WO2018105352A1 - 光学フィルムならびにこれを有する画像表示装置の前面板、画像表示装置、画像表示機能付きミラ-、抵抗膜式タッチパネルおよび静電容量式タッチパネル - Google Patents
光学フィルムならびにこれを有する画像表示装置の前面板、画像表示装置、画像表示機能付きミラ-、抵抗膜式タッチパネルおよび静電容量式タッチパネル Download PDFInfo
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- WO2018105352A1 WO2018105352A1 PCT/JP2017/041315 JP2017041315W WO2018105352A1 WO 2018105352 A1 WO2018105352 A1 WO 2018105352A1 JP 2017041315 W JP2017041315 W JP 2017041315W WO 2018105352 A1 WO2018105352 A1 WO 2018105352A1
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- layer
- resin film
- film
- image display
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- G06F3/0445—Digitisers, e.g. for touch screens or touch pads, characterised by the transducing means by capacitive means using two or more layers of sensing electrodes, e.g. using two layers of electrodes separated by a dielectric layer
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- B32B23/08—Layered products comprising a layer of cellulosic plastic substances, i.e. substances obtained by chemical modification of cellulose, e.g. cellulose ethers, cellulose esters, viscose comprising such cellulosic plastic substance 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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Definitions
- the present invention relates to an optical film, a front plate of an image display device having the optical film, an image display device, a mirror with an image display function, a resistive touch panel, and a capacitive touch panel.
- Patent Document 1 includes a base material and a hard coat layer laminated on at least one surface of the base material, and has an in-plane retardation of 6000 nm or more and 40000 nm or less. A hard coat film is described.
- Patent Document 2 a plurality of resin films with a hard coat layer including a base layer containing a thermoplastic resin and a hard coat layer containing a curable resin formed on the base layer are laminated. A laminate is described.
- the surface of the front panel of the touch panel may be keyed on a daily basis with a stylus pen, when using a resin film for the front panel, etc. It is important that this resin film is sufficiently filled.
- the keystroke durability can be improved by increasing the thickness of the resin film.
- the smoothness decreases, deforms, or becomes difficult to peel off from the carrier during the production of the thick film resin film.
- it takes a considerable amount of time to form a thick resin film and in particular, in the case of solution casting, the drying process for removing the residual solvent becomes longer, which is a problem of production efficiency. Will also occur.
- the present invention has been made in view of the above problems, an optical film excellent in both keystroke durability and manufacturability, and a front plate of an image display apparatus having the same, an image display apparatus, and a mirror with an image display function It is an object to provide a resistive touch panel and a capacitive touch panel.
- the present inventors tend to improve manufacturing suitability by adopting a method of bonding a resin film to produce a single thick optical film.
- a method of bonding a resin film to produce a single thick optical film it is difficult to obtain an optical film having sufficient keying durability by this method, and after adopting a resin film having a specific tensile elastic modulus as these resin films, the resin films are placed between the resin films.
- an optical film excellent in keystroke durability can be obtained by laminating and laminating using an adhesive layer having a difference in tensile modulus within a specific range.
- the present invention has been further studied based on these findings and has been completed.
- At least the first resin film (A), the adhesive layer (B), and the second resin film (C) are laminated in this order, Tensile elastic modulus EA at 25 ° C. of the first resin film (A), tensile elastic modulus EB at 25 ° C. of the adhesive layer (B), and tensile elastic modulus EC at 25 ° C. of the second resin film (C). Satisfies the following formulas (1) to (5), An optical film in which the total thickness of the first resin film (A), the adhesive layer (B), and the second resin film (C) is greater than 100 ⁇ m.
- the optical film as described in any one. (1) A front plate of an image display device comprising the optical film according to any one of (9). (11) An image display device comprising the front plate according to (10) and an image display element. (12) The image display device according to (11), wherein the image display element is a liquid crystal display element. (13) The image display device according to (11), wherein the image display element is an organic electroluminescence display element. (14) The image display device according to any one of (11) to (13), wherein the image display element is an in-cell touch panel display element. (15) The image display device according to any one of (11) to (13), wherein the image display element is an on-cell touch panel display element. (16) A resistive touch panel having the front plate according to (10). (17) A capacitive touch panel having the front plate according to (10). (18) A mirror with an image display function using the image display device according to (11).
- a numerical range expressed using “to” means a range including numerical values described before and after “to” as a lower limit value and an upper limit value.
- acryl or “(meth) acryl” is simply described, it means methacryl and / or acryl.
- acryloyl or “(meth) acryloyl” simply means methacryloyl and / or acryloyl.
- the weight average molecular weight (Mw) can be measured as a molecular weight in terms of polystyrene by GPC unless otherwise specified.
- GPC device HLC-8220 manufactured by Tosoh Corporation
- G3000HXL + G2000HXL is used as the column
- the flow rate is 1 mL / min at 23 ° C.
- detection is performed by RI.
- the eluent can be selected from THF (tetrahydrofuran), chloroform, NMP (N-methyl-2-pyrrolidone), m-cresol / chloroform (manufactured by Shonan Wako Pure Chemical Industries, Ltd.) and dissolves.
- the optical film of the present invention can be suitably used as a front plate of a touch panel, and can also be suitably used as an optical film such as a polarizing film, a retardation film, and a brightness enhancement film for liquid crystal display.
- the optical film of the present invention is composed of a resin film, has excellent keystroke durability, can be suitably used as a front panel of a touch panel, etc., and is excellent in manufacturing suitability. Further, the front plate of the image display device of the present invention, the image display device, the mirror with an image display function, the resistive touch panel and the capacitive touch panel have the optical film of the present invention and have excellent keystroke durability. Can show.
- FIG. 5 is a schematic diagram illustrating an intersection between a first electrode 11 and a second electrode 21 in FIG. 4.
- FIG. 5 is a schematic diagram showing an embodiment of a first dummy electrode 11A that the first conductive layer 8 in the active area S1 in FIG. 4 may have.
- FIG. 1 A preferred embodiment of the optical film of the present invention is shown in FIG.
- the optical film 4A shown in FIG. 1 includes at least a first resin film (A), an adhesive layer (B), and a second resin film (C) (in FIG. 1, they are indicated by reference numerals 1A, 2A, and 1B in this order). Is an optical film laminated in this order.
- the first resin film (A) has a tensile elastic modulus EA at 25 ° C.
- the adhesive layer (B) has a tensile elastic modulus EB at 25 ° C.
- the second resin film (C) at 25 ° C.
- the tensile elastic modulus EC satisfies the following formulas (1) to (5).
- the thickness of the optical film that is, the total thickness of the first resin film (A), the adhesive layer (B), and the second resin film (C) is greater than 100 ⁇ m.
- the optical film of this invention can implement
- the optical film of the present invention is a laminate, the thickness of each film can be suppressed, so that it is excellent in production suitability.
- the resin film and the adhesive layer may be isotropic or anisotropic.
- a tensile elasticity modulus is computed by the method of the below-mentioned Example description.
- the tensile elastic modulus of the resin film can be changed depending on, for example, the type of resin constituting the resin film. Generally, the tensile elastic modulus tends to increase by increasing the molecular weight and / or crystallinity of the resin. Moreover, the resin film can increase the tensile elastic modulus in the stretching direction by stretching. Also when a resin film consists of a multilayer, it means the tensile elasticity modulus as a resin film.
- the tensile elastic modulus EA at 25 ° C. of the first resin film (A) and the tensile elastic modulus EC at 25 ° C. of the second resin film (C) are each independently 2.
- 5 GPa or more is preferable, 3.0 GPa or more is more preferable, 3.5 GPa or more is more preferable, and 4.0 GPa or more is most preferable.
- the upper limit is not particularly limited, but 12.0 GPa or less is practical.
- the tensile elastic modulus of the adhesive layer (B) (hereinafter also simply referred to as “adhesive layer”) can be changed, for example, depending on the type of resin constituting the adhesive layer, and generally increases the molecular weight and crystallinity of the resin. This tends to increase the tensile modulus.
- the adhesive layer has a crosslinkable group, the tensile modulus can be increased by improving the degree of crosslinking of the adhesive layer by adding a crosslinking agent or the like.
- the adhesive layer contains a polymerizable composition
- the polymerizable group equivalent of the compound having a polymerizable group (the value obtained by dividing the molecular weight of this compound by the total number of polymerizable groups contained in this compound) is reduced.
- a highly elastic substance such as inorganic particles
- a compound containing a rigid molecular structure such as an adamantane skeleton
- the adhesive layer (B) is preferably 2.5 GPa or more, more preferably 3.0 GPa or more, more preferably 3.5 GPa or more, from the viewpoint of further improving the keystroke durability.
- the above is more preferable, 4.5 GPa or more is particularly preferable, and 5.0 GPa or more is most preferable.
- the upper limit is not particularly limited, but 12.0 GPa or less is practical.
- the absolute value of the difference between the tensile elastic modulus EC at 25 ° C. of the second resin film (C) and the tensile elastic modulus EB at 25 ° C. of the adhesive layer (B) represented by the above formula (2) (
- 0.5 GPa or less is more preferable, 2.0 GPa or less is more preferable, 1.5 GPa or less is particularly preferable, and 1.0 GPa or less is most preferable.
- the optical film of the present invention has at least a three-layer structure in which a first resin film (A), an adhesive layer (B), and a second resin film (C) are laminated, and each resin film (A) and ( C) and the adhesive layer (B) may be a single layer or multiple layers.
- the thickness of the optical film of the present invention is preferably 120 ⁇ m or more, more preferably 150 ⁇ m or more, further preferably 180 ⁇ m or more, and further preferably 220 ⁇ m or more.
- the upper limit is practically 320 ⁇ m or less.
- the thickness of the resin film is preferably independently from 50 to 160 ⁇ m, more preferably from 60 to 160 ⁇ m, still more preferably from 80 to 160 ⁇ m, and particularly preferably from 100 to 160 ⁇ m, from the viewpoint of keystroke durability and manufacturability.
- the total thickness of the first resin film and the second resin film is preferably 100 to 320 ⁇ m, more preferably 160 to 320 ⁇ m, and even more preferably 200 to 320 ⁇ m from the viewpoint of keystroke durability.
- the thickness of the adhesive layer is preferably 10 nm or more from the viewpoint of bonding the first resin film and the second resin film, and is preferably 10 nm to 10 ⁇ m, more preferably 10 nm to 5 ⁇ m, more preferably 10 nm to 5 nm from the viewpoint of reducing interference unevenness. 1 ⁇ m is more preferable.
- the retardation in the in-plane direction at a wavelength of 550 nm of the optical film is preferably smaller than 6000 nm, preferably 1000 nm or less, more preferably 500 nm or less, and even more preferably 50 nm or less from the viewpoint of reducing interference unevenness.
- the retardation in the in-plane direction of the optical film means that the linearly polarized light is incident on the optical film and the light passing through the optical film is converted into two linearly polarized light along the fast axis and the slow axis.
- R (unit: nm) represented by the following formula (A) from the refractive index Nx at the fast axis, the refractive index Ny at the slow axis, and the thickness d (unit: nm) of the optical film. ).
- R d ⁇ (Nx ⁇ Ny) (A)
- the retardation in the in-plane direction at a wavelength of 550 nm in the present invention and the specification is measured by making light having a wavelength of 550 nm incident in the normal direction of the film or layer to be measured in KOBRA 21ADH (manufactured by Oji Scientific Instruments). .
- the wavelength selection filter can be exchanged manually, or the measurement value can be converted by a program or the like.
- the in-plane retardation can also be measured using AxoScan (AXOMETRICS).
- Resin film (resin film material) If the resin film used for this invention satisfy
- Resin films include, for example, acrylic resin films, polycarbonate (PC) resin films, cellulose ester resin films such as triacetyl cellulose (TAC) resin films, polyethylene terephthalate (PET) resin films, and polyolefin resin films.
- the cellulose ester resin film is more preferable from the viewpoint of moisture permeability.
- the acrylic resin film refers to a polymer or copolymer resin film formed from one or more compounds selected from the group consisting of acrylic acid esters and methacrylic acid esters.
- An example of the acrylic resin film is a polymethyl methacrylate resin (PMMA) film.
- the weight average molecular weight of the resin is preferably 10,000 to 1,000,000, more preferably 100,000 to 1,000,000 from the viewpoint of increasing the tensile modulus.
- the structure of the resin film is not limited, and may be a single layer or a laminated film composed of two or more layers, but a laminated film of two or more layers is preferable.
- the number of laminated films is preferably 2 to 10 layers, more preferably 2 to 5 layers, and even more preferably 2 or 3 layers.
- a film having a composition different from that of the outer layer and a layer other than the outer layer (core layer or the like) is preferable.
- the outer layers are preferably films having the same composition.
- a film having a laminated structure of TAC-a / TAC-b / TAC-a, acrylic-a / PC / acryl-a and PET-a / PET-b / PET-a, and polycarbonate resin A single layer film may be mentioned.
- a film for example, Tac-a
- a film with the same symbol (a or b) indicates a film having the same composition.
- the resin film may contain an additive in addition to the above-described resin.
- the additive include inorganic particles, matte particles, ultraviolet absorbers, fluorine-containing compounds, surface conditioners, leveling agents and the like described in the hard coat layer described later.
- the melt film forming method described later as a resin melt obtained by mixing and melting the additive and the resin, and in the solution film forming method described later, the solvent (described in the hard coat described later), the resin and the above can be applied.
- a dope liquid in which an additive is mixed it can be used for forming a resin film.
- the thickness of the resin film hardly changes before and after the production of the optical film of the present invention.
- the resin film used for this invention may have an easily bonding layer.
- the easy-adhesion layer the contents of the polarizer-side easy-adhesion layer and the method for producing the polarizer-side easy-adhesion layer described in paragraphs 0098 to 0133 of JP-A-2015-224267 are described in the present specification in accordance with the present invention. Can be incorporated.
- the easy adhesion layer is a layer constituting the resin film (A) or (C) in the optical film of the present invention
- the tensile elastic modulus of the resin film (A) or (C) is a resin including the easy adhesion layer. It means the tensile elastic modulus of the film (A) or (C).
- the resin film may be formed by any method, and examples thereof include a melt film forming method and a solution film forming method.
- melt film forming method smoothing>
- the resin film is formed by the melt film forming method, it is preferable to include a melting step of melting the resin with an extruder, a step of extruding the molten resin from a die into a sheet shape, and a step of forming the film into a film shape.
- a melt resin filtration step may be provided after the melt step, or cooling may be performed when extruding into a sheet.
- the method for producing the resin film includes a melting step of melting the resin with an extruder, a filtration step of filtering the molten resin through a filtration device in which a filter is installed, and extruding the filtered resin from a die into a sheet shape, It has the film formation process which solidifies by cooling on a cooling drum, and shape
- a resin film can be manufactured.
- the pore size of the filter used in the molten resin filtration step is 1 ⁇ m or less, foreign matters can be sufficiently removed.
- the method for forming a resin film can include the following steps.
- the method for producing the resin film includes a melting step of melting the resin with an extruder. It is preferable to dry the resin or a mixture of the resin and the additive to a moisture content of 200 ppm or less, and then introduce the resin into a single screw (single screw) or twin screw extruder and melt it. At this time, in order to suppress decomposition of the resin, it is also preferable to melt in nitrogen or vacuum.
- the detailed conditions can be carried out according to these publications with the aid of Patent Nos. 4926661 ⁇ 0051> to ⁇ 0052> (US2013 / 0100378 publication ⁇ 0085> to ⁇ 0086>) and are described in these publications. The contents are incorporated herein.
- the extruder is preferably a single screw kneading extruder. Furthermore, it is also preferable to use a gear pump in order to increase the delivery accuracy of the molten resin (melt).
- the method for producing the resin film includes a filtration step of filtering the molten resin through a filtration device provided with a filter, and the pore size of the filter used in the filtration device is preferably 1 ⁇ m or less. Only one set of filtration devices having such a filter having a pore diameter range may be installed in the filtration step, or two or more sets may be installed.
- the method for producing the resin film includes a film forming step of forming an unstretched resin film by extruding the filtered resin into a sheet form from a die and bringing the resin into close contact with a cooling drum to cool and solidify.
- the melted (and kneaded) and filtered resin (melt containing resin) is extruded from the die into a sheet, it may be extruded as a single layer or multiple layers.
- a layer containing an ultraviolet absorber and a layer not containing an ultraviolet absorber may be laminated.
- a three-layer structure including an ultraviolet absorber as an inner layer suppresses deterioration of a polarizer due to ultraviolet rays. The bleed-out of the ultraviolet absorber can be suppressed, which is preferable.
- the preferred inner layer thickness (ratio to the total layer) of the obtained resin film is preferably 50% or more and 95% or less, more preferably 60% or more and 90% or less, Preferably they are 70% or more and 85% or less.
- Such lamination can be performed by using a feed block die or a multi-manifold die.
- a resin (melt containing resin) extruded from a die is extruded onto a cooling drum (casting drum), cooled and solidified, and an unstretched resin film (raw fabric) Is preferred.
- the temperature of the resin extruded from the die is preferably 280 ° C. or higher and 320 ° C. or lower, and more preferably 285 ° C. or higher and 310 ° C. or lower. It is preferable that the temperature of the resin extruded from the die in the melting step is 280 ° C. or more, because the remaining melt of the raw material resin can be reduced and the generation of foreign matters can be suppressed. It is preferable that the temperature of the resin extruded from the die in the melting step is 320 ° C. or less because the decomposition of the resin can be reduced and the generation of foreign matters can be suppressed.
- the temperature of the resin extruded from the die can be measured in a non-contact manner with a radiation thermometer (manufactured by Hayashi Denko, model number: RT61-2, used at an emissivity of 0.95).
- the resin film it is preferable to use an electrostatic application electrode when the resin is brought into close contact with the cooling drum in the film forming step. Accordingly, the resin can be strongly adhered onto the cooling drum so that the film surface shape is not roughened.
- the temperature of the resin when it is in close contact with the cooling drum is preferably 280 ° C. or higher.
- the electrical conductivity of the resin is increased, the resin can be strongly adhered to the cooling drum by electrostatic application, and the film surface roughness can be suppressed.
- the temperature of the resin when in close contact with the cooling drum can be measured in a non-contact manner with a radiation thermometer (manufactured by Hayashi Denko, model number: RT61-2, used at an emissivity of 0.95).
- the method for producing the resin film includes a stretching step of uniaxially or biaxially stretching an unstretched resin film.
- the longitudinal stretching step step of stretching in the same direction as the film transport direction
- the resin film is heated and the roller group has a difference in peripheral speed (that is, the transport speed is different). Is stretched in the transport direction.
