 ⁇ 10 cross cut was made on the UV curable resin layer (prism layer), and then a 18 mm wide tape (Nichiban Co., Ltd.) Cellophane tape (registered trademark) “CT-18”) was affixed and the peeled surface was observed after abrupt peeling at a 180 ° peel angle. If the peeled area was less than 5%, A, 5% to 20% If less than B, 20% or more but less than 50% C, and 50% or more 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.
- IC Polyurethane resin
- Polyurethane resin (IE) without carbon-carbon double bond 80 parts by weight of a polycarbonate polyol composed of 1,6-hexanediol and diethyl carbonate having a number average molecular weight of 2000, 4 parts by weight of polyethylene glycol having a number average molecular weight of 400, 12 parts by weight of methylenebis (4-cyclohexylisocyanate), dimethylolbutanoic acid 4 An aqueous dispersion obtained by neutralizing a urethane resin consisting of parts by weight with triethylamine.
- Acrylic resin (IIB): Aqueous dispersion of acrylic resin polymerized with the following composition: Emulsion polymer of ethyl acrylate / n-butyl acrylate / methyl methacrylate / N-methylol acrylamide / acrylic acid 65/21/10/2/2 (% by weight) (emulsifier: Anionic surfactant)
- Oxazoline compound (IIIA) 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)
- UV curable compound (ic): Naphthoxyethyl acrylate / UV curable compound (iia): Ethylene glycol modified bisphenol A acrylate (ethylene glycol chain 8)
- UV curable compound (iib): Ethylene glycol modified bisphenol A acrylate (ethylene glycol chain 10)
- the composition 1 shown in Table 2 below 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, and the film obtained above is applied from above.
- the coating film was stacked in such a direction that the layer was in contact with the resin, the 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.
- Examples 2 to 23 A polyester film was obtained in the same manner as in Example 1 except that the coating composition and the compound composition of the ultraviolet curable resin layer were changed as shown in Tables 1 and 2 in Example 1. The obtained polyester film was as shown in Table 3 and had good adhesion and luminance.
- Comparative Examples 1 to 5 A polyester film was obtained in the same manner as in Example 1 except that the coating composition and the compound composition of the ultraviolet curable resin layer were changed as shown in Tables 1 and 2 in Example 1. When the obtained coating film was evaluated, it was as shown in Table 3, and the adhesiveness was not sufficient and the luminance was low.