- the preheating temperature in the longitudinal stretching step is preferably Tg ⁇ 40 ° C. or more and Tg + 60 ° C. or less, more preferably Tg ⁇ 20 ° C. or more and Tg + 40 ° C. or less, more preferably Tg or more, Tg + 30 ° C. with respect to the glass transition temperature (Tg) of the resin film.
- the stretching temperature in the longitudinal stretching step is preferably Tg or more and Tg + 60 ° C. or less, more preferably Tg + 2 ° C. or more and Tg + 40 ° C. or less, and further preferably Tg + 5 ° C. or more and Tg + 30 ° C. or less.
- the draw ratio in the machine direction is preferably 1.0 to 2.5 times, more preferably 1.1 to 2 times.
- the lateral stretching is performed in the width direction by a lateral stretching step (step of stretching in a direction perpendicular to the film transport direction).
- a tenter can be suitably used. The tenter grips both ends of the resin film in the width direction with clips and stretches in the transverse direction. By this transverse stretching, the tensile elastic modulus of the resin film in the optical film can be increased.
- the transverse stretching is preferably carried out using a tenter, and the preferred stretching temperature is preferably Tg or more and Tg + 60 ° C. or less, more preferably Tg + 2 ° C. or more and Tg + 40 ° C. or less with respect to the glass transition temperature (Tg) of the resin film. More preferably, they are Tg + 4 degreeC or more and Tg + 30 degreeC or less.
- the draw ratio is preferably 1.0 or more and 5.0 or less, and more preferably 1.1 or more and 4.0 or less. It is also preferable to relax in the longitudinal direction, the lateral direction, or both after the transverse stretching.
- the variation of the thickness depending on the position in the width direction and the longitudinal direction is 10% or less, preferably 8% or less, more preferably 6% or less, further preferably 4% or less, and most preferably 2% or less. preferable.
- the variation in thickness can be obtained as follows.
- the stretched resin film 12 is sampled by 10 m (meters), except for 20% at both ends in the film width direction, 50 points are sampled at equal intervals from the center of the film in the width direction and the longitudinal direction, and the thickness is measured.
- Th TD-av A thickness average value Th TD-av , a maximum value Th TD-max , and a minimum value Th TD-min in the width direction are obtained, (Th TD-max -Th TD-min ) ⁇ Th TD-av ⁇ 100 [%] Is the variation in thickness in the width direction.
- the thickness average value Th MD-av in the longitudinal direction, the maximum value Th MD-max , and the minimum value Th MD-min are obtained, (Th MD-max -Th MD-min ) ⁇ Th MD-av ⁇ 100 [%] Is the variation of the thickness in the longitudinal direction.
- the above stretching process can improve the thickness accuracy of the resin film.
- the stretched resin film can be wound into a roll in the winding process. At that time, the winding tension of the resin film is preferably 0.02 kg / mm 2 or less.
- melt film formation is described in ⁇ 0134>- ⁇ 0148> of JP-A-2015-224267, and the stretching process is described in JP-A-2007-137028 in accordance with the present invention. It can be incorporated herein.
- the first resin film (A) and the second resin film (C) are the same film, from the point that the optical film is difficult to bend and exhibits better keystroke durability.
- the same film means that the resin materials constituting the resin film are the same (for example, both are TAC films).
- the molecular weight of resin is the same, it is more preferable that the molecular weight and crystallinity degree of resin are the same, and it is still more preferable that the molecular weight, crystallinity degree, and extending
- the first resin film (A) and the second resin film (C) have the same thickness.
- “same” is not limited to being completely identical, but includes being substantially identical. Specifically, it is manufactured by the same manufacturing method (conditions such that the film thickness, stretching, and the like are the same), and errors that occur under these conditions are included.
- ) between the tensile elastic modulus EA at 25 ° C. of the first resin film (A) and the tensile elastic modulus EC at 25 ° C. of the second resin film (C) is preferably small.
- 4.0 GPa or less is preferable, 3.0 GPa or less is more preferable, 2.0 GPa or less is further preferable, and 1.0 GPa or less is particularly preferable.
- Adhesive layer (component that can constitute the adhesive layer)
- An adhesive layer is a layer which plays the role which bonds resin films together, and adhere
- the adhesive layer is preferably formed using a composition containing a component (adhesive) that exhibits adhesiveness by drying or reaction.
- an adhesive layer formed using a composition containing a component that exhibits adhesiveness by a curing reaction (hereinafter referred to as “curable composition”) is a cured layer obtained by curing the curable composition.
- the adhesive layer may be a layer in which the resin accounts for 50% by mass or more, preferably 70% by mass or more of the layer.
- the resin a single resin or a mixture of a plurality of resins may be used.
- the proportion of the resin is the proportion of the resin mixture.
- the resin mixture include a mixture of a certain resin and a resin having a structure obtained by modifying a part of the resin, a mixture of resins obtained by reacting different polymerizable compounds, and the like.
- an adhesive having any appropriate property, form and adhesion mechanism can be used.
- an adhesive for example, a water-soluble adhesive, an ultraviolet curable adhesive, an emulsion adhesive, a latex adhesive, a mastic adhesive, a multilayer adhesive, a paste adhesive, and a foam adhesive , Supported film adhesives, thermoplastic adhesives, hot melt adhesives, thermosetting adhesives, heat activated adhesives, heat seal adhesives, thermosetting adhesives, contact adhesives, pressure sensitive Adhesives, polymerization-type adhesives, solvent-type adhesives, solvent-active adhesives and the like can be mentioned, and water-soluble adhesives and UV-curable adhesives are preferred.
- a water-soluble adhesive is preferably used in terms of excellent transparency, adhesiveness, workability, product quality and economy.
- the water-soluble adhesive can contain natural or synthesized water-soluble components such as protein, starch, and synthetic resin.
- the synthetic resin include resole resin, urea resin, melamine resin, polyethylene oxide resin, polyacrylamide resin, polyvinyl pyrrolidone resin, polyacrylic ester resin, polymethacrylic ester resin, polypolyvinyl alcohol resin, polyacrylic resin and cellulose. Derivatives.
- a water-soluble adhesive containing a polyvinyl alcohol resin or a cellulose derivative is preferable in terms of excellent adhesiveness when the resin film is bonded. That is, the adhesive layer in the present invention preferably contains a polyvinyl alcohol resin or a cellulose derivative.
- the cellulose derivative means a modified cellulose.
- a cellulose derivative A well-known cellulose derivative can be used.
- HEC hydroxyethyl cellulose
- the weight average molecular weight of the resin is preferably 1000 or more, more preferably 10,000 or more, from the viewpoint of increasing the tensile modulus.
- Components optionally contained in the composition containing the adhesive include cross-linking agents (boric acid and Safelink SPM-01 (trade name, manufactured by Nippon Synthetic Chemical Co., Ltd.)), and durability improvers (potassium iodide, etc.) It is done.
- the adhesive layer can be formed, for example, by applying a coating solution containing an adhesive to at least one surface of the resin film and drying. Any appropriate method can be adopted as a method for preparing the coating solution.
- a coating solution for example, a commercially available solution or dispersion may be used, a solvent may be further added to the commercially available solution or dispersion, and the solid content may be used by dissolving or dispersing in various solvents. Also good.
- the adhesive layer may be a cured layer obtained by curing the active energy ray-curable composition.
- the active energy ray-curable composition for forming the adhesive layer is a cationic polymerizable compound such as an epoxy compound, more specifically described in JP-A-2004-245925, as the active energy curable component.
- numerator like this is preferable.
- an epoxy compound for example, an aromatic polyhydroxy compound, which is a raw material of an aromatic epoxy compound represented by diglycidyl ether of bisphenol A, can be obtained by nuclear hydrogenation and glycidyl ether.
- the active energy ray-curable composition for forming the adhesive layer comprises a cationic initiator or a Lewis acid upon irradiation with a polymerization initiator, for example, an active energy ray, in addition to a cationically polymerizable compound typified by an epoxy compound.
- a photocationic polymerization initiator for initiating polymerization of the cationically polymerizable compound, and a photobase generator for generating a base upon irradiation with light may be contained.
- the optical film of the present invention has at least two resin films and an adhesive layer for bonding the two resin films, and the resin film has a surface opposite to the surface having the adhesive layer (the other side). May also have an adhesive layer.
- a known polarizing plate protective film can be provided on the other surface via an adhesive layer.
- the compositions for forming the respective adhesive layers may be the same or different, but from the viewpoint of productivity, both surfaces are formed from the same composition. It is preferable to have an adhesive layer.
- the surface to which the adhesive layer is applied may be subjected to a surface treatment such as saponification treatment, corona discharge treatment, or plasma treatment before the adhesion layer is applied.
- saponification treatment for example, adhesiveness with a polarizer material such as polyvinyl alcohol can be enhanced by subjecting a cellulose ester resin film to an alkali saponification treatment.
- saponification method the methods described in JP-A-2007-86748, paragraph number ⁇ 0211> and paragraph number ⁇ 0212> can be used.
- the alkali saponification treatment for the cellulose ester resin film is preferably performed in a cycle in which the film surface is immersed in an alkali solution, neutralized with an acidic solution, washed with water and dried.
- the alkaline solution include potassium hydroxide solution and sodium hydroxide solution.
- the concentration of hydroxide ions is preferably in the range of 0.1 to 5.0 mol / L, and more preferably in the range of 0.5 to 4.0 mol / L.
- the alkaline solution temperature is preferably in the range of room temperature to 90 ° C, and more preferably in the range of 40 to 70 ° C.
- a well-known method can be used for the method of bonding resin films together using an adhesive.
- the resin film (C) or (A) is brought close to one surface of the strip-shaped long resin film (A) or (C) moving in the horizontal direction or the vertical direction, and the resin film Applying an adhesive to be the adhesive layer (B) between (A) and the resin film (C) and applying pressure with a pinch roll to bond the resin film (A) and the resin film (C) together it can.
- the applied adhesive may be diluted with a solvent so that the material constituting the adhesive layer (B) can be applied. In that case, the solvent in the adhesive layer (B) is dried, and the adhesion between the resin film (A) and the resin film (C) is completed.
- the drying temperature at this time depends on the solvent type in the adhesive layer (B) and the resin type and thickness of the resin film (A) and the resin film (C).
- the solvent in the adhesive layer (B) is water. Is preferably 30 to 85 ° C., more preferably 45 to 80 ° C.
- the adhesive agent which becomes an adhesive bond layer (B) is apply
- the resin film (C) or (A) is brought close to the surface on which the adhesive layer (B) is formed at the same moving speed, and the resin film (A) and the resin film ( Between C), the solvent which swells an adhesive bond layer (B) is apply
- the drying temperature at this time depends on the solvent type and the resin type and thickness of the resin film (A) and the resin film (C). For example, when the solvent is water, it is preferably 30 to 85 ° C., more preferably Is 45-80 ° C.
- Hard coat layer (HC layer) In the present invention, from the viewpoint of surface hardness, at least one of the first resin film (A) and the second resin film (C) is the surface opposite to the side on which the adhesive layer (B) is provided. It is preferable to have a hard coat layer, and it is more preferable that either one of the resin films has. In this case, the hard coat layer is not regarded as a layer constituting the resin film (A) or (C) in the optical film of the present invention, and the tensile modulus of the resin film (A) or (C) is determined by the hard coat layer. It means the tensile elastic modulus of the resin film (A) or (C) not containing. As an embodiment of the optical film having the HC layer, as shown in FIG.
- the first resin film 1A, the adhesive layer d2A, and the second resin film 1B are laminated in this order, and the first resin film 1A is bonded.
- An optical film 4B having a hard coat layer 3A on the surface opposite to the surface having the layer 2A may be mentioned.
- the HC layer may be made of any material as long as the desired pencil hardness can be imparted to the optical film.
- the optical film of the present invention also exhibits the effects of the present invention when it has an HC layer on at least one of the first resin film (A) and the second resin film (C).
- this invention is not limited to the following aspect.
- HC layer obtained by curing a curable composition for forming a hard coat layer (HC layer)
- the HC layer used in the present invention can be obtained by curing the curable composition for forming an HC layer by irradiating it with active energy rays.
- active energy rays refer to ionizing radiation, and include X-rays, ultraviolet rays, visible light, infrared rays, electron beams, ⁇ rays, ⁇ rays, ⁇ rays and the like.
- the curable composition for HC layer formation used for forming the HC layer includes at least one component having a property of being cured by irradiation with active energy rays (hereinafter also referred to as “active energy ray curable component”).
- the active energy ray-curable component is preferably at least one polymerizable compound selected from the group consisting of radical polymerizable compounds and cationic polymerizable compounds.
- the “polymerizable compound” is a compound containing one or more polymerizable groups in one molecule.
- the polymerizable group is a group that can participate in the polymerization reaction, and specific examples include groups contained in various polymerizable compounds described below.
- the HC layer used in the present invention may have a single layer structure or a laminated structure of two or more layers, but an HC layer having a single layer structure or a laminated structure of two or more layers described in detail below is preferable.
- the curable composition for forming an HC layer having a one-layer structure As a preferred embodiment of the curable composition for forming an HC layer having a one-layer structure, as a first embodiment, at least one polymerizable compound having two or more ethylenically unsaturated groups in one molecule is used.
- the curable composition for HC layer formation containing can be mentioned.
- An ethylenically unsaturated group means a functional group containing an ethylenically unsaturated double bond.
- the 2nd aspect can mention the curable composition for HC layer formation containing an at least 1 type of radically polymerizable compound and an at least 1 type of cationically polymerizable compound.
- the curable composition for HC layer formation of a 1st aspect examples include esters of polyhydric alcohol and (meth) acrylic acid [
- esters of polyhydric alcohol and (meth) acrylic acid For example, ethylene glycol di (meth) acrylate, butanediol di (meth) acrylate, hexanediol di (meth) acrylate, 1,4-cyclohexanediacrylate, pentaerythritol tetra (meth) acrylate, pentaerythritol tri (meth) acrylate, Trimethylolpropane tri (meth) acrylate, trimethylolethane tri (meth) acrylate, dipentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate.
- (meth) acrylate described in the present specification is used in the meaning of one or both of acrylate and methacrylate.
- the “(meth) acryloyl group” described later is used to mean one or both of an acryloyl group and a methacryloyl group.
- “(Meth) acryl” is used to mean one or both of acrylic and methacrylic.
- polymeric compound only 1 type may be used and 2 or more types from which a structure differs may be used together.
- each component described in this specification may be used alone or in combination of two or more different structures.
- content of each component shall refer to those total content, when using 2 or more types from which a structure differs together.
- Polymerization of the polymerizable compound having an ethylenically unsaturated group can be performed by irradiation with active energy rays in the presence of a radical photopolymerization initiator.
- the curable composition for forming an HC layer according to the second aspect includes at least one radical polymerizable compound and at least one cationic polymerizable compound.
- the HC layer forming curable composition more preferably contains a radical photopolymerization initiator and a cationic photopolymerization initiator.
- this embodiment is referred to as a second embodiment (1).
- the radical polymerizable compound preferably contains one or more urethane bonds in one molecule together with two or more radical polymerizable groups in one molecule.
- this embodiment is referred to as a second embodiment (2).
- the HC layer obtained by curing the curable composition for forming an HC layer of the second aspect (2) preferably has a structure derived from a) of 15 to 15 when the total solid content of the HC layer is 100% by mass. 70% by mass, 25-80% by mass of the structure derived from b), 0.1-10% by mass of c), and 0.1-10% by mass of d).
- the HC layer-forming curable composition of the second embodiment (2) has the above a) when the total solid content of the HC layer-forming curable composition is 100% by mass.
- the content is preferably 15 to 70% by mass.
- the “alicyclic epoxy group” refers to a monovalent functional group having a cyclic structure in which an epoxy ring and a saturated hydrocarbon ring are condensed.
- the curable composition for forming an HC layer according to the second aspect includes at least one radical polymerizable compound and at least one cationic polymerizable compound.
- the radically polymerizable compound in the second aspect (1) contains two or more radically polymerizable groups selected from the group consisting of an acryloyl group and a methacryloyl group in one molecule.
- the radical polymerizable compound may contain, for example, 2 to 10 radical polymerizable groups selected from the group consisting of an acryloyl group and a methacryloyl group, preferably 2 to 6 in a molecule. Can do.
- radical polymerizable compound a radical polymerizable compound having a molecular weight of 200 or more and less than 1000 is preferable.
- molecular weight shall mean the weight average molecular weight measured in polystyrene conversion by gel permeation chromatography (GPC) about a multimer. The following measurement conditions can be mentioned as an example of the specific measurement conditions of a weight average molecular weight.
- GPC device HLC-8120 (manufactured by Tosoh Corporation) Column: TSK gel Multipore HXL-M (manufactured by Tosoh, inner diameter 7.8 mm ⁇ column length 30.0 cm)
- Eluent Tetrahydrofuran
- the radical polymerizable compound preferably contains one or more urethane bonds in one molecule.
- the number of urethane bonds contained in one molecule of the radical polymerizable compound is preferably 1 or more, more preferably 2 or more, more preferably 2 to 5, for example, 2 be able to.
- a radically polymerizable compound containing two urethane bonds in one molecule a radically polymerizable group selected from the group consisting of an acryloyl group and a methacryloyl group is bonded to only one urethane bond directly or via a linking group. It may be bonded to two urethane bonds directly or via a linking group.
- it is preferable that one or more radically polymerizable groups selected from the group consisting of acryloyl group and methacryloyl group are bonded to two urethane bonds bonded via a linking group.
- the radically polymerizable group selected from the group consisting of a urethane bond and an acryloyl group and a methacryloyl group may be directly bonded, and from the group consisting of a urethane bond and an acryloyl group and a methacryloyl group.
- the linking group is not particularly limited, and examples thereof include a linear or branched saturated or unsaturated hydrocarbon group, a cyclic group, and a group composed of a combination of two or more thereof.
- the number of carbon atoms of the hydrocarbon group is, for example, about 2 to 20, but is not particularly limited.
- Examples of the cyclic structure contained in the cyclic group include an aliphatic ring (such as a cyclohexane ring) and an aromatic ring (such as a benzene ring and a naphthalene ring).
- the above group may be unsubstituted or may have a substituent.
- the group described may have a substituent or may be unsubstituted.
- examples of the substituent include an alkyl group (for example, an alkyl group having 1 to 6 carbon atoms), a hydroxyl group, an alkoxy group (for example, an alkoxy group having 1 to 6 carbon atoms), a halogen atom (for example, a fluorine atom) , Chlorine atom, bromine atom), cyano group, amino group, nitro group, acyl group, carboxy group and the like.
- the radically polymerizable compound described above can be synthesized by a known method. Moreover, it is also possible to obtain as a commercial item. For example, as an example of the synthesis method, an alcohol, a polyol, and / or a hydroxyl group-containing compound such as a hydroxyl group-containing (meth) acrylic acid is reacted with an isocyanate, or, if necessary, a urethane compound obtained by the above reaction ( The method of esterifying with (meth) acrylic acid can be mentioned. “(Meth) acrylic acid” means one or both of acrylic acid and methacrylic acid.
- UV-1400B UV-1700B, UV-6300B, UV-7550B, UV-7600B, UV-7600B, Same UV-7605B, Same UV-7610B, Same UV-7620EA, Same UV-7630B, Same UV-7640B, Same UV-6 30B, UV-7000B, UV-7510B, UV-7461TE, UV-3000B, UV-3200B, UV-3210EA, UV-3310EA, UV-3310B, UV-3310B, UV-3500BA, UV-3500 3520TL, UV-3700B, UV-6100B, UV-6640B, UV-2000B,
- purple light UV-2750B manufactured by Nippon Synthetic Chemical Industry Co., Ltd.
- UL-503LN manufactured by Kyoeisha Chemical Co., Ltd.
- Unidic 17-806 manufactured by Dainippon Ink & Chemicals, Inc., 17-813, V-4030, V-4000BA, and Daicel.
- Examples include EB-1290K manufactured by UCB, Hicorp AU-2010 and AU-2020 manufactured by Tokushi.
- the radical polymerizable compound containing one or more urethane bonds in one molecule has been described.
- the compound may have no urethane bond.
- the curable composition for HC layer formation of the second aspect (1) is added to a radical polymerizable compound containing two or more radical polymerizable groups selected from the group consisting of acryloyl group and methacryloyl group in one molecule.
- One or more radically polymerizable compounds other than the radically polymerizable compound may be contained.
- a radical polymerizable compound containing two or more radically polymerizable groups selected from the group consisting of acryloyl group and methacryloyl group in one molecule and one or more urethane bonds in one molecule is used as the first radical. Radical polymerization that does not correspond to the first radical polymerizable compound, regardless of whether or not two or more radical polymerizable groups selected from the group consisting of acryloyl group and methacryloyl group are contained in one molecule.
- the functional compound is referred to as “second radical polymerizable compound”.
- the second radical polymerizable compound may or may not have one or more urethane bonds in one molecule.
- first radical polymerizable compound / second radical polymerizable compound 3/1 to 1/30
- the ratio is 2/1 to 1/20, more preferably 1/1 to 1/10.
- Radical polymerizable compound containing two or more radical polymerizable groups selected from the group consisting of acryloyl group and methacryloyl group of the curable composition for forming an HC layer of the second aspect (1) is preferably 30% by mass or more, more preferably 50% by mass or more, and further preferably 70% by mass or more with respect to 100% by mass of the total composition.
- the content is preferably 98% by mass or less, more preferably 95% by mass or less, and still more preferably 90% by mass or less with respect to 100% by mass of the total composition.
- the content of the first radical polymerizable compound of the curable composition for forming an HC layer of the second aspect (1) is preferably 30% by mass or more with respect to 100% by mass of the total composition. More preferably, it is 50 mass% or more, More preferably, it is 70 mass% or more.
- the content of the first radical polymerizable compound is preferably 98% by mass or less, more preferably 95% by mass or less, and 90% by mass or less with respect to 100% by mass of the total composition. More preferably it is.
- the second radical polymerizable compound is preferably a radical polymerizable compound having two or more radical polymerizable groups in one molecule and having no urethane bond.
- the radically polymerizable group contained in the second radically polymerizable compound is preferably an ethylenically unsaturated group, and in one aspect, a vinyl group is preferable.
- the ethylenically unsaturated group is preferably a radical polymerizable group selected from the group consisting of an acryloyl group and a methacryloyl group.
- the second radical polymerizable compound preferably has at least one radical polymerizable group selected from the group consisting of an acryloyl group and a methacryloyl group in one molecule and does not have a urethane bond.
- the second radical polymerizable compound includes one or more radical polymerizable groups selected from the group consisting of acryloyl group and methacryloyl group in one molecule as radical polymerizable compounds, and radical polymerizable groups other than these. One or more of these can also be included.
- the number of radical polymerizable groups contained in one molecule of the second radical polymerizable compound is preferably at least 2, more preferably 3 or more, and further preferably 4 or more.
- the number of radical polymerizable groups contained in one molecule of the second radical polymerizable compound is, for example, 10 or less in one embodiment, but may be more than 10.
- the second radical polymerizable compound is preferably a radical polymerizable compound having a molecular weight of 200 or more and less than 1000.
- Examples of the second radical polymerizable compound include the following. However, the present invention is not limited to the following exemplified compounds.
- a functional (meth) acrylate is mentioned.
- Two or more kinds of the second radical polymerizable compounds may be used in combination.
- a mixture “DPHA” manufactured by Nippon Kayaku Co., Ltd.
- dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate can be preferably used.
- polyester (meth) acrylate and epoxy (meth) acrylate having a weight average molecular weight of 200 to less than 1000 are also preferable.
- Commercially available products include, as polyester (meth) acrylate, trade name Beam Set 700 series manufactured by Arakawa Chemical Industries, such as Beam Set 700 (6 functional), Beam Set 710 (4 functional), Beam Set 720 (3 functional), and the like. It is done.
- epoxy (meth) acrylate trade name SP series made by Showa High Polymer, such as SP-1506, 500, SP-1507, 480, VR series, such as VR-77, trade name EA-, manufactured by Shin-Nakamura Chemical Co., Ltd. 1010 / ECA, EA-11020, EA-1025, EA-6310 / ECA and the like.
- the second radical polymerizable compound examples include the following exemplified compounds A-9 to A-11.
- the curable composition for forming an HC layer according to the second aspect (2) which is a preferred aspect of the second aspect, comprises b) a radical polymerizable compound containing 3 or more ethylenically unsaturated groups in one molecule.
- a radical polymerizable compound containing 3 or more ethylenically unsaturated groups in one molecule is also referred to as “component b” below.
- component b) examples include esters of polyhydric alcohol and (meth) acrylic acid, vinylbenzene and its derivatives, vinyl sulfone, (meth) acrylamide, and the like.
- a radical polymerizable compound containing three or more radical polymerizable groups selected from the group consisting of acryloyl group and methacryloyl group in one molecule is preferable.
- a specific example is an ester of polyhydric alcohol and (meth) acrylic acid, and a compound having three or more ethylenically unsaturated groups in one molecule.
- a resin containing three or more radically polymerizable groups selected from the group consisting of acryloyl groups and methacryloyl groups in one molecule is also preferred.
- the resin containing three or more radically polymerizable groups selected from the group consisting of acryloyl group and methacryloyl group in one molecule include polyester resins, polyether resins, acrylic resins, epoxy resins, and urethane resins.
- polymers such as polyfunctional compounds such as alkyd resins, spiroacetal resins, polybutadiene resins, polythiol polyene resins and polyhydric alcohols.
- radical polymerizable compound containing 3 or more radical polymerizable groups selected from the group consisting of acryloyl group and methacryloyl group in one molecule include the exemplified compounds shown in paragraph 0096 of JP-A-2007-256844. Etc.
- radically polymerizable compounds containing 3 or more radically polymerizable groups selected from the group consisting of acryloyl group and methacryloyl group in one molecule include KAYARAD DPHA, DPHA-2C, and PET manufactured by Nippon Kayaku.
- UV-1400B Purple light UV-1400B, UV-1700B, UV-6300B, UV-7550B, UV-7600B, UV-7605B, UV-7610B, UV-7620EA, UV-7630B, UV-7630B, UV-7640B UV-6630B, UV-7000B, UV-7510B, UV-7461TE, UV-3000B, UV-3200B, UV-3210EA, UV-3310EA, UV-3310EA, UV-3310B, UV-3500BA , UV-3520TL, UV-3700B, UV-6100B, UV-6640B, UV-2000B, UV-2010B, UV-2250EA, UV-2750B (manufactured by Nippon Synthetic Chemical), UL-503LN (Manufactured by Kyoeisha Chemical), Unidic 17-806, 17- 13, V-4030, V-4000BA (Dainippon Ink Chemical Co., Ltd.), EB-1290K, EB-220, EB-5129, EB-1830, EB-4358
- the HC layer obtained by curing the curable composition for forming an HC layer of the second aspect (2) is preferably derived from the above a) when the total solid content of the HC layer is 100% by mass.
- the structure may contain 15 to 70% by mass, the structure derived from the above b) from 25 to 80% by mass, the above c) from 0.1 to 10% by mass, and the d) from 0.1 to 10% by mass.
- the structure derived from b) is preferably contained in an amount of 40 to 75% by mass, more preferably 60 to 75% by mass when the total solid content of the HC layer is 100% by mass.
- the HC layer-forming curable composition of the second aspect (2) has a component b) of 40 to 75% by mass when the total solid content of the HC layer-forming curable composition is 100% by mass. %, Preferably 60 to 75% by mass.
- the curable composition for forming an HC layer according to the second aspect includes at least one radical polymerizable compound and at least one cationic polymerizable compound.
- Any cationically polymerizable compound can be used without any limitation as long as it has a polymerizable group capable of cationic polymerization (cationic polymerizable group).
- the number of cationically polymerizable groups contained in one molecule is at least one.
- the cationic polymerizable compound may be a monofunctional compound containing one cationic polymerizable group in one molecule or a polyfunctional compound containing two or more.
- the number of cationically polymerizable groups contained in the polyfunctional compound is not particularly limited, but is 2 to 6 per molecule, for example. Further, two or more cationically polymerizable groups contained in one molecule of the polyfunctional compound may be the same, or two or more kinds having different structures may be used.
- the cationically polymerizable compound preferably has one or more radically polymerizable groups in one molecule together with the cationically polymerizable group.
- the above description of the radically polymerizable compound can be referred to.
- it is an ethylenically unsaturated group
- the ethylenically unsaturated group is more preferably a radical polymerizable group selected from the group consisting of a vinyl group, an acryloyl group, and a methacryloyl group.
- the number of radically polymerizable groups in one molecule of the cationically polymerizable compound having a radically polymerizable group is at least 1, preferably 1 to 3, and more preferably 1.
- Preferred examples of the cationic polymerizable group include an oxygen-containing heterocyclic group and a vinyl ether group.
- the cationically polymerizable compound may contain one or more oxygen-containing heterocyclic groups and one or more vinyl ether groups in one molecule.
- the oxygen-containing heterocycle may be a single ring or a condensed ring. Those having a bicyclo skeleton are also preferred.
- the oxygen-containing heterocycle may be a non-aromatic ring or an aromatic ring, and is preferably a non-aromatic ring.
- Specific examples of the monocycle include an epoxy ring, a tetrahydrofuran ring, and an oxetane ring.
- an oxabicyclo ring can be mentioned as what has a bicyclo skeleton.
- the cationically polymerizable group containing an oxygen-containing heterocyclic ring is contained in the cationically polymerizable compound as a monovalent substituent or a divalent or higher polyvalent substituent.
- the above condensed ring is a product in which one or more oxygen-containing heterocycles and one or more ring structures other than the oxygen-containing heterocycle are condensed, even if two or more oxygen-containing heterocycles are condensed.
- the ring structure other than the oxygen-containing heterocycle include, but are not limited to, cycloalkane rings such as a cyclohexane ring.
- the cationically polymerizable compound may contain a partial structure other than the cationically polymerizable group.
- a partial structure is not particularly limited, and may be a linear structure, a branched structure, or a cyclic structure. These partial structures may contain one or more heteroatoms such as oxygen atoms and nitrogen atoms.
- a compound containing a cyclic structure can be mentioned as the cationically polymerizable group or as a partial structure other than the cationically polymerizable group.
- the cyclic structure contained in the cyclic structure-containing compound is, for example, one per molecule and may be two or more.
- the number of cyclic structures contained in the cyclic structure-containing compound is, for example, 1 to 5 per molecule, but is not particularly limited.
- a compound containing two or more cyclic structures in one molecule may contain the same cyclic structure, or may contain two or more types of cyclic structures having different structures.
- cyclic structure contained in the cyclic structure-containing compound is an oxygen-containing heterocyclic ring. The details are as described above.
- Cationic polymerizability obtained by dividing the molecular weight (hereinafter referred to as “B”) by the number of cationic polymerizable groups (hereinafter referred to as “C”) contained in one molecule of the cationic polymerizable compound.
- the cation polymerizable group equivalent is preferably 50 or more.
- requires a cationically polymerizable group equivalent can be an epoxy group (epoxy ring). That is, in one aspect, the cationically polymerizable compound is an epoxy ring-containing compound.
- the epoxy ring-containing compound is obtained by dividing the molecular weight by the number of epoxy rings contained in one molecule from the viewpoint of improving the adhesion between the HC layer obtained by curing the HC layer forming curable composition and the resin film.
- the epoxy group equivalent is preferably less than 150.
- the epoxy group equivalent of an epoxy ring containing compound is 50 or more, for example.
- the molecular weight of the cationic polymerizable compound is preferably 500 or less, and more preferably 300 or less.
- the cationically polymerizable compound having a molecular weight in the above range tends to easily penetrate into the resin film, and can contribute to improving the adhesion between the HC layer obtained by curing the curable composition for HC layer formation and the resin film. I guess.
- the curable composition for HC layer formation of the second aspect (2) includes a) an alicyclic epoxy group and an ethylenically unsaturated group, and the number of alicyclic epoxy groups contained in one molecule is one. And the number of ethylenically unsaturated groups contained in one molecule is 1, and the cationically polymerizable compound having a molecular weight of 300 or less is included.
- the a) will be referred to as “a) component”.
- Examples of the ethylenically unsaturated group include radical polymerizable groups including an acryloyl group, a methacryloyl group, a vinyl group, a styryl group, and an allyl group. Among them, an acryloyl group, a methacryloyl group, and C (O) OCH ⁇ CH 2 An acryloyl group and a methacryloyl group are more preferable.
- the number of alicyclic epoxy groups and ethylenically unsaturated groups in one molecule is preferably one each.
- the molecular weight of the component is 300 or less, preferably 210 or less, and more preferably 200 or less.
- R represents a monocyclic hydrocarbon or a bridged hydrocarbon
- L represents a single bond or a divalent linking group
- Q represents an ethylenically unsaturated group.
- R in the general formula (1) is a monocyclic hydrocarbon
- the monocyclic hydrocarbon is preferably an alicyclic hydrocarbon, and more preferably an alicyclic group having 4 to 10 carbon atoms.
- An alicyclic group having 5 to 7 carbon atoms is more preferable, and an alicyclic group having 6 carbon atoms is particularly preferable.
- Preferable specific examples include a cyclobutyl group, a cyclopentyl group, a cyclohexyl group and a cycloheptyl group, and a cyclohexyl group is more preferable.
- R in the general formula (1) is a bridged hydrocarbon
- the bridged hydrocarbon is preferably a bicyclic bridged hydrocarbon (bicyclo ring) or a tricyclic bridged hydrocarbon (tricyclo ring).
- Specific examples include bridged hydrocarbons having 5 to 20 carbon atoms, such as norbornyl group, bornyl group, isobornyl group, tricyclodecyl group, dicyclopentenyl group, dicyclopentanyl group, tricyclopentenyl group.
- the divalent linking group is preferably a divalent aliphatic hydrocarbon group.
- the carbon number of the divalent aliphatic hydrocarbon group is preferably in the range of 1 to 6, more preferably in the range of 1 to 3, and still more preferably 1.
- the divalent aliphatic hydrocarbon group is preferably a linear, branched or cyclic alkylene group, more preferably a linear or branched alkylene group, and even more preferably a linear alkylene group.
- Examples of Q include ethylenically unsaturated groups including an acryloyl group, a methacryloyl group, a vinyl group, a styryl group, and an allyl group.
- an acryloyl group, a methacryloyl group, and C (O) OCH ⁇ CH 2 are preferable, and acryloyl More preferred are groups and methacryloyl groups.
- component a) examples include various compounds exemplified in JP-A-10-17614, paragraph 0015, compounds represented by the following general formula (1A) or (1B), 1,2-epoxy-4- A vinyl cyclohexane etc. can be mentioned. Especially, the compound represented by the following general formula (1A) or (1B) is more preferable. In addition, the compound represented by the following general formula (1A) is also preferably an isomer thereof.
- R 1 represents a hydrogen atom or a methyl group
- L 2 represents a divalent aliphatic hydrocarbon group having 1 to 6 carbon atoms.
- the carbon number of the divalent aliphatic hydrocarbon group represented by L 2 in the general formulas (1A) and (1B) is in the range of 1 to 6, and more preferably in the range of 1 to 3. More preferably, it has 1 carbon.
- the divalent aliphatic hydrocarbon group is preferably a linear, branched or cyclic alkylene group, more preferably a linear or branched alkylene group, and even more preferably a linear alkylene group.
- the HC layer obtained by curing the curable composition for forming an HC layer of the second aspect (2) preferably has a structure derived from a) of 15 to 15 when the total solid content of the HC layer is 100% by mass.
- the content is preferably 70% by mass, more preferably 18 to 50% by mass, and still more preferably 22 to 40% by mass.
- the HC layer-forming curable composition of the second aspect (2) is 15 to 70 masses when the a) component is 100 mass% of the total solid content of the HC layer-forming curable composition. %, Preferably 18 to 50% by mass, more preferably 22 to 40% by mass.
- a nitrogen-containing heterocyclic ring As another example of the cyclic structure contained in the cyclic structure-containing compound, a nitrogen-containing heterocyclic ring can be mentioned.
- the nitrogen-containing heterocyclic ring-containing compound is a preferred cationically polymerizable compound from the viewpoint of improving the adhesion between the HC layer obtained by curing the HC layer forming curable composition and the resin film.
- the nitrogen-containing heterocycle-containing compound include isocyanurate rings (nitrogen-containing heterocycles contained in the exemplified compounds B-1 to B-3 described later) and glycoluril rings (nitrogen-containing heterocycles contained in the exemplified compound B-10 described later).
- a compound having at least one nitrogen-containing heterocyclic ring selected from the group consisting of (ring) per molecule is preferable.
- a compound containing an isocyanurate ring is a more preferable cationic polymerizable compound from the viewpoint of improving the adhesion between the HC layer obtained by curing the HC layer forming curable composition and the resin film.
- the present inventors infer that this is because the isocyanurate ring is excellent in affinity with the resin constituting the resin film. From this point, a resin film including an acrylic resin film is more preferable, and a surface directly in contact with the HC layer obtained by curing the curable composition for forming an HC layer is more preferably an acrylic resin film surface.
- an alicyclic structure can be exemplified.
- the alicyclic structure include a cyclo ring, a dicyclo ring, and a tricyclo ring structure, and specific examples include a dicyclopentanyl ring and a cyclohexane ring.
- the cationically polymerizable compound described above can be synthesized by a known method. Moreover, it is also possible to obtain as a commercial item.
- cationic polymerizable compound containing an oxygen-containing heterocycle examples include, for example, 3,4-epoxycyclohexylmethyl methacrylate (commercially available product such as Daicel Cyclomer M100), 3,4-epoxy.
- Cyclohexylmethyl-3 ′, 4′-epoxycyclohexanecarboxylate for example, commercially available products such as UVR6105 and UVR6110 manufactured by Union Carbide and CELLOXIDE 2021 manufactured by Daicel Chemical
- bis (3,4-epoxycyclohexylmethyl) adipate for example, union car UVR6128 manufactured by Bite
- vinyl cyclohexylene monoepoxide for example, CELLOXIDE 2000 manufactured by Daicel Chemical Industries
- ⁇ -caprolactone-modified 3,4-epoxycyclohexylmethyl 3 ′, 4′-epoch Cycyclohexanecarboxylate for example, CELLOXIDE 2081 manufactured by Daicel Chemical Industries
- 1-methyl-4- (2-methyloxiranyl) -7-oxabicyclo [4,1,0] heptane for example, CELLOXIDE 3000 manufactured by Daicel Chemical Industries
- the cationic polymerizable compound containing a vinyl ether group examples include 1,4-butanediol divinyl ether, 1,6-hexanediol divinyl ether, nonanediol divinyl ether, and cyclohexanediol divinyl ether. , Cyclohexanedimethanol divinyl ether, triethylene glycol divinyl ether, trimethylolpropane trivinyl ether, pentaerythritol tetravinyl ether, and the like.
- the cationically polymerizable compound containing a vinyl ether group those having an alicyclic structure are also preferable.
- JP-A-8-143806, JP-A-8-283320, JP-A-2000-186079, JP-A-2000-327672, JP-A-2004-315778, Compounds exemplified in Kaikai 2005-29632 and the like can also be used.
- exemplary compounds B-1 to B-14 are shown as specific examples of the cationically polymerizable compound, but the present invention is not limited to the following specific examples.
- preferred embodiments of the HC layer forming curable composition include the following modes. It is more preferable to satisfy one or more of the following aspects, it is more preferable to satisfy two or more, still more preferable to satisfy three or more, and still more preferable to satisfy all. In addition, it is also preferable that one cationically polymerizable compound satisfy
- a nitrogen-containing heterocyclic ring-containing compound is included.
- the nitrogen-containing heterocycle of the nitrogen-containing heterocycle-containing compound is selected from the group consisting of an isocyanurate ring and a glycoluril ring.
- the nitrogen-containing heterocyclic ring-containing compound is more preferably an isocyanurate ring-containing compound. More preferably, the isocyanurate ring-containing compound is an epoxy ring-containing compound containing one or more epoxy rings in one molecule.
- the cationic polymerizable compound includes a cationic polymerizable compound having a cationic polymerizable group equivalent of less than 150.
- an epoxy group-containing compound having an epoxy group equivalent of less than 150 is included.
- the cationically polymerizable compound contains an ethylenically unsaturated group.
- an oxetane ring-containing compound containing one or more oxetane rings in one molecule is included together with other cationically polymerizable compounds.
- the oxetane ring-containing compound is a compound that does not contain a nitrogen-containing heterocycle.
- the content of the cation polymerizable compound in the curable composition for forming an HC layer is preferably 10 parts by mass or more with respect to 100 parts by mass of the total content of the radical polymerizable compound and the cation polymerizable compound. Preferably it is 15 mass parts or more, More preferably, it is 20 mass parts or more. Further, the content of the cationic polymerizable compound in the curable composition for forming an HC layer is 50 parts by mass or less with respect to 100 parts by mass of the total content of the radical polymerizable compound and the cationic polymerizable compound. preferable.
- the content of the cationic polymerizable compound in the curable composition for forming an HC layer is preferably 100 parts by mass of the total content of the first radical polymerizable compound and the cationic polymerizable compound. It is 0.05 mass part or more, More preferably, it is 0.1 mass part or more, More preferably, it is 1 mass part or more.
- the content of the cationic polymerizable compound is preferably 50 parts by mass or less with respect to 100 parts by mass of the total content of the first radical polymerizable compound and the cationic polymerizable compound, and 40 masses. It is more preferable that the amount is not more than parts.
- the compound which has both a cationically polymerizable group and a radically polymerizable group shall be classified into a cationically polymerizable compound, and shall prescribe
- the curable composition for HC layer formation preferably contains a polymerization initiator, and more preferably contains a photopolymerization initiator.
- the curable composition for forming an HC layer containing a radical polymerizable compound preferably contains a radical photopolymerization initiator, and the curable composition for forming an HC layer containing a cationic polymerizable compound contains a cationic photopolymerization initiator. It is preferable. Only one radical photopolymerization initiator may be used, or two or more radical photopolymerization initiators having different structures may be used in combination. The same applies to the cationic photopolymerization initiator. Hereafter, each photoinitiator is demonstrated one by one.
- the radical photopolymerization initiator may be any radical photopolymerization initiator as long as it can generate a radical as an active species by light irradiation, and a known radical photopolymerization initiator can be used without any limitation. it can.
- Specific examples include, for example, diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, benzyldimethyl ketal, 4- (2-hydroxyethoxy) phenyl- (2-hydroxy-2-propyl) ) Ketone, 1-hydroxycyclohexyl phenyl ketone, 2-methyl-2-morpholino (4-thiomethylphenyl) propan-1-one, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butanone, 2 -Hydroxy-2-methyl-1- [4- (1-methylvinyl) phenyl] propanone oligomer, 2-hydroxy-1- ⁇ 4- [4- (2-hydroxy-2-methyl-propionyl) -benzyl] Acetophenones such as phenyl ⁇ -2-methyl-propan-1-one; 1,2-octanedi 1- [4- (phenylthio)-, 2- (O-benzoyloxime)
- Ruphosphine oxides and the like.
- radical photopolymerization initiators and auxiliaries can be synthesized by known methods, and can also be obtained as commercial products.
- the content of the radical photopolymerization initiator in the curable composition for forming an HC layer may be appropriately adjusted within a range in which the polymerization reaction (radical polymerization) of the radical polymerizable compound proceeds well, and is not particularly limited. Absent.
- the amount is, for example, in the range of 0.1 to 20 parts by weight, preferably 0.5 to 10 parts by weight, more preferably 1 to 100 parts by weight of the radical polymerizable compound contained in the curable composition for forming an HC layer. It is in the range of ⁇ 10 parts by mass.
- Any cationic photopolymerization initiator may be used as long as it can generate a cation as an active species by light irradiation, and any known cationic photopolymerization initiator can be used without any limitation. it can. Specific examples include known sulfonium salts, ammonium salts, iodonium salts (for example, diaryl iodonium salts), triaryl sulfonium salts, diazonium salts, iminium salts, and the like.
- cationic photopolymerization initiators represented by formulas (25) to (28) shown in paragraphs 0050 to 0053 of JP-A-8-143806, paragraphs of JP-A-8-283320
- the cationic photopolymerization initiator can be synthesized by a known method, and is also available as a commercial product. Examples of commercially available products include CI-1370, CI-2064, CI-2397, CI-2624, CI-2939, CI-2734, CI-2758, CI-2823, CI-2855, and CI-5102 manufactured by Nippon Soda.
- PHOTOINITIATOR 2047 manufactured by Rhodia, UVI-6974, UVI-6990 manufactured by Union Carbide, and CPI-10P manufactured by San Apro can be used.
- a diazonium salt, an iodonium salt, a sulfonium salt, and an iminium salt are preferable from the viewpoints of sensitivity of the photopolymerization initiator to light and stability of the compound. In terms of weather resistance, iodonium salts are most preferred.
- iodonium salt-based cationic photopolymerization initiators include, for example, B2380 manufactured by Tokyo Chemical Industry, Midori Chemical BBI-102, WPI-113 manufactured by Wako Pure Chemical Industries, WPI-124 manufactured by Wako Pure Chemical Industries, Examples thereof include WPI-169 manufactured by Koyo Pure Chemical Industries, WPI-170 manufactured by Wako Pure Chemical Industries, and DTBPI-PFBS manufactured by Toyo Gosei.
- the content of the cationic photopolymerization initiator in the curable composition for forming an HC layer may be appropriately adjusted within a range in which the polymerization reaction (cationic polymerization) of the cationic polymerizable compound proceeds favorably, and is not particularly limited. Absent. For example, it is in the range of 0.1 to 200 parts by weight, preferably 1 to 150 parts by weight, and more preferably 2 to 100 parts by weight with respect to 100 parts by weight of the cationically polymerizable compound.
- photopolymerization initiators As other photopolymerization initiators, the photopolymerization initiators described in paragraphs 0052 to 0055 of JP-A-2009-204725 can also be mentioned, and the contents of this publication are incorporated in the present invention.
- the curable composition for HC layer formation contains at least 1 type of component which has a property hardened
- the curable composition for HC layer formation can contain the inorganic particle whose average primary particle diameter is less than 2 micrometers. From the viewpoint of improving the hardness of the front plate having the HC layer obtained by curing the curable composition for forming the HC layer (and further improving the hardness of the liquid crystal panel having the front plate), the curable composition for forming the HC layer and this composition are used.
- the HC layer obtained by curing the material preferably contains inorganic particles having an average primary particle size of less than 2 ⁇ m.
- the average primary particle size of the inorganic particles is preferably in the range of 10 nm to 1 ⁇ m, more preferably in the range of 10 nm to 100 nm, and still more preferably in the range of 10 nm to 50 nm.
- the particles were observed with a transmission electron microscope (magnification 500,000 to 2,000,000 times), and 100 randomly selected particles (primary particles) were observed.
- the average primary particle size is determined by the average value of the particle sizes.
- examples of the inorganic particles include silica particles, titanium dioxide particles, zirconium oxide particles, and aluminum oxide particles. Of these, silica particles are preferred.
- the surface of the inorganic particles is preferably treated with a surface modifier containing an organic segment in order to increase the affinity with the organic component contained in the HC layer forming curable composition.
- a surface modifier those having a functional group capable of forming a bond with the inorganic particle or adsorbing to the inorganic particle and a functional group having high affinity with the organic component in the same molecule are preferable.
- the surface modifier having a functional group capable of binding or adsorbing to inorganic particles include silane surface modifiers, metal alkoxide surface modifiers such as aluminum, titanium, and zirconium, phosphate groups, sulfate groups, sulfonate groups, and carboxyl groups.
- a surface modifier having an anionic group such as an acid group is preferred.
- the functional group having high affinity with the organic component include a functional group having hydrophilicity / hydrophobicity similar to that of the organic component, a functional group capable of being chemically bonded to the organic component, and the like.
- a functional group that can be chemically bonded to an organic component is preferable, and an ethylenically unsaturated group or a ring-opening polymerizable group is more preferable.
- a preferred inorganic particle surface modifier is a metal alkoxide surface modifier or a polymerizable compound having an anionic group and an ethylenically unsaturated group or ring-opening polymerizable group in the same molecule.
- Specific examples of the surface modifier include the following exemplified compounds S-1 to S-8.
- X represents a hydrogen atom or a methyl group
- the surface modification of the inorganic particles with the surface modifier is preferably performed in a solution.
- a surface modifier is present together, or after inorganic particles are mechanically dispersed, the surface modifier is added and stirred, or the inorganic particles are mechanically dispersed.
- the surface may be modified before heating (if necessary, heated, dried and then heated, or changed in pH (power of hydrogen)), and then dispersed.
- the solvent for dissolving the surface modifier an organic solvent having a large polarity is preferable. Specific examples include known solvents such as alcohols, ketones and esters.
- the content of the inorganic particles is preferably 5 to 40% by mass and more preferably 10 to 30% by mass when the total solid content of the HC layer forming curable composition is 100% by mass.
- the shape of the primary particles of the inorganic particles may be spherical or non-spherical, but the primary particles of the inorganic particles are preferably spherical, and in the HC layer obtained by curing the curable composition for HC layer formation, It is more preferable from the viewpoint of further improving the hardness that the inorganic particles (primary particles) are present as higher-order particles of non-spherical secondary particles or more connected to each other.
- the inorganic particles include ELCOM V-8802 (spherical silica particles having an average primary particle size of 15 nm manufactured by JGC Catalysts and Chemicals), ELCOM V-8803 (deformed silica particles manufactured by JGC Catalysts and Chemicals), MiBK-SD ( (Spherical silica particles with an average primary particle size of 10-20 nm manufactured by Nissan Chemical Industries), MEK-AC-2140Z (spherical silica particles with an average primary particle size of 10-20 nm manufactured by Nissan Chemical Industries), MEK-AC-4130 (Nissan Chemical Industries) Spherical silica particles having an average primary particle size of 45 nm, MiBK-SD-L (spherical silica particles having an average primary particle size of 40 to 50 nm manufactured by Nissan Chemical Industries), MEK-AC-5140Z (average primary by Nissan Chemical Industries, Ltd.) And spherical silica particles having a particle diameter of 85 nm).
- Matte particles mean particles having an average primary particle diameter of 2 ⁇ m or more, and may be inorganic particles, organic particles, or particles of an inorganic / organic composite material.
- the shape of the mat particles may be spherical or non-spherical.
- the average primary particle size of the mat particles is preferably in the range of 2 to 20 ⁇ m, more preferably in the range of 4 to 14 ⁇ m, and still more preferably in the range of 6 to 10 ⁇ m.
- the mat particles include inorganic particles such as silica particles and TiO 2 particles, and organic particles such as crosslinked acrylic particles, crosslinked acrylic-styrene particles, crosslinked styrene particles, melamine resin particles, and benzoguanamine resin particles.
- the mat particles are preferably organic particles, and more preferably crosslinked acrylic particles, crosslinked acrylic-styrene particles, and crosslinked styrene particles.
- the mat particles preferably have a content per unit volume in the HC layer obtained by curing the curable composition for forming an HC layer of 0.10 g / cm 3 or more, and 0.10 g / cm 3 to 0.40 g / More preferably, it is cm 3 , and more preferably 0.10 g / cm 3 to 0.30 g / cm 3 .
- the curable composition for HC layer formation contains a ultraviolet absorber.
- the ultraviolet absorber include benzotriazole compounds and triazine compounds.
- the benzotriazole compound is a compound having a benzotriazole ring, and specific examples include various benzotriazole ultraviolet absorbers described in paragraph 0033 of JP2013-111835A.
- the triazine compound is a compound having a triazine ring, and specific examples thereof include various triazine-based UV absorbers described in paragraph 0033 of JP2013-111835A.
- the content of the ultraviolet absorber in the resin film is, for example, about 0.1 to 10 parts by mass with respect to 100 parts by mass of the resin contained in the film, but is not particularly limited.
- the UV absorber reference can also be made to paragraph 0032 of JP2013-111835A.
- ultraviolet rays refer to light having an emission center wavelength in the wavelength band of 200 to 380 nm.
- the curable composition for HC layer formation contains fluorine-containing compounds, such as a leveling agent and an antifouling agent.
- a fluorine-containing polymer is preferably used.
- a fluoroaliphatic group-containing polymer described in Japanese Patent No. 5175831 can be mentioned.
- a fluoroaliphatic group-containing polymer having a fluoroaliphatic group-containing monomer represented by the general formula (1) constituting the fluoroaliphatic group-containing polymer and having a content of 50% by mass or less of the total polymerization units is used as a leveling agent. You can also.
- the antifouling agent preferably contains a fluorine-containing compound.
- the fluorine-containing compound preferably has a perfluoropolyether group and a polymerizable group (preferably a radically polymerizable group), has a perfluoropolyether group and a polymerizable group, and the polymerizable group is contained in one molecule. It is more preferable to have a plurality. By setting it as such a structure, the effect of abrasion resistance improvement can be exhibited more effectively.
- the fluorine-containing compound may be any of a monomer, an oligomer and a polymer, but is preferably an oligomer (fluorine-containing oligomer).
- a leveling agent and an antifouling agent described in (vi) other components described later can also be contained.
- antifouling agent that can be used in the present invention, in addition to the above, materials described in paragraphs 0012 to 0101 of JP2012-088699A can be used, and the contents of this gazette are incorporated in the present specification. .
- an antifouling agent demonstrated above what was synthesize
- commercially available products RS-90, RS-78 manufactured by DIC, etc. can be preferably used.
- the content is preferably 0.01 to 7% by mass, preferably 0.05 to 5% by mass of the solid content of the curable composition for HC layer formation. % Is more preferable, and 0.1 to 2% by mass is more preferable.
- the curable composition for HC layer formation may contain only 1 type of antifouling agents, and may contain 2 or more types. When 2 or more types are contained, it is preferable that the total amount becomes the said range.
- the curable composition for HC layer formation can also be set as the structure which does not contain an antifouling agent substantially.
- the curable composition for HC layer formation contains a solvent.
- a solvent an organic solvent is preferable, and one or more organic solvents can be mixed and used in an arbitrary ratio.
- the organic solvent include alcohols such as methanol, ethanol, propanol, n-butanol and i-butanol; ketones such as acetone, methyl isobutyl ketone, methyl ethyl ketone and cyclohexanone; cellosolves such as ethyl cellosolve; toluene And aromatics such as xylene; glycol ethers such as propylene glycol monomethyl ether; acetates such as methyl acetate, ethyl acetate and butyl acetate; diacetone alcohol and the like.
- cyclohexanone, methyl ethyl ketone, methyl isobutyl ketone, and methyl acetate are preferable, and it is more preferable to use cyclohexanone, methyl ethyl ketone, methyl isobutyl ketone, and methyl acetate in an arbitrary ratio.
- the optical film excellent in abrasion resistance, punching property, and adhesiveness is obtained.
- the amount of the solvent in the curable composition for forming the HC layer can be appropriately adjusted as long as the application suitability of the composition can be ensured.
- the solvent can be 50 to 500 parts by mass, preferably 80 to 200 parts by mass with respect to 100 parts by mass of the total amount of the polymerizable compound and the photopolymerization initiator.
- the solid content of the HC-forming curable composition is preferably 10 to 90% by mass, more preferably 50 to 80% by mass, and particularly preferably 65 to 75% by mass.
- the curable composition for HC layer formation can contain 1 or more types of well-known additive in arbitrary quantity.
- the additive include a surface conditioner, a leveling agent, a polymerization inhibitor, and a polyrotaxane.
- a commercially available antifouling agent or an antifouling agent that can be prepared by a known method can also be included.
- the additive is not limited to these, and various additives that can be generally added to the curable composition for HC layer formation can be used.
- the curable composition for HC layer formation can also contain a well-known solvent in arbitrary amounts.
- the curable composition for HC layer formation can be prepared by mixing the various components described above simultaneously or sequentially in an arbitrary order.
- the preparation method is not particularly limited, and a known stirrer or the like can be used for the preparation.
- the optical film of the present invention preferably has an embodiment in which the HC layer 3A in FIG. 2 has at least the first HC layer and the second HC layer in this order from the resin film 1A side. Even if the 1st HC layer is located in the surface of 1 A of resin films, you may have another layer in between. Similarly, even if the second HC layer is located on the surface of the first HC layer, another layer may be provided therebetween. From the viewpoint of improving the adhesion between the first HC layer and the second HC layer, the second HC layer is located on the surface of the first HC layer, that is, both layers are at least part of the film surface. It is preferable to contact.
- the first HC layer and the second HC layer may each be one layer or two or more layers, but one layer is preferable.
- the optical film of the present invention when used for a touch panel, it is preferable to dispose the optical film so that the second HC layer is on the front side of the image display element.
- the second HC layer is preferably disposed on the surface side of the optical film, particularly on the outermost surface.
- the first HC layer of the present invention is formed from the first curable composition for HC layer formation.
- the first curable composition for HC layer formation is different from the polymerizable compound 1 having a radical polymerizable group, and having a cationic polymerizable group and a radical polymerizable group in the same molecule, and different from the polymerizable compound 1.
- the content of the polymerizable compound 2 is 51% by mass or more.
- the first curable composition for HC layer formation may have another polymerizable compound different from the polymerizable compound 1 and the polymerizable compound 2.
- the other polymerizable compound is preferably a polymerizable compound having a cationic polymerizable group.
- the cationic polymerizable group has the same meaning as the cationic polymerizable group described in the polymerizable compound 2, and the preferred range is also the same.
- a nitrogen-containing heterocyclic ring-containing compound containing a cationic polymerizable group is preferable as the other polymerizable compound.
- the adhesiveness between the resin film and the first HC layer can be improved more effectively.
- the nitrogen-containing heterocycle include isocyanurate rings (nitrogen-containing heterocycles contained in exemplified compounds B-1 to B-3 described later) and glycoluril rings (nitrogen-containing heterocycles contained in exemplified compound B-10 described later).
- a nitrogen-containing heterocyclic ring selected from the group consisting of is exemplified, and an isocyanurate ring is more preferable.
- the number of cationic groups possessed by other polymerizable compounds is preferably 1 to 10, more preferably 2 to 5.
- the resin film is preferably a resin film including an acrylic resin film. By setting it as such a structure, it exists in the tendency for the adhesiveness of a resin film and a 1st HC layer to improve more.
- Specific examples of the other polymerizable compounds include the above-described exemplary compounds B-1 to B-14, but the present invention is not limited to the specific examples described above.
- the description of the above-mentioned polymerization initiator, inorganic particles, matte particles, ultraviolet absorbers, fluorine-containing compounds, solvents and other components can be preferably applied.
- the first HC layer forming curable composition preferably includes a solvent
- the second HC layer forming curable composition preferably includes an antifouling agent.
- the thickness of the HC layer is preferably 3 ⁇ m to 100 ⁇ m, more preferably 5 ⁇ m to 70 ⁇ m, and even more preferably 10 ⁇ m to 50 ⁇ m.
- HC layer pencil hardness The higher the pencil hardness of the HC layer, the better. Specifically, 5H or higher is preferable, and 7H or higher is more preferable.
- the HC layer can be formed by applying the curable composition for forming the HC layer directly on the resin film or through another layer such as an easy-adhesion layer and irradiating with active energy rays.
- the coating can be performed by a known coating method such as a dip coating method, an air knife coating method, a curtain coating method, a roller coating method, a die coating method, a wire bar coating method, or a gravure coating method.
- the HC layer can also be formed as an HC layer having a laminated structure of two or more layers (for example, about 2 to 5 layers) by simultaneously or sequentially applying two or more kinds of compositions having different compositions.
- An HC layer can be formed by irradiating the applied curable composition for forming an HC layer with active energy rays.
- the curable composition for HC layer formation contains a radical polymerizable compound, a cationic polymerizable compound, a radical photopolymerization initiator, and a cationic photopolymerization initiator
- the polymerization reaction of the radical polymerizable compound and the cationic polymerizable compound is performed.
- Each can be initiated and advanced by the action of a radical photopolymerization initiator and a cationic photopolymerization initiator. What is necessary is just to determine the wavelength of the light to irradiate according to the kind of polymeric compound and polymerization initiator to be used.
- Light sources for light irradiation include high-pressure mercury lamps that emit light in the 150 to 450 nm wavelength band, ultrahigh-pressure mercury lamps, carbon arc lamps, metal halide lamps, xenon lamps, chemical lamps, electrodeless discharge lamps, and LEDs (Light Emitting Diodes). Etc. Moreover, the light irradiation amount is generally in the range of 30 ⁇ 3000mJ / cm 2, preferably in the range of 100 ⁇ 1500mJ / cm 2. You may perform a drying process as needed in one or both before and after light irradiation. The drying process can be performed by blowing warm air, disposing in a heating furnace, conveying in the heating furnace, or the like. When the curable composition for HC layer formation contains a solvent, the heating temperature may be set to a temperature at which the solvent can be removed by drying, and is not particularly limited. Here, the heating temperature refers to the temperature of warm air or the atmospheric temperature in the heating furnace.
- Articles having an optical film As articles containing the optical film of the present invention, keystroke durability and manufacturing suitability are improved in various industries including the home appliance industry, electrical and electronic industry, automobile industry, and housing industry. Can be listed as various articles. Specific examples include an image display device such as a touch sensor, a touch panel, and a liquid crystal display device, a window glass of an automobile, a window glass of a house, and the like.
- an image display device such as a touch sensor, a touch panel, and a liquid crystal display device, a window glass of an automobile, a window glass of a house, and the like.
- the optical film of the present invention is preferably used as an optical film used for a front plate for an image display device, and more preferably an optical film used for a front plate of an image display element of a touch panel.
- the touch panel that can use the optical film of the present invention is not particularly limited, and can be appropriately selected according to the purpose. For example, a surface capacitive touch panel, a projected capacitive touch panel, a resistive touch panel Etc. Details will be described later. Note that the touch panel includes a so-called touch sensor.
- the layer structure of the touch panel sensor electrode part in the touch panel is either a bonding method in which two transparent electrodes are bonded, a method in which transparent electrodes are provided on both surfaces of a single substrate, a single-sided jumper or a through-hole method, or a single-area layer method. But you can.
- the image display device having the optical film of the present invention is an image display device having a front plate having the optical film of the present invention and an image display element.
- the image display device can be used for an image display device such as a liquid crystal display (LCD), a plasma display panel, an electroluminescence display, a cathode tube display device, and a touch panel.
- LCD liquid crystal display
- plasma display panel a plasma display panel
- electroluminescence display a cathode tube display device
- a touch panel a touch panel.
- the liquid crystal display device As the liquid crystal display device, a TN (Twisted Nematic) type, a STN (Super-Twisted Nematic) type, a TSTN (Triple Super Twisted Nematic) type, a multi-domain type, a VA (Vertical Alignment In) type, an IPS type, an IPS type OCB (Optically Compensated Bend) type etc. are mentioned.
- the image display device preferably has improved brittleness and excellent handling properties, does not impair display quality due to surface smoothness and wrinkles, and can reduce light leakage during a wet heat test. That is, in the image display device having the optical film of the present invention, the image display element is preferably a liquid crystal display element.
- an image display device having a liquid crystal display element there can be cited, for example, Sony P made by Sony Ericsson.
- the image display element is preferably an organic electroluminescence (EL) display element.
- EL organic electroluminescence
- a known technique can be applied to the organic electroluminescence display element without any limitation.
- Examples of the image display device having an organic electroluminescence display element include a product manufactured by Samsunung Corporation and GALAXY SII.
- the image display element is preferably an in-cell touch panel display element.
- the in-cell touch panel display element has a touch panel function built into the image display element cell.
- publicly known techniques such as Japanese Unexamined Patent Application Publication No. 2011-76602 and Japanese Unexamined Patent Application Publication No. 2011-222009 can be applied without any limitation.
- Examples of the image display device having the in-cell touch panel display element include Sony P. manufactured by Ericsson Corporation.
- the image display element is on-cell (On-cell).
- -Cell A touch panel display element is also preferable.
- the on-cell touch panel display element is one in which a touch panel function is arranged outside the image display element cell.
- JP 2012-88683 A a known technique such as JP 2012-88683 A can be applied without any limitation.
- Examples of the image display device having an on-cell touch panel display element include GALXY SII manufactured by SAMSUNG.
- the touch panel having the optical film of the present invention is a touch panel including a touch sensor by bonding a touch sensor film to the optical film of the present invention.
- the optical film of the present invention has an HC layer
- a touch sensor film it is preferable that it is a conductive film in which the conductive layer was formed.
- the conductive film is preferably a conductive film in which a conductive layer is formed on an arbitrary support.
- the material of the conductive layer is not particularly limited, and for example, indium tin oxide (ITO), tin oxide and tin titanium oxide (ATO), copper, Examples thereof include silver, aluminum, nickel, chromium, and alloys thereof.
- the conductive layer is preferably an electrode pattern. Moreover, it is also preferable that it is a transparent electrode pattern.
- the electrode pattern may be a pattern of a transparent conductive material layer or a pattern of an opaque conductive material layer.
- oxides such as ITO and ATO, silver nanowires, carbon nanotubes, and conductive polymers can be used.
- the opaque conductive material layer is a metal layer.
- the metal layer any metal having conductivity can be used, and silver, copper, gold, aluminum and the like are preferably used.
- the metal layer may be a single metal or alloy, or may be one in which metal particles are bound by a binder. Further, blackening treatment or rust prevention treatment is applied to the metal surface as necessary. In the case of using a metal, it is possible to form a substantially transparent sensor portion and a peripheral wiring portion all together.
- the conductive layer preferably includes a plurality of fine metal wires. It is preferable that the fine metal wire is made of silver or an alloy containing silver. There is no restriction
- the conductive layer is made of an oxide.
- the oxide is more preferably made of indium oxide containing tin oxide or tin oxide containing antimony.
- a conductive layer in which a conductive layer consists of an oxide A well-known conductive layer can be used.
- the conductive layer preferably includes a plurality of fine metal wires, and the fine metal wires are preferably arranged in a mesh shape or a random shape, and the fine metal wires are more preferably arranged in a mesh shape.
- the fine metal wires are arranged in a mesh shape, and the fine metal wires are made of silver or an alloy containing silver.
- the touch sensor film also preferably has a conductive layer on both sides.
- the resistive touch panel having the optical film of the present invention is a resistive touch panel having a front plate having the optical film of the present invention.
- the resistive touch panel has a basic configuration in which a conductive film of a pair of upper and lower substrates having a conductive film is arranged via a spacer so that the conductive films face each other.
- the configuration of the resistive touch panel is known, and any known technique can be applied without any limitation in the present invention.
- the capacitive touch panel having the optical film of the present invention is a capacitive touch panel having a front plate having the optical film of the present invention.
- Examples of the capacitive touch panel system include a surface capacitive type and a projected capacitive type.
- the projected capacitive touch panel has a basic configuration in which an X-axis electrode and a Y-axis electrode orthogonal to the X electrode are arranged via an insulator.
- an aspect in which the X electrode and the Y electrode are formed on different surfaces on a single substrate, an aspect in which the X electrode, the insulator layer, and the Y electrode are formed in the above order on a single substrate.
- Examples include an embodiment in which an X electrode is formed on one substrate and a Y electrode is formed on another substrate (in this embodiment, a configuration in which two substrates are bonded together is the above basic configuration).
- the configuration of the capacitive touch panel is known, and any known technique can be applied without any limitation in the present invention.
- FIG. 3 an example of a structure of embodiment of an electrostatic capacitance type touch panel is shown.
- the touch panel 2 is used in combination with a display device.
- the display device is arranged and used on the protective layer 7B side in FIG. 3, that is, on the display device side.
- the optical film 4C side is the viewing side (that is, the side on which the operator of the touch panel visually recognizes the image on the display device).
- the optical film 4C of the present invention is used by being bonded to the conductive film 1 for a touch panel.
- the conductive film 1 for a touch panel has a conductive member 6A (first conductive layer 8) and a conductive member 6B (second conductive layer 9) on both surfaces of a flexible transparent insulating substrate 5, respectively.
- the conductive member 6A and the conductive member 6B constitute at least an electrode as a touch panel, a peripheral wiring, an external connection terminal, and a connector part, which will be described later. Moreover, as shown in FIG. 3, even if the transparent protective layer 7A and the protective layer 7B are disposed so as to cover the conductive member 6A and the conductive member 6B for the purpose of flattening or protecting the conductive members 6A and 6B. Good.
- the optical film 4C may be provided with a decorative layer that shields a peripheral region S2 described later.
- the material of the transparent insulating substrate 5 examples include glass, PET (polyethylene terephthalate), PEN (polyethylene naphthalate), COP (cycloolefin polymer), COC (cycloolefin polymer), PC (polycarbonate), and the like.
- the thickness of the transparent insulating substrate 5 is preferably 20 to 200 ⁇ m.
- An adhesive layer (not shown in the drawing) may be provided between the optical film 4C and the conductive film 1 for touch panel.
- an optical transparent adhesive sheet Optical Clear Adhesive
- an optical transparent adhesive resin Optical Clear Resin
- the 8146 series manufactured by 3M can be preferably used as the optically transparent adhesive sheet.
- a preferable value of the dielectric constant of the adhesive layer is 4.0 to 6.0, and more preferably 5.0 to 6.0.
- the protective layer 7A and the protective layer 7B for example, organic films such as gelatin, acrylic resin, and urethane resin, and inorganic films such as silicon dioxide can be used.
- the thickness is preferably 10 nm or more and 100 nm or less.
- the relative dielectric constant is preferably 2.5 to 4.5.
- the concentration of the halogen impurity in the protective layer 7A and the protective layer 7B is preferably 50 ppm or less, and more preferably contains no halogen impurity. According to this aspect, corrosion of the conductive member 6A and the conductive member 6B can be suppressed.
- a transparent active area S ⁇ b> 1 is defined in the conductive film for touch panel 1, and a peripheral area S ⁇ b> 2 is defined outside the active area S ⁇ b> 1.
- the active area S1 the first conductive layer 8 formed on the front surface (first surface) of the transparent insulating substrate 5 and the second conductive layer 8 formed on the back surface (second surface) of the transparent insulating substrate 5 are provided.
- the conductive layer 9 is disposed so as to overlap each other.
- the first conductive layer 8 and the second conductive layer 9 are arranged in a state of being insulated from each other via the transparent insulating substrate 5.
- the first conductive layer 8 on the front surface of the transparent insulating substrate 5 extends in the first direction D1 and is arranged in parallel in the second direction D2 orthogonal to the first direction D1.
- One electrode 11 is formed, and a plurality of second electrodes 21 each extending along the second direction D2 and arranged in parallel in the first direction D1 are formed by the second conductive layer 9 on the back surface of the transparent insulating substrate 5. Is formed.
- the plurality of first electrodes 11 and the plurality of second electrodes 21 constitute detection electrodes of the touch panel 2.
- the electrode width of the first electrode 11 and the second electrode 21 is preferably 1 to 5 mm, and the pitch between the electrodes is preferably 3 to 6 mm.
- a plurality of first peripheral wirings 12 connected to the plurality of first electrodes 11 are formed on the front surface of the transparent insulating substrate 5 in the peripheral region S2, and a plurality of first peripheral wirings 12 are formed at the edge of the transparent insulating substrate 5.
- One external connection terminal 13 is arranged and a first connector portion 14 is formed at each end of each first electrode 11.
- One end portion of the corresponding first peripheral wiring 12 is connected to the first connector portion 14, and the other end portion of the first peripheral wiring 12 is connected to the corresponding first external connection terminal 13.
- a plurality of second peripheral wirings 22 connected to the plurality of second electrodes 21 are formed on the back surface of the transparent insulating substrate 5 in the peripheral region S2, and a plurality of second external wirings are formed at the edge of the transparent insulating substrate 5.
- the connection terminals 23 are arranged and the second connector portions 24 are formed at both ends of the respective second electrodes 21.
- One end portion of the corresponding second peripheral wiring 22 is connected to the second connector portion 24, and the other end portion of the second peripheral wiring 22 is connected to the corresponding second external connection terminal 23.
- the conductive film 1 for a touch panel has a conductive member 6A including a first electrode 11, a first peripheral wiring 12, a first external connection terminal 13, and a first connector part 14 on the front surface of the transparent insulating substrate 5, On the back surface of the transparent insulating substrate 5, the conductive member 6 ⁇ / b> B including the second electrode 21, the second peripheral wiring 22, the second external connection terminal 23, and the second connector portion 24 is provided.
- the first electrode 11 and the first peripheral wiring 12 are connected via the first connector portion 14, but the first electrode 11 and the first peripheral wiring 12 are not provided without providing the first connector portion 14.
- the configuration may be such that the and are directly connected.
- the second electrode 21 and the second peripheral wiring 22 may be directly connected without providing the second connector portion 24.
- the widths of the first connector part 14 and the second connector part 24 are preferably not less than 1/3 of the width of the electrode to be connected and not more than the width of the electrode.
- the shape of the first connector portion 14 and the second connector portion 24 may be a solid film shape, or may be a frame shape or a mesh shape as disclosed in International Publication WO2013 / 088905.
- the first peripheral wiring 12 and the second peripheral wiring 22 preferably have a wiring width of 10 ⁇ m or more and 200 ⁇ m or less, and a minimum wiring interval (minimum wiring distance) of 20 ⁇ m or more and 100 ⁇ m or less.
- Each peripheral wiring may be covered with a protective insulating film made of urethane resin, acrylic resin, epoxy resin or the like. By providing the protective insulating film, migration and rust of peripheral wiring can be prevented.
- the insulating film does not contain a halogen impurity.
- the thickness of the protective insulating film is preferably 1 to 20 ⁇ m.
- the first external connection terminal 13 and the second external connection terminal 23 are formed with a terminal width larger than the wiring width of the first peripheral wiring 12 and the second peripheral wiring 22 for the purpose of improving electrical connection with the flexible wiring board.
- the terminal width of the first external connection terminal 13 and the second external connection terminal 23 is preferably 0.1 mm to 0.6 mm, and the terminal length is preferably 0.5 mm to 2.0 mm.
- the transparent insulating substrate 5 corresponds to a substrate having a first surface and a second surface facing the first surface, the first conductive layer 8 is disposed on the first surface (surface), and the second surface.
- the second conductive layer 9 is disposed on the (back surface).
- the transparent insulating substrate 5, the first conductive layer 8, and the second conductive layer 9 are shown in direct contact with each other, but the transparent insulating substrate 5, the first conductive layer 8, and the second conductive layer are shown.
- one or more functional layers such as an adhesion reinforcing layer, an undercoat layer, a hard coat layer, and an optical adjustment layer can be formed.
- FIG. 5 shows an intersection between the first electrode 11 and the second electrode 21.
- the first electrode 11 disposed on the front surface of the transparent insulating substrate 5 is formed by a mesh pattern M1 composed of the first metal fine wires 15, and the second electrode disposed on the back surface of the transparent insulating substrate 5.
- 21 is also formed by the mesh pattern M2 made of the second fine metal wires 25.
- the second metal fine wire 25 is shown by a dotted line.
- the mesh pattern a pattern in which the same mesh (standard cell) as shown in FIG. It may be a regular hexagon or another polygon.
- the narrow angle of the rhombus is preferably 20 ° or more and 70 ° or less from the viewpoint of reducing moire with the pixels of the display device.
- the distance between mesh centers (mesh pitch) is preferably 100 to 600 ⁇ m from the viewpoint of visibility. It is preferable that the mesh pattern M1 composed of the first fine metal wires 15 and the mesh pattern M2 composed of the second fine metal wires 25 have the same shape. Further, as shown in FIG.
- the mesh pattern M1 made of the first fine metal wires 15 and the mesh pattern M2 made of the second fine metal wires 25 are shifted by a distance corresponding to half the mesh pitch, and the mesh pitch is viewed from the viewing side. It is preferable from a viewpoint of visibility to arrange
- the shape of the mesh is a random pattern, or a regular cell that gives a randomness of about 10% to the pitch of a rhombus regular cell as disclosed in JP2013-214545A A semi-random shape imparted with a certain randomness in the shape may also be used.
- a dummy mesh pattern is formed between the first electrodes 11 adjacent to each other and between the second electrodes 21 adjacent to each other, insulated from the electrodes formed by the first metal thin wires 15 and the second metal thin wires 25, respectively. It may be.
- the dummy mesh pattern is preferably formed in the same mesh shape as the mesh pattern forming the electrodes.
- the method of bonding the touch panel 2 and the display device is a method of directly bonding using a transparent adhesive (direct bonding method) or a method of bonding only the periphery of the touch panel 2 and the display device using a double-sided tape ( There is an air gap method), but either method may be used.
- a protective film may be separately provided on the conductive member 6B or the protective layer 7B.
- the protective film for example, a PET film with a hard coat (thickness 20 to 150 ⁇ m) is used, and an optical transparent adhesive sheet (Optical Clear Adhesive) can be used to be attached to the conductive member 6B or the protective layer 7B. .
- an optical transparent adhesive sheet (Optical Clear Adhesive) or an optical transparent adhesive resin (Optical Clear Resin) can be used, and the preferred thickness is 10 ⁇ m or more and 100 ⁇ m. It is as follows.
- the optical transparent adhesive sheet for example, 8146 series manufactured by 3M Company can be preferably used.
- the transparent dielectric used in the direct bonding method has a relative dielectric constant smaller than that of the transparent adhesive layer described above.
- a preferable value of the relative dielectric constant of the transparent adhesive used in the direct bonding method is 2.0 to 3.0.
- the visible light reflectance of each of the surface on the viewing side of the first metal fine wire 15 and the surface on the viewing side of the second metal fine wire 25 is 5% or less in that the effect of the present invention is more excellent. preferable. Furthermore, it is more preferable that it is less than 1%.
- the visible light reflectance is measured as follows. First, using a UV-visible spectrophotometer V660 (single reflection measurement unit SLM-721) manufactured by JASCO Corporation, a reflection spectrum is measured at a measurement wavelength of 350 nm to 800 nm and an incident angle of 5 degrees. The regular reflection light of the aluminum vapor deposition plane mirror is used as the baseline. The Y value (color matching function JIS Z9701-1999) of the XYZ color system D65 light source 2 degree visual field is calculated from the obtained reflection spectrum using a color calculation program manufactured by JASCO Corporation, and is set as the visible light reflectance.
- the first metal fine wire 15 and the second metal fine wire 25 As a material constituting the first metal fine wire 15 and the second metal fine wire 25, metals such as silver, aluminum, copper, gold, molybdenum, chromium, and alloys thereof can be used, and these can be used as a single layer or a laminate. Can be used. From the viewpoint of the appearance of fine metal wires and the reduction of moire, the first metal fine wires 15 and the second metal fine wires 25 preferably have a line width of 0.5 ⁇ m or more and 5 ⁇ m or less. The first metal fine wire 15 and the second metal fine wire 25 may be straight, broken, curved, or wavy.
- the thickness of the 1st metal fine wire 15 and the 2nd metal fine wire 25 is 0.1 micrometer or more from a viewpoint of resistance value, and it is preferable that it is 3 micrometers or less from a viewpoint of the visibility from an oblique direction. More preferable thickness is 1/2 or less with respect to the line
- a blackening layer may be provided on the viewing side of the first metal fine wire 15 and the second metal fine wire 25.
- the conductive member 6 ⁇ / b> A including the first electrode 11, the first peripheral wiring 12, the first external connection terminal 13, and the first connector portion 14 can be formed of a material constituting the first metal thin wire 15. Therefore, the conductive members 6A including the first electrode 11, the first peripheral wiring 12, the first external connection terminal 13, and the first connector portion 14 are all formed of the same metal and with the same thickness, and can be formed simultaneously. The same applies to the conductive member 6B including the second electrode 21, the second peripheral wiring 22, the second external connection terminal 23, and the second connector portion 24.
- the sheet resistance of the first electrode 11 and the second electrode 21 is preferably 0.1 ⁇ / ⁇ or more and 200 ⁇ / ⁇ or less, particularly 10 ⁇ / ⁇ or more and 100 ⁇ / ⁇ or less when used for a projected capacitive touch panel. It is preferable that
- the first conductive layers 8 arranged on the front surface of the transparent insulating substrate 5 in the active area S1 are arranged between the plurality of first electrodes 11, respectively.
- a plurality of first dummy electrodes 11A may be provided. These first dummy electrodes 11 ⁇ / b> A are insulated from the plurality of first electrodes 11, and have a first mesh pattern M ⁇ b> 1 composed of a large number of first cells C ⁇ b> 1, similarly to the first electrode 11.
- the first dummy electrode 11A adjacent to the first electrode 11 is electrically insulated by providing a disconnection having a width of 5 ⁇ m or more and 30 ⁇ m or less on a thin metal wire arranged along the continuous first mesh pattern M1. is doing.
- the second conductive layer 9 disposed on the back surface of the transparent insulating substrate 5 in the active area S1 includes a plurality of second dummy electrodes respectively disposed between the plurality of second electrodes 21. You may have. These second dummy electrodes are insulated from the plurality of second electrodes 21 and, like the second electrodes 21, have a second mesh pattern M2 composed of a large number of second cells C2.
- the second dummy electrode adjacent to the second electrode 21 is electrically insulated by providing a disconnection having a width of 5 ⁇ m or more and 30 ⁇ m or less on a thin metal wire arranged along the continuous second mesh pattern M2. ing.
- a shape in which disconnection is formed only at the boundary line between the second electrode 21 and the first dummy electrode adjacent to the second electrode 21 may be formed. May be.
- the conductive film 1 for a touch panel includes a first electrode 11, a first peripheral wiring 12, a first external connection terminal 13, and a first connector portion 14 on the front surface of the transparent insulating substrate 5. 6A is formed, and the conductive member 6B including the second electrode 21, the second peripheral wiring 22, the second external connection terminal 23, and the second connector portion 24 is formed on the back surface of the transparent insulating substrate 5. .
- the 1st electrode 11 consists of the 1st conductive layer 8 in which the 1st metal fine wire 15 is arranged along the 1st mesh pattern M1, and the 2nd electrode 21 is the 2nd along the 2nd mesh pattern M2.
- the second conductive layer 9 in which the fine metal wires 25 are arranged, and the first conductive layer 8 and the second conductive layer 9 are arranged so as to overlap each other in the active area S1 as shown in FIG. Shall be.
- the formation method of these conductive members 6A and 6B is not particularly limited. For example, ⁇ 0067> to ⁇ 0083> in JP 2012-185813 A, ⁇ 0115> to ⁇ 0126> in JP 2014-209332 A, or ⁇ 0216> to ⁇ 0215 in JP 2015-5495 A.
- the conductive members 6A and 6B can be formed by exposing and developing a photosensitive material having an emulsion layer containing a photosensitive silver halide salt as described in>.
- a metal thin film is formed on each of the front and back surfaces of the transparent insulating substrate 5 and a resist is printed in a pattern on each metal thin film, or the resist applied on the entire surface is exposed and developed to form a pattern.
- These conductive members can also be formed by etching and etching the metal in the opening.
- a method of printing a paste containing fine particles of the material constituting the conductive member on the front and back surfaces of the transparent insulating substrate 5 and subjecting the paste to metal plating, the fine particles of the material constituting the conductive member A method using an ink jet method using an ink containing, a method of forming ink containing fine particles of a material constituting a conductive member by screen printing, a method of forming a groove in the transparent insulating substrate 5, and applying a conductive ink to the groove A microcontact printing patterning method or the like can be used.
- the conductive member 6A including the first electrode 11, the first peripheral wiring 12, the first external connection terminal 13, and the first connector portion 14 is disposed on the front surface of the transparent insulating substrate 5, and is transparent.
- the conductive member 6 ⁇ / b> B including the second electrode 21, the second peripheral wiring 22, the second external connection terminal 23, and the second connector portion 24 is disposed on the back surface of the insulating substrate 5, but is not limited thereto.
- the conductive member 6A and the conductive member 6B may be arranged on one surface side of the transparent insulating substrate 5 via an interlayer insulating film. Furthermore, it can also be set as the structure of 2 sheets.
- the conductive member 6A is disposed on the surface of the first transparent insulating substrate
- the conductive member 6B is disposed on the surface of the second transparent insulating substrate
- the first transparent insulating substrate and the second transparent insulating substrate are optically transparent. It can also be used by sticking together using an adhesive sheet (Optical Clear Adhesive).
- the conductive member 6A and the conductive member 6B may be arranged on the surface of the optical film 4C shown in FIG. 3 via an interlayer insulating film.
- the present invention can be applied to the electrode pattern shape disclosed in FIG. 7 or FIG. 20 of the published WO2013 / 094728, and can also be applied to the electrode patterns of capacitive touch panels having other shapes. Further, the present invention can also be applied to a touch panel having a configuration in which the detection electrode is only on one side of the substrate, such as an electrode configuration without an intersecting portion disclosed in US2012 / 0262414.
- the touch panel can be used in combination with other functional films, and is a function for improving image quality that prevents azimuth using a substrate having a high retardation value disclosed in Japanese Patent Application Laid-Open No. 2014-13264.
- a combination with a circularly polarizing plate for improving the visibility of an electrode of a film or a touch panel disclosed in Japanese Patent Application Laid-Open No. 2014-142462 is also possible.
- the optical film of the present invention may have a reflective layer (a linearly polarized reflective layer or a circularly polarized reflective layer) on the surface of one resin film opposite to the surface having the adhesive layer.
- a reflective layer a linearly polarized reflective layer or a circularly polarized reflective layer
- Such an optical film is preferably used as an optical film used for a front plate of a mirror with an image display function by being combined with an image display element.
- An adhesive layer may be provided between the optical film of the present invention and the reflective layer.
- an optical transparent adhesive sheet Optical Clear Adhesive
- an optical transparent adhesive resin Optical Clear Resin
- the image display element used in the mirror with an image display function is not particularly limited, and examples thereof include an image display element suitably used in the above-described image display device.
- the mirror with an image display function is configured by arranging an image display element on the side of the half mirror having the linearly polarized light reflecting layer or the circularly polarized light reflecting layer.
- the half mirror and the image display element may be in direct contact, or another layer may be interposed between the half mirror and the image display element.
- an air layer may exist between the image display element and the half mirror, or an adhesive layer may exist.
- the surface on the half mirror side with respect to the image display element may be referred to as the front surface.
- the mirror with an image display function can be used, for example, as a vehicle rearview mirror (inner mirror).
- the mirror with an image display function may have a frame, a housing, a support arm for attaching to the vehicle body, and the like for use as a rearview mirror.
- the mirror with an image display function may be formed for incorporation into a rearview mirror. In such a mirror with an image display function, it is possible to specify the vertical and horizontal directions during normal use.
- the mirror with an image display function may be a plate shape or a film shape, and may have a curved surface.
- the front surface of the mirror with an image display function may be flat or curved. It is possible to provide a wide mirror that can be viewed in a wide angle by making the convex curved surface the front side by curving. Such a curved front surface can be produced using a curved half mirror.
- the curve may be in the vertical direction, the horizontal direction, or the vertical direction and the horizontal direction.
- the curvature of the curvature may be 500 to 3000 mm, and more preferably 1000 to 2500 mm.
- the radius of curvature is the radius of the circumscribed circle when the circumscribed circle of the curved portion is assumed in the cross section.
- Reflection layer a reflective layer that can function as a transflective layer may be used. That is, at the time of image display, the reflective layer functions so that an image is displayed on the front surface of the mirror with an image display function by transmitting light emitted from a light source included in the image display element, while image non-display is performed. Sometimes, the reflection layer functions to reflect at least a part of incident light from the front surface direction and transmit the reflected light from the image display element so that the front surface of the mirror with an image display function becomes a mirror. That's fine.
- a polarizing reflection layer is used as the reflection layer.
- the polarization reflection layer may be a linear polarization reflection layer or a circular polarization reflection layer.
- Linear polarization reflection layer Examples of the linearly polarized light reflecting layer include (i) a linearly polarized light reflecting plate having a multilayer structure, (ii) a polarizer formed by laminating thin films having different birefringence, (iii) a wire grid type polarizer, and (iv) a polarizing prism. And (v) a scattering anisotropic polarizing plate.
- a multilayer laminated thin film in which dielectric materials having different refractive indexes are laminated on a support from an oblique direction by a vacuum vapor deposition method or a sputtering method can be mentioned.
- the number of types is not limited to two or more. It may be.
- the number of laminated layers is preferably 2 to 20 layers, more preferably 2 to 12 layers, still more preferably 4 to 10 layers, and particularly preferably 6 to 8 layers.
- the method for forming the dielectric thin film is not particularly limited and may be appropriately selected depending on the purpose.
- a vacuum vapor deposition method such as ion plating and ion beam
- a physical vapor deposition method such as sputtering ( PVD method) and chemical vapor deposition method (CVD method).
- the vacuum evaporation method or the sputtering method is preferable, and the sputtering method is particularly preferable.
- a polarizer formed by laminating thin films having different birefringence for example, a polarizer described in JP-T-9-506837 can be used.
- a polarizer can be formed using a wide variety of materials by processing under conditions selected to obtain a refractive index relationship.
- one of the first materials needs to have a different refractive index than the second material in the chosen direction.
- This refractive index difference can be achieved in a variety of ways, including stretching, extrusion, or coating during or after film formation.
- a commercial product can be used as a polarizer in which thin films having different birefringence are laminated. Examples of the commercial product include DBEF (registered trademark) (manufactured by 3M).
- a wire grid type polarizer is a polarizer that transmits one of polarized light and reflects the other by birefringence of a fine metal wire.
- the wire grid polarizer is a periodic arrangement of metal wires, and is mainly used as a polarizer in the terahertz wave band. In order for the wire grid to function as a polarizer, the wire interval needs to be sufficiently smaller than the wavelength of the incident electromagnetic wave.
- metal wires are arranged at equal intervals. The polarization component in the polarization direction parallel to the longitudinal direction of the metal wire is reflected by the wire grid polarizer, and the polarization component in the perpendicular polarization direction is transmitted through the wire grid polarizer.
- wire grid polarizer Commercially available products can be used as the wire grid polarizer, and examples of commercially available products include wire grid polarizing filter 50 ⁇ 50, NT46-636 (trade name) manufactured by Edmund Optics.
- the circularly polarized light reflecting layer examples include a circularly polarized light reflecting layer including a linearly polarized light reflecting plate and a quarter wavelength plate, and a circularly polarized light reflecting layer including a cholesteric liquid crystal layer (hereinafter, for the sake of distinction, “Pol ⁇ / 4 circularly polarized light reflecting layer “or” cholesteric circularly polarized light reflecting layer ").
- the linearly polarized light reflecting plate and the quarter wavelength plate are arranged so that the slow axis of the ⁇ / 4 wavelength plate is 45 ° with respect to the polarized light reflecting axis of the linearly polarized light reflecting plate. Just do it.
- the quarter wave plate and the linearly polarized light reflecting plate may be bonded by, for example, an adhesive layer.
- the linearly polarized light reflecting plate is arranged so as to be a surface close to the image display element.
- the quarter wavelength plate and the linearly polarized light reflecting plate are arranged in this order with respect to the optical film.
- the light for image display from the image display element can be efficiently converted into circularly polarized light and emitted from the front surface of the mirror with an image display function.
- the polarization reflection axis of the linearly polarized light reflecting plate may be adjusted so as to transmit this linearly polarized light.
- the thickness of the Pol ⁇ / 4 circularly polarized light reflecting layer is preferably in the range of 2.0 ⁇ m to 300 ⁇ m, and more preferably in the range of 8.0 ⁇ m to 200 ⁇ m.
- the linearly polarized light reflecting plate those described above as the linearly polarized light reflecting layer can be used.
- the quarter wavelength plate a quarter wavelength plate described later can be used.
- the cholesteric circularly polarized light reflection layer includes at least one cholesteric liquid crystal layer.
- the cholesteric liquid crystal layer included in the cholesteric circularly polarized light reflection layer may be any layer that exhibits selective reflection in the visible light region.
- the circularly polarized light reflecting layer may include two or more cholesteric liquid crystal layers, and may include other layers such as an alignment layer.
- the circularly polarized light reflecting layer is preferably composed only of a cholesteric liquid crystal layer. Further, when the circularly polarized light reflection layer includes a plurality of cholesteric liquid crystal layers, it is preferable that they are in direct contact with adjacent cholesteric liquid crystal layers.
- the circularly polarized light reflection layer includes three or more cholesteric liquid crystal layers such as three layers and four layers.
- the thickness of the cholesteric circularly polarized light reflecting layer is preferably in the range of 2.0 ⁇ m to 300 ⁇ m, and more preferably in the range of 8.0 to 200 ⁇ m.
- the “cholesteric liquid crystal layer” means a layer in which a cholesteric liquid crystal phase is fixed.
- the cholesteric liquid crystal layer is sometimes simply referred to as a liquid crystal layer.
- the cholesteric liquid crystal phase selectively reflects circularly polarized light of either right circularly polarized light or left circularly polarized light in a specific wavelength region and selectively transmits circularly polarized light of the other sense. It is known to show.
- the circularly polarized light selective reflection is sometimes simply referred to as selective reflection.
- films formed from a composition containing a polymerizable liquid crystal compound have been known as films containing a layer in which a cholesteric liquid crystal phase exhibiting circularly polarized light selective properties is fixed. You can refer to the law.
- the cholesteric liquid crystal layer may be a layer in which the orientation of the liquid crystal compound in the cholesteric liquid crystal phase is maintained.
- the polymerizable liquid crystal compound is placed in the orientation state of the cholesteric liquid crystal phase and then irradiated with ultraviolet rays.
- Any layer may be used as long as it is polymerized and cured by heating or the like to form a layer having no fluidity, and at the same time, the layer is changed to a state in which the orientation is not changed by an external field or an external force.
- the polymerizable liquid crystal compound may have a high molecular weight due to a curing reaction and may no longer have liquid crystallinity.
- the central wavelength and the half width of selective reflection of the cholesteric liquid crystal layer can be obtained as follows.
- the center wavelength and half width of selective reflection can be expressed by the following formula.
- Center wavelength of selective reflection ( ⁇ 1 + ⁇ 2) / 2
- Half width ( ⁇ 2- ⁇ 1)
- center wavelength of selective reflection means the center wavelength when measured from the normal direction of the cholesteric liquid crystal layer.
- the center wavelength of selective reflection can be adjusted by adjusting the pitch of the helical structure.
- the n value and the P value it is possible to adjust the center wavelength ⁇ for selectively reflecting either the right circularly polarized light or the left circularly polarized light with respect to light having a desired wavelength.
- n ⁇ P the center wavelength of selective reflection when a light ray passes at an angle of ⁇ 2 with respect to the normal direction of the cholesteric liquid crystal layer (the spiral axis direction of the cholesteric liquid crystal layer) is ⁇ d
- ⁇ d n 2 ⁇ P ⁇ cos ⁇ 2
- the center wavelength of selective reflection of the cholesteric liquid crystal layer included in the circularly polarized light reflecting layer it is possible to prevent the visibility of the image from being viewed obliquely. Also, the visibility of the image from an oblique direction can be intentionally reduced. This is useful because, for example, it is possible to prevent peeping in a smartphone or a personal computer.
- the mirror with an image display function having the optical film of the present invention may appear in the image and the mirror reflection image viewed from an oblique direction.
- the center wavelength of selective reflection in the infrared region is specifically 780 to 900 nm, preferably 780 to 850 nm.
- the cholesteric liquid crystal layer having a central wavelength of selective reflection is provided in the infrared light region, it is preferable that the cholesteric liquid crystal layer having a central wavelength of selective reflection in the visible light region is closest to the image display element.
- the pitch of the cholesteric liquid crystal phase depends on the type of chiral agent used together with the polymerizable liquid crystal compound or the concentration of the chiral agent, a desired pitch can be obtained by adjusting these.
- a desired pitch can be obtained by adjusting these.
- the circularly polarized light reflection layer has a cholesteric liquid crystal layer having a central wavelength of selective reflection in the red light wavelength region and a central wavelength of selective reflection in the green light wavelength region. It is preferable to include a cholesteric liquid crystal layer having a cholesteric liquid crystal layer having a central wavelength of selective reflection in the wavelength range of blue light.
- the reflective layer is, for example, a cholesteric liquid crystal layer having a central wavelength of selective reflection in 400 nm to 500 nm, a cholesteric liquid crystal layer having a central wavelength of selective reflection in 500 nm to 580 nm, and a cholesteric liquid crystal having a central wavelength of selective reflection in 580 nm to 700 nm. It is preferable to include a layer.
- the circularly polarized light reflection layer includes a plurality of cholesteric liquid crystal layers
- the cholesteric liquid crystal layer closer to the image display element has a longer selective reflection center wavelength.
- the central wavelength of selective reflection that each cholesteric liquid crystal layer has is 5 nm or more with the peak wavelength of light emission of the image display element. It is preferable to make them different. This difference is more preferably 10 nm or more.
- the peak wavelength may be a peak wavelength in the visible light region of the emission spectrum.
- the above-described red light emission peak wavelength ⁇ R, green light emission peak wavelength ⁇ G, and blue light emission peak wavelength ⁇ B of the image display element Any one or more selected from the group consisting of:
- the selective reflection center wavelength of the cholesteric liquid crystal layer is different from the above-described red light emission peak wavelength ⁇ R, green light emission peak wavelength ⁇ G, and blue light emission peak wavelength ⁇ B of the image display element by 5 nm or more. It is preferable that the difference is 10 nm or more.
- the central wavelength of selective reflection of all the cholesteric liquid crystal layers is different from the peak wavelength of light emitted from the image display element by 5 nm or more, preferably 10 nm or more. do it.
- the image display element is a display element for full color display showing an emission peak wavelength ⁇ R for red light, an emission peak wavelength ⁇ G for green light, and an emission peak wavelength ⁇ B for blue light in the emission spectrum during white display.
- the central wavelengths of all selective reflections of the cholesteric liquid crystal layer may be different from each other by ⁇ R, ⁇ G, and ⁇ B by 5 nm or more, preferably by 10 nm or more.
- the central wavelength of selective reflection of the cholesteric liquid crystal layer to be used according to the emission wavelength range of the image display element and the usage mode of the circularly polarized light reflection layer, a bright image can be displayed with high light utilization efficiency.
- the usage mode of the circularly polarized light reflecting layer include an incident angle of light to the circularly polarized light reflecting layer, an image observation direction, and the like.
- each cholesteric liquid crystal layer a cholesteric liquid crystal layer whose spiral sense is either right or left is used.
- the sense of reflected circularly polarized light in the cholesteric liquid crystal layer coincides with the sense of a spiral.
- the spiral senses of the plurality of cholesteric liquid crystal layers may all be the same or different. That is, either the right or left sense cholesteric liquid crystal layer may be included, or both the right and left sense cholesteric liquid crystal layers may be included.
- the spiral senses of the plurality of cholesteric liquid crystal layers are all the same.
- the spiral sense at that time may be determined according to the sense of circularly polarized light of the sense obtained as each cholesteric liquid crystal layer that is emitted from the image display element and transmitted through the quarter-wave plate.
- a cholesteric liquid crystal layer having a spiral sense that transmits the circularly polarized light of the sense obtained from the image display element and transmitted through the quarter-wave plate may be used.
- ⁇ n can be adjusted by adjusting the kind of the polymerizable liquid crystal compound and the mixing ratio thereof, or by controlling the temperature at the time of fixing the alignment.
- a plurality of cholesteric liquid crystal layers having the same period P and the same spiral sense may be stacked. By laminating cholesteric liquid crystal layers having the same period P and the same spiral sense, the circularly polarized light selectivity at a specific wavelength can be increased.
- the half mirror may further include a quarter wavelength plate, a high Re (in-plane retardation) retardation film, a cholesteric circularly polarized light reflection layer, It is preferable to include a quarter wave plate in this order.
- a quarter-wave plate between the image display element and the cholesteric circularly polarized reflection layer, in particular, the light from the image display element displaying an image by linearly polarized light is converted into circularly polarized light and reflected by cholesteric circularly polarized light. It is possible to enter the layer.
- the light reflected by the circularly polarized light reflection layer and returning to the image display element side can be greatly reduced, and a bright image can be displayed.
- a cholesteric circularly polarized light reflection layer can be configured not to generate sense circularly polarized light reflected to the image display element side by using a quarter wavelength plate, an image by multiple reflection between the image display element and the half mirror is possible. Display quality is unlikely to deteriorate. That is, for example, the central wavelength of selective reflection of the cholesteric liquid crystal layer included in the cholesteric circularly polarized light reflection layer is substantially the same as the emission peak wavelength of blue light in the emission spectrum when the image display element displays white (for example, the difference is less than 5 nm). Even in this case, the light emitted from the image display element can be transmitted to the front side without causing the circularly polarized light reflection layer to generate the sense circularly polarized light reflected to the image display side.
- the quarter-wave plate used in combination with the cholesteric circularly polarized reflective layer is preferably angle-adjusted so that the image becomes brightest when bonded to the image display element. That is, the relationship between the polarization direction of the linearly polarized light (transmission axis) and the slow axis of the quarter-wave plate so that the linearly polarized light is transmitted best, particularly for an image display element displaying an image by linearly polarized light. Is preferably adjusted. For example, in the case of a single layer type quarter wave plate, it is preferable that the transmission axis and the slow axis form an angle of 45 °.
- the light emitted from the image display element displaying an image by linearly polarized light is circularly polarized light of either right or left sense after passing through the quarter wavelength plate.
- the circularly polarized light reflecting layer may be formed of a cholesteric liquid crystal layer having a twist direction that transmits the circularly polarized light having the above-described sense.
- the quarter wavelength plate may be a retardation layer that functions as a quarter wavelength plate in the visible light region.
- the quarter-wave plate include a single-layer quarter-wave plate and a broadband quarter-wave plate in which a quarter-wave plate and a half-wave retardation plate are stacked.
- the front phase difference of the former 1 ⁇ 4 wavelength plate may be a length that is 1 ⁇ 4 of the emission wavelength of the image display element. Therefore, for example, when the emission wavelength of the image display element is 450 nm, 530 nm, and 640 nm, the wavelength of 450 nm is 112.5 nm ⁇ 10 nm, preferably 112.5 nm ⁇ 5 nm, more preferably 112.5 nm, and 530 nm.
- reverse dispersion such that the phase difference is 160 nm ⁇ 10 nm, preferably 160 nm ⁇ 5 nm, more preferably 160 nm at a wavelength of 640 nm.
- a retardation layer is most preferable as a quarter-wave plate, but a retardation plate having a small retardation wavelength dispersion or a forward dispersion retardation plate can also be used.
- Reverse dispersion means the property that the absolute value of the phase difference becomes larger as the wavelength becomes longer, and “forward dispersion” means the property that the absolute value of the phase difference becomes larger as the wavelength becomes shorter.
- the laminated quarter-wave plate is formed by laminating a quarter-wave plate and a half-wave retardation plate at an angle of 60 ° with the slow axis, and the side of the half-wave retardation plate is linearly polarized. It is arranged on the incident side and the slow axis of the half-wave retardation plate is used so as to cross 15 ° or 75 ° with respect to the polarization plane of the incident linearly polarized light. Can be suitably used because of its good resistance.
- ⁇ / 4 wavelength plate is not particularly limited and can be appropriately selected depending on the purpose.
- a quartz plate a stretched polycarbonate film, a stretched norbornene polymer film, a transparent film oriented containing inorganic particles having birefringence such as strontium carbonate, and an inorganic dielectric obliquely on a support
- a deposited thin film For example, a deposited thin film.
- ⁇ / 4 wavelength plate for example, (1) a birefringent film having a large retardation and a birefringence having a small retardation described in JP-A-5-27118 and JP-A-5-27119 A retardation film obtained by laminating the optical films so that their optical axes are orthogonal to each other, (2) a polymer film having a ⁇ / 4 wavelength at a specific wavelength described in JP-A-10-68816 And a retardation film which can be obtained by laminating a polymer film made of the same material and having a ⁇ / 2 wavelength at the same wavelength to obtain a ⁇ / 4 wavelength in a wide wavelength region, (3) JP-A-10-90521 (4) International Publication No.
- a commercially available product can be used as the ⁇ / 4 wavelength plate. Examples of the commercially available product include Pure Ace (registered trademark) WR (polycarbonate film manufactured by Teijin Limited).
- the quarter wavelength plate may be formed by aligning and fixing a polymerizable liquid crystal compound or a polymer liquid crystal compound.
- a liquid crystal composition is applied to the surface of a temporary support, an alignment film, or a front plate, and a polymerizable liquid crystal compound in the liquid crystal composition is formed into a nematic alignment in a liquid crystal state, and then photocrosslinked. It can be formed by immobilization by thermal crosslinking. Details of the liquid crystal composition and the production method will be described later.
- a quarter-wave plate is formed by applying a liquid crystal composition on a surface of a temporary support, an alignment film, or a front plate to form a nematic alignment in a liquid crystal state and then cooling the composition containing a polymer liquid crystal compound. It may be a layer obtained by immobilizing.
- the ⁇ / 4 wave plate may be in direct contact with the cholesteric circularly polarized light reflection layer, may be adhered by an adhesive layer, and is preferably in direct contact.
- a preparation material and a preparation method of a quarter-wave plate formed from a cholesteric liquid crystal layer and a liquid crystal composition will be described.
- the material used for forming the quarter wavelength plate include a liquid crystal composition containing a polymerizable liquid crystal compound.
- the material used for forming the cholesteric liquid crystal layer include a liquid crystal composition containing a polymerizable liquid crystal compound and a chiral agent (optically active compound).
- the cholesteric liquid crystal layer as a temporary support, a support, an alignment film, a high Re retardation film, and a lower layer is prepared by mixing the liquid crystal composition, which is further mixed with a surfactant or a polymerization initiator as necessary, and dissolved in a solvent. Alternatively, it can be applied to a quarter wavelength plate or the like, and after alignment aging, the liquid crystal composition can be fixed by curing to form a cholesteric liquid crystal layer and / or a quarter wavelength plate.
- a polymerizable rod-shaped liquid crystal compound may be used.
- the polymerizable rod-like liquid crystal compound include rod-like nematic liquid crystal compounds.
- rod-like nematic liquid crystal compounds include azomethines, azoxys, cyanobiphenyls, cyanophenyl esters, benzoic acid esters, cyclohexanecarboxylic acid phenyl esters, cyanophenylcyclohexanes, cyano-substituted phenylpyrimidines, alkoxy-substituted phenylpyrimidines.
- Phenyldioxanes, tolanes and alkenylcyclohexylbenzonitriles are preferably used. Not only low-molecular liquid crystal compounds but also high-molecular liquid crystal compounds can be used.
- the polymerizable liquid crystal compound can be obtained by introducing a polymerizable group into the liquid crystal compound.
- the polymerizable group include an unsaturated polymerizable group, an epoxy group, and an aziridinyl group, preferably an unsaturated polymerizable group, and particularly preferably an ethylenically unsaturated polymerizable group.
- the polymerizable group can be introduced into the molecule of the liquid crystal compound by various methods.
- the number of polymerizable groups possessed by the polymerizable liquid crystal compound is preferably 1 to 6, more preferably 1 to 3. Examples of polymerizable liquid crystal compounds are described in Makromol. Chem. 190, 2255 (1989), Advanced Materials, 5, 107 (1993), US Pat. No.
- the content of the polymerizable liquid crystal compound in the liquid crystal composition is preferably 80 to 99.9% by mass, and preferably 85 to 99% with respect to the solid content mass (mass excluding the solvent) of the liquid crystal composition. It is more preferably 5% by mass, particularly preferably 90 to 99% by mass.
- the material used for forming the cholesteric liquid crystal layer preferably contains a chiral agent.
- the chiral agent has a function of inducing a helical structure of a cholesteric liquid crystal phase.
- the chiral agent may be selected according to the purpose because the helical sense or helical pitch induced by the compound is different.
- the chiral agent is not particularly limited, and is a compound that is usually used (for example, Liquid Crystal Device Handbook, Chapter 3-4-3, TN, chiral agent for STN, 199 pages, Japan Society for the Promotion of Science, 142nd Committee, 1989. ), Isosorbide and isomannide derivatives can be used.
- a chiral agent generally contains an asymmetric carbon atom, but an axially asymmetric compound or a planar asymmetric compound containing no asymmetric carbon atom can also be used as the chiral agent.
- the axial asymmetric compound or the planar asymmetric compound include binaphthyl, helicene, paracyclophane, and derivatives thereof.
- the chiral agent may have a polymerizable group. When both the chiral agent and the liquid crystal compound have a polymerizable group, they are derived from the repeating unit derived from the polymerizable liquid crystal compound and the chiral agent by a polymerization reaction between the polymerizable chiral agent and the polymerizable liquid crystal compound.
- the polymerizable group possessed by the polymerizable chiral agent is preferably the same group as the polymerizable group possessed by the polymerizable liquid crystal compound. Therefore, the polymerizable group of the chiral agent is also preferably an unsaturated polymerizable group, an epoxy group or an aziridinyl group, more preferably an unsaturated polymerizable group, and an ethylenically unsaturated polymerizable group. Particularly preferred.
- the chiral agent may be a liquid crystal compound.
- the content of the chiral agent in the liquid crystal composition is preferably 0.01 mol% to 200 mol%, more preferably 1 mol% to 30 mol%, based on the amount of the polymerizable liquid crystal compound.
- the liquid crystal composition used in the present invention preferably contains a polymerization initiator.
- the polymerization initiator to be used is preferably a photopolymerization initiator that can start the polymerization reaction by ultraviolet irradiation.
- photopolymerization initiators include ⁇ -carbonyl compounds (described in US Pat. No. 2,367,661 and US Pat. No. 2,367,670), acyloin ethers (described in US Pat. No. 2,448,828), ⁇ -hydrocarbons.
- a substituted aromatic acyloin compound (described in US Pat. No.
- the content of the photopolymerization initiator in the liquid crystal composition is preferably 0.1 to 20% by mass, more preferably 0.5% to 5% by mass with respect to the amount of the polymerizable liquid crystal compound. .
- the liquid crystal composition may optionally contain a crosslinking agent in order to improve the film strength after curing and improve the durability.
- a crosslinking agent one that can be cured by ultraviolet rays, heat, moisture, or the like can be suitably used.
- polyfunctional acrylate compounds such as a trimethylol propane tri (meth) acrylate and a pentaerythritol tri (meth) acrylate
- Glycidyl (meth) acrylate And epoxy compounds such as ethylene glycol diglycidyl ether
- aziridine compounds such as 2,2-bishydroxymethylbutanol-tris [3- (1-aziridinyl) propionate] and 4,4-bis (ethyleneiminocarbonylamino) diphenylmethane
- Isocyanate compounds such as methylene diisocyanate and biuret type isocyanate
- vinyltrimethoxysilane and N- (2-amino) Chill) 3-aminopropyl alkoxysilane compounds such as trimethoxysilane.
- the catalyst normally used can be used according to the reactivity of a crosslinking agent, and productivity can be improved in addition to film
- the content of the crosslinking agent in the liquid crystal composition is preferably 3% by mass to 20% by mass, and more preferably 5% by mass to 15% by mass. When the content of the crosslinking agent is not less than the above lower limit, an effect of improving the crosslinking density can be obtained. Moreover, the stability of the layer formed can be maintained by setting it as the said upper limit or less.
- an alignment control agent that contributes to stable or rapid planar alignment may be added.
- the alignment control agent include fluorine (meth) acrylate polymers described in paragraphs [0018] to [0043] of JP-A-2007-272185 and paragraphs [0031] to [0034] of JP-A-2012-203237. And compounds represented by the formulas (I) to (IV) as described above.
- 1 type may be used independently and 2 or more types may be used together.
- the addition amount of the alignment control agent in the liquid crystal composition is preferably 0.01% by mass to 10% by mass, more preferably 0.01% by mass to 5% by mass with respect to the total mass of the polymerizable liquid crystal compound. 0.02% by mass to 1% by mass is particularly preferable.
- the liquid crystal composition may contain at least one selected from various additives such as a surfactant for adjusting the surface tension of the coating film and making the thickness uniform, and a polymerizable monomer.
- a surfactant for adjusting the surface tension of the coating film and making the thickness uniform and a polymerizable monomer.
- a polymerization inhibitor, an antioxidant, an ultraviolet absorber, a light stabilizer, a colorant, metal oxide fine particles, and the like may be added as long as the optical performance is not deteriorated. Can be added.
- organic solvent is used preferably.
- the organic solvent is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include ketones, alkyl halides, amides, sulfoxides, heterocyclic compounds, hydrocarbons, esters and ethers. It is done. These may be used individually by 1 type and may use 2 or more types together. Among these, ketones are particularly preferable in consideration of environmental load.
- the method for applying the liquid crystal composition to the temporary support, the alignment film, the high Re retardation film, the quarter wavelength plate, and / or the lower cholesteric liquid crystal layer is not particularly limited and is appropriately selected according to the purpose.
- wire bar coating method, curtain coating method, extrusion coating method, direct gravure coating method, reverse gravure coating method, die coating method, spin coating method, dip coating method, spray coating method and slide coating method etc. Is mentioned. It can also be carried out by transferring a liquid crystal composition separately coated on a support. The liquid crystal molecules are aligned by heating the applied liquid crystal composition.
- cholesteric alignment may be performed, and in forming the quarter-wave plate, nematic alignment is preferable.
- the heating temperature is preferably 200 ° C. or lower, and more preferably 130 ° C. or lower.
- the heating temperature is preferably 25 ° C. to 120 ° C., more preferably 30 ° C. to 100 ° C.
- the aligned liquid crystal compound can be further polymerized to cure the liquid crystal composition.
- the polymerization may be either thermal polymerization or photopolymerization by light irradiation, but photopolymerization is preferred. It is preferable to use ultraviolet rays for light irradiation.
- the irradiation energy is preferably 20mJ / cm 2 ⁇ 50J / cm 2, 100mJ / cm 2 ⁇ 1,500mJ / cm 2 is more preferable.
- light irradiation may be performed under heating conditions or in a nitrogen atmosphere.
- the irradiation ultraviolet wavelength is preferably 350 nm to 430 nm.
- the polymerization reaction rate is preferably high from the viewpoint of stability, preferably 70% or more, and more preferably 80% or more.
- the polymerization reaction rate can be determined by measuring the consumption ratio of the polymerizable functional group using an IR absorption spectrum.
- each cholesteric liquid crystal layer is not particularly limited as long as it exhibits the above characteristics, but is preferably in the range of 1.0 to 150 ⁇ m, more preferably in the range of 2.5 to 100 ⁇ m.
- the thickness of the quarter-wave plate formed from the liquid crystal composition is not particularly limited, but is preferably 0.2 to 10 ⁇ m, more preferably 0.5 to 2 ⁇ m.
- Example 1 Production of resin film> (1) Preparation of core layer cellulose acylate dope The following composition was put into a mixing tank and stirred to prepare a core layer cellulose acylate dope solution.
- Core layer cellulose acylate dope solution • cellulose acetate having an acetyl substitution degree of 2.88 and a weight average molecular weight of 260,000 100 parts by mass • phthalate oligomer A having the following structure: 10 parts by mass • a compound represented by the following formula I (A -1) 4 parts by mass-UV absorber represented by the following formula II (manufactured by BASF) 2.7 parts by mass-light stabilizer (manufactured by BASF, trade name: TINUVIN123) 0.18 parts by mass-N-alkenyl Propylene diamine triacetic acid (manufactured by Nagase ChemteX Corporation, trade name: Teclan DO) 0.02 parts by mass, methylene chloride (first solvent) 430 parts by mass, methylene chloride (
- Phthalate oligomer A weight average molecular weight: 750
- UV absorber represented by Formula II Formula II:
- outer layer cellulose acylate dope 10 parts by mass of the following inorganic particle-containing composition was added to 90 parts by mass of the above core layer cellulose acylate dope to prepare an outer layer cellulose acylate dope.
- Inorganic particle-containing composition-silica particles having an average primary particle size of 20 nm manufactured by Nippon Aerosil Co., Ltd., trade name: AEROSIL R972
- first solvent 2 parts by mass-methylene chloride
- second solvent 11 parts by mass ⁇
- Core layer cellulose acylate dope solution 1 part by mass
- the thickness unevenness of the entire casting band was 0.5% or less.
- An initial film was formed on the obtained cast film by applying quick dry air having a wind speed of 8 m / s, a gas concentration of 16%, and a temperature of 60 ° C. to the cast film surface. Thereafter, 140 ° C. drying air was blown from the upstream side of the upper part of the casting band. From the downstream side, 120 ° C. drying air and 60 ° C. drying air were blown. After the residual solvent amount was about 33% by mass, it was peeled off from the band. Next, both ends in the width direction of the obtained film were fixed with a tenter clip, and a film having a solvent residual amount of 3 to 15% by mass was dried while being stretched 1.06 times in the transverse direction.
- Second resin film (C) A second resin film (C) having a thickness of 100 ⁇ m was produced by the same production method as that for the first resin film (A).
- the saponified resin films (A) and (C) are simply referred to as resin films (A) and (C).
- resin films (A) and (C) are simply referred to as resin films (A) and (C).
- Adjustment of adhesive layer forming liquid> Using the adhesive layer (B) forming liquids A-1 to A-11 shown in Table 1 below, the resin films (A) and (C) were bonded by the following method. Details of each step in the bonding and an explanation of the compounds used are shown below.
- PVA-117H Kuraray Poval PVA-117H (trade name, manufactured by Kuraray Co., Ltd.), polyvinyl alcohol Gosenex Z410: trade name (manufactured by Nippon Synthetic Chemical Co., Ltd.), acetoacetyl-modified polyvinyl alcohol HEC: hydroxyethyl cellulose, weight average molecular weight 74,000
- a laminate with a hard coat layer was produced by the following method. Details of each step in the production of the laminate with a hard coat layer and an explanation of the compounds used are shown below.
- DPHA Mixture of dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate (manufactured by Nippon Kayaku Co., Ltd., trade name: KAYARAD DPHA) Cyclomer M100: 3,4-epoxycyclohexylmethyl methacrylate (Daicel, trade name)
- RS-90 antifouling agent, manufactured by DIC, fluorine-containing oligomer having radical polymerizable group P-112: leveling agent, compound P-112 described in paragraph 0053 of Japanese Patent No. 5175831
- HC layer Preparation of hard coat layer (HC layer)> The components shown in Table 2 above were mixed and filtered through a polypropylene filter having a pore size of 10 ⁇ m to prepare HC layer forming curable compositions HC-1 and HC-2. On the surface of the resin film (A) opposite to the adhesive layer (B) of the prepared laminate, the HC layer forming curable composition HC-1 was applied and cured to form a hard coat layer. .
- the coating and curing methods were as follows. In the die coating method using the slot die described in Example 1 of Japanese Patent Application Laid-Open No.
- the HC layer forming curable composition was applied at a conveyance speed of 30 m / min, and dried at an ambient temperature of 60 ° C. for 150 seconds. did. After that, under an atmosphere of nitrogen purge, using an air-cooled metal halide lamp (manufactured by Eye Graphics Co., Ltd.) having an oxygen concentration of about 0.1% by volume, irradiating ultraviolet rays with an illuminance of 20 mW / cm 2 and an irradiation amount of 30 mJ / cm 2. Then, the coated curable composition for forming an HC layer was cured to form a hard coat layer HC-1, and then wound up.
- an air-cooled metal halide lamp manufactured by Eye Graphics Co., Ltd.
- the HC layer forming curable composition HC-2 shown in Table 2 is applied to the surface of the hard coat layer HC-1 formed above, and dried and cured under the same conditions as the formation of the hard coat layer HC-1. Then, the second HC layer was formed, and the optical film of Example 1 was produced.
- Example 2 to 8 Optical films of Examples 2 to 8 were produced in the same manner as Example 1 except that the adhesive layer forming liquids A-2 to A-8 were used in place of the adhesive layer forming liquid A-1.
- Example 9 An optical film of Example 9 was produced in the same manner as in Example 2 except that instead of the resin films (A) and (C), a PET resin film produced as described below was used.
- a PET resin film produced as described below was used.
- the reaction liquid temperature was maintained at 60 ° C., trimethylbenzylammonium hydroxide as an isocyanurate conversion catalyst was added, and phosphoric acid was added to stop the reaction when the conversion to isocyanurate reached 48%. .
- unreacted HDI was removed with the thin film distillation apparatus, and the isocyanate type compound a was obtained.
- the obtained isocyanate compound a had a viscosity at 25 ° C. of 25,000 mPa ⁇ s, an isocyanate group content of 19.9% by mass, a number average molecular weight of 1080, and an average number of isocyanate groups of 5.1.
- reaction solution temperature was cooled to 60 ° C., 72 parts by weight of diethyl malonate and 0.88 part by weight of a 28% by weight methanol solution of sodium methylate were added and maintained for 4 hours, and then 2-ethylhexyl acid phosphate 0. 86 parts by weight were added. Subsequently, 43.3 parts by mass of diisopropylamine was added, and the reaction solution temperature was maintained at 70 ° C. for 5 hours. This reaction solution was analyzed by gas chromatography, and it was confirmed that the reaction rate of diisopropylamine was 70% to obtain isocyanate compound A (solid content concentration 70% by mass, effective NCO group mass 5.3% by mass). .
- organotin compound Elastotron Cat.21 manufactured by Daiichi Kogyo Seiyaku Co., Ltd.
- an ethylene glycol solution of antimony trioxide was continuously supplied, and the reaction was conducted with stirring at a temperature in the reaction vessel of 250 ° C. and an average residence time of about 4.3 hours. At this time, antimony trioxide was continuously added so that the amount of Sb added was 150 mass ppm (mass parts per million) in terms of element.
- This reaction product was transferred to a second esterification reaction vessel and reacted with stirring at a temperature in the reaction vessel of 250 ° C. and an average residence time of 1.2 hours.
- the mixture was transferred to the second polycondensation reaction tank, and under stirring, the reaction was performed under the conditions of a reaction tank temperature of 276 ° C., a reaction tank pressure of 5 torr (6.67 ⁇ 10 ⁇ 4 MPa) and a residence time of about 1.2 hours ( Polycondensation).
- the reaction mixture was further transferred to a third polycondensation reaction tank, and reacted under the conditions of a reaction tank temperature of 278 ° C., a reaction tank pressure of 1.5 torr (2.0 ⁇ 10 ⁇ 4 MPa) and a residence time of 1.5 hours ( Polycondensation) to obtain a reaction product (polyethylene terephthalate (PET)).
- PET polyethylene terephthalate
- composition for the second layer shown below By drying the composition for the second layer shown below until the water content becomes 20 mass ppm or less, and then charging it into the hopper of a uniaxial kneading extruder having a diameter of 50 mm and melting it at 300 ° C. with the extruder.
- a resin melt was prepared for forming a second layer located between the first and third layers.
- the raw material polyester 1 After drying the raw material polyester 1 until the water content becomes 20 ppm by mass or less, it is put into a hopper of a single screw kneading extruder having a diameter of 30 mm and melted at 300 ° C. by the extruder. Thus, a resin melt for forming the first layer and the third layer was prepared.
- the resin melt extruded from the extruder for layer II in the two-layer / three-layer merge block is the inner layer.
- the resin melt extruded from the extruder for the I layer and the III layer was laminated so as to become an outer layer, and extruded from a die having a width of 120 mm into a sheet shape.
- the molten resin sheet extruded from the die was extruded onto a cooling cast drum set at a surface temperature of 25 ° C., and was brought into close contact with the cooling cast drum using an electrostatic application method.
- the film after cooling was peeled from the drum using a peeling roll disposed opposite to the cooling cast drum to obtain an unstretched film.
- the discharge amount of each extruder was adjusted so that the ratio of the thicknesses of the I layer, the II layer, and the III layer was 10:80:10.
- the unstretched film is heated using a heated roll group and an infrared heater so that the film surface temperature is 95 ° C., and then 4.0 rolls in the vertical direction from the film transport direction with the roll group having a difference in peripheral speed.
- the resin film having a thickness of 100 ⁇ m was obtained by double-stretching.
- Example 10 instead of the resin films (A) and (C), a polycarbonate film having a thickness of 100 ⁇ m (in-plane retardation at 550 nm was 140 nm) produced by referring to Japanese Patent No. 3325560 [Example 3] was used. Except that, the optical film of Example 10 was produced in the same manner as in Example 2. In Table 3 below, the polycarbonate film is described as PC.
- Example 11 The optical film of Example 11 was produced in the same manner as in Example 2 except that the acrylic resin films produced as described below were used for the resin films (A) and (C).
- ⁇ Production of acrylic resin film> A pellet of acrylic resin (trade name: Sumipex EX) manufactured by Sumitomo Chemical Co., Ltd. is charged into a single screw extruder with an extrusion diameter of 65 mm, melted, melted and integrated by a multi-manifold method, and each layer film after drying The thickness was controlled to 5 ⁇ m / 90 ⁇ m / 5 ⁇ m and extruded through a T-die having a set temperature of 260 ° C. The obtained film-like product was sandwiched between a pair of metal rolls and molded to produce an acrylic resin film having a thickness of 100 ⁇ m.
- the acrylic resin film is described as PMMA.
- Examples 15 to 18 Optical films of Examples 15 to 18 were produced in the same manner as in Example 2 except that the adhesive layer (B) after drying was coated so as to have the thickness shown in Table 3 below.
- Examples 19 to 20 Optical films of Examples 19 to 20 were produced in the same manner as Example 16 except that the adhesive layer forming liquids A-10 to A-11 were used in place of the adhesive layer forming liquid A-2.
- Comparative Example 3 An optical film of Comparative Example 3 was prepared in the same manner as Example 3 except that the resin film (C) was changed to a norbornene-based resin film (trade name “Zeonor ZF14” manufactured by Nippon Zeon Co., Ltd.) having a thickness of 100 ⁇ m. did.
- Comparative Example 4 The optical film of Comparative Example 4 was produced in the same manner as in Example 11 except that the resin film (C) was changed to the resin film described in Example 1 and the adhesive layer forming solution A-7 was used.
- Comparative Example 5 The optical film of Comparative Example 5 was produced in the same manner as in Example 11 except that the resin film (A) was changed to the resin film described in Example 1 and the adhesive layer forming solution A-7 was used.
- each adhesive layer formation liquid used above casts so that the film thickness after drying may be set to 20 micrometers using an applicator on a glass plate (thickness 1mm), and atmospheric temperature After drying at 80 ° C. for 10 minutes or more, it was peeled from the glass plate. Using the obtained sample of the adhesive layer, it was tested and calculated in the same manner as the tensile modulus of the resin film.
- Thickness was measured by observing with a scanning electron microscope (SEM) by the following method. After exposing the cross section of each constituent member (resin film, adhesive layer and HC layer) or a member including each constituent member (for example, a liquid crystal panel or a part thereof) by an ordinary method such as ion beam or microtome, the exposed cross section The cross section was observed with SEM. In cross-sectional observation, various thicknesses were obtained as an arithmetic average of thicknesses at three equal points excluding both ends when the width direction of the member was equally divided into four.
- SEM scanning electron microscope
- the optical films of Examples and Comparative Examples are both a first HC layer (HC1) having a thickness of 15 ⁇ m and a second HC layer having a thickness of 5 ⁇ m on the first resin film (A). (HC2) in this order.
- the thickness of an optical film means the total thickness of a resin film (A), an adhesive layer (B), and a resin film (C).
- the optical films of Comparative Examples 1 to 3 having a tensile modulus of elasticity lower than 2.0 GPa in any one of the resin film (A), the adhesive layer (B), and the resin film (C) Comparative Example 4 in which either the difference in tensile elastic modulus between the resin film (A) and the adhesive layer (B) or the difference in tensile elastic modulus between the resin film (C) and the adhesive layer (B) is greater than 4.0 GPa
- the optical film of 5 and the optical film of Comparative Example 6 having a small optical film thickness of 81 ⁇ m both produced dents during 100 keystrokes (Evaluation E).
- the keystroke durability (stylus durability) was insufficient.
- the tensile elastic modulus of the resin film (A), the adhesive layer (B) and the resin film (C) satisfies the formulas (1) to (5), and the thickness of the optical film is greater than 100 ⁇ m.
- the thickness of the optical film is greater than 100 ⁇ m.
- Example 3 in which the tensile elastic modulus EB of the adhesive layer (B) is 3.3 GPa is 2.3 GPa.
- Example 1 which was as high as 5.5 GPa showed better keystroke durability.
- Example 1 and 2.8 GPa which are as small as 0.7 GPa
- Example 2 which is as small as 0.8 GPa shows better keystroke durability than Example 6 which is 3.4 GB and Example 7 which is smaller.
- Example 2 which is as large as 201 ⁇ m showed superior keystroke durability compared to Example 12 where the thickness of the optical film was 101 ⁇ m, Example 13 and Example 14 where the thickness was 161 ⁇ m.
- the optical film of the present invention When the optical film of the present invention