- the coated film of the present invention can be suitably used, for example, as a backlight unit member for a liquid crystal display for applications requiring an ultraviolet curable resin layer having high luminance.
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Abstract
Description
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。
TEM(株式会社日立ハイテクノロジーズ製「H-7650」加速電圧100V)を使用して塗布層を観察し、粒子10個の粒径の平均値を平均粒径とした。
ポリウレタン樹脂を減圧乾燥後、NMR(Bruker Biospin社製「AVANCEIII600」)を用いて、1Hと13Cの各ピークを帰属し、計算により求めた。
塗布層の表面をRuO4で染色し、エポキシ樹脂中に包埋した。その後、超薄切片法により作成した切片をRuO4で染色し、塗布層断面をTEM(上記と同じ)を用いて測定し、10箇所の平均値を塗布層の膜厚とした。
塗布層側に紫外線硬化性樹脂化合物を膜厚10μmで平坦に配置し、紫外線で硬化させ、平坦な紫外線硬化性樹脂層を形成した。紫外線硬化性樹脂層側の屈折率を屈折計(株式会社アタゴ製「SL-NA-B」)を用いて測定した。
塗布フィルムを60℃、90%RHの環境下で24時間処理した後、紫外線硬化性樹脂層(プリズム層)に10×10のクロスカットをして、その上に18mm幅のテープ(ニチバン株式会社製セロテープ(登録商標)「CT-18」)を貼り付け、180度の剥離角度で急激にはがした後の剥離面を観察し、剥離面積が5%未満ならばA、5%以上20%未満ならB、20%以上50%未満ならC、50%以上ならばDとした。
輝度測定装置(株式会社トプコン製「BM-7」)を用いて、輝度を測定し、比較例1と比較して輝度が2%以上向上している場合をA、向上しているが2%未満である場合をB、同等以下である場合をC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、エチレングリコール60重量部、エチルアシッドフォスフェートを生成ポリエステルに対して30ppm、触媒として酢酸マグネシウム・四水和物を生成ポリエステルに対して100ppmを窒素雰囲気下、260℃でエステル化反応をさせた。引き続いて、テトラブチルチタネートを生成ポリエステルに対して50ppm添加し、2時間30分かけて280℃まで昇温すると共に、絶対圧力0.3kPaまで減圧し、さらに80分、溶融重縮合させ、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、エチレングリコール60重量部、触媒として酢酸マグネシウム・四水和物を生成ポリエステルに対して900ppmを窒素雰囲気下、225℃でエステル化反応をさせた。引き続いて、正リン酸を生成ポリエステルに対して3500ppm、二酸化ゲルマニウムを生成ポリエステルに対して70ppm添加し、2時間30分かけて280℃まで昇温すると共に、絶対圧力0.4kPaまで減圧し、さらに85分、溶融重縮合させ、極限粘度0.64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、溶融重合前に平均粒径2μmのシリカ粒子を0.3重量部添加する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ポリエステル(C)を得た。
(化合物例)
・炭素-炭素二重結合を有するポリウレタン樹脂(IA):
ヒドロキシエチルアクリレートユニット:ジシクロヘキシルメタンジイソシアネートユニット:ヘキサメチレンジイソシアネート3量体ユニット:カプロラクトンユニット:エチレングリコールユニット:ジメチロールプロパン酸ユニット=18:12:22:26:18:4(mol%)から形成される炭素-炭素二重結合部の重量が2.0重量%であるポリウレタン樹脂。
ヒドロキシエチルアクリレートユニット:ジシクロヘキシルメタンジイソシアネートユニット:ヘキサメチレンジイソシアネート3量体ユニット:カプロラクトンユニット:エチレングリコールユニット:ジメチロールプロパン酸ユニット=23:12:22:24:15:4(mol%)から形成される炭素-炭素二重結合部の重量が2.6重量%であるポリウレタン樹脂。
ヒドロキシエチルアクリレートユニット:ジシクロヘキシルメタンジイソシアネートユニット:ヘキサメチレンジイソシアネート3量体ユニット:カプロラクトンユニット:エチレングリコールユニット:ジメチロールプロパン酸ユニット=8:10:20:38:20:4(mol%)から形成される炭素-炭素二重結合部の重量が1.0重量%であるポリウレタン樹脂。
ヒドロキシエチルアクリレートユニット:ジシクロヘキシルメタンジイソシアネートユニット:ヘキサメチレンジイソシアネート3量体ユニット:カプロラクトンユニット:エチレングリコールユニット:ジメチロールプロパン酸ユニット=6:10:20:38:22:4(mol%)から形成される炭素-炭素二重結合部の重量が0.7重量%であるポリウレタン樹脂。
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80重量部、数平均分子量400のポリエチレングリコール4重量部、メチレンビス(4-シクロヘキシルイソシアネート)12重量部、ジメチロールブタン酸4重量部からなるウレタン樹脂をトリエチルアミンで中和した水分散体。
下記組成で共重合したポリエステル樹脂の水分散体
モノマー組成:(酸成分)テレフタル酸/イソフタル酸/5-ソジウムスルホイソフタル酸//(ジオール成分)エチレングリコール/1,4-ブタンジオール/ジエチレングリコール=56/40/4//70/20/10(mol%)
・アクリル樹脂(IIB):
下記組成で重合したアクリル樹脂の水分散体
エチルアクリレート/n-ブチルアクリレート/メチルメタクリレート/N-メチロールアクリルアミド/アクリル酸=65/21/10/2/2(重量%)の乳化重合体(乳化剤:アニオン系界面活性剤)
オキサゾリン基及びポリアルキレンオキシド鎖を有するアクリルポリマー「エポクロスWS-500」(株式会社日本触媒製、1-メトキシ-2-プロパノール溶剤約38重量%を含有するタイプ)
ポリグリセロールポリグリシジルエーテルである「デナコールEX-521」(ナガセケムテックス株式会社製)。
平均粒径0.07μmのシリカゾル
(化合物例)
・紫外線硬化性化合物(ia):
2-ビフェノキシエチルアクリレート
・紫外線硬化性化合物(ib):
4,4’-(9-フルオレニリデン)ビス(2-フェノキシエチルアクリレート)
・紫外線硬化性化合物(ic):
ナフトキシエチルアクリレート
・紫外線硬化性化合物(iia):
エチレングリコール変性ビスフェノールAアクリレート(エチレングリコール鎖=8)
・紫外線硬化性化合物(iib):
エチレングリコール変性ビスフェノールAアクリレート(エチレングリコール鎖=10)
・紫外線硬化性化合物(iic):
ヘキサンジオールジアクリレート
・光重合開始剤(iii):
ジフェニル(2,4,6-トリメチルベンゾイル)ホスフィンオキサイド
ポリエステル(A)、(B)、(C)をそれぞれ89%、5%、6%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285℃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両面に、下記表1に示す塗布液1を塗布し、テンターに導き、横方向に120℃で4.0倍延伸し、225℃で熱処理を行った後、横方向に2%弛緩し、塗布層の膜厚(乾燥後)が0.03μmの塗布層を有する厚さ125μmのポリエステルフィルムを得た。
実施例1において、塗布剤組成および紫外線硬化性樹脂層の化合物組成を表1および表2に示すとおり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。得られたポリエステルフィルムは表3に示すとおりであり密着性、輝度ともに良好であった。
実施例1において、塗布剤組成および紫外線硬化性樹脂層の化合物組成を表1および表2に示すとおり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。得られた塗布フィルムを評価したところ、表3に示すとおりであり、密着性が十分でないものや輝度が低いものであった。
Claims (5)
- ポリエステルフィルムの少なくとも片面に塗布層を有し、当該塗布層表面に屈折率が1.57以上である紫外線硬化性樹脂層を有する塗布フィルムであって、前記塗布層が、紫外線硬化性樹脂層を形成する化合物中に含有される炭素-炭素二重結合と反応性を有する炭素-炭素二重結合を含有するポリウレタン樹脂を含有する塗布液から形成された塗布層であることを特徴とする塗布フィルム。
- ポリウレタン樹脂に含有される炭素-炭素二重結合が、アクリレート基、メタクリレート基、ビニル基、アリル基の群から選択された何れかである請求項1に記載の塗布フィルム。
- 屈折率が1.57以上である紫外線硬化性樹脂層が、縮合多環式芳香族構造、ビフェニル構造、およびフルオレン構造の群から選ばれる少なくとも1種の構造を有する紫外線硬化性樹脂層である請求項1又は2に記載の塗布フィルム。
- 紫外線硬化性樹脂層が光学機能層である請求項2又は3に記載の塗布フィルム。
- 光学機能層がマイクロレンズ層またはプリズム層である請求項4に記載の塗布フィルム。
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WO2015015900A1 (ja) * | 2013-07-28 | 2015-02-05 | 三菱樹脂株式会社 | 塗布フィルム |
JP2015024596A (ja) * | 2013-07-28 | 2015-02-05 | 三菱樹脂株式会社 | 積層ポリエステルフィルム |
JP2015025086A (ja) * | 2013-07-28 | 2015-02-05 | 三菱樹脂株式会社 | 積層ポリエステルフィルム |
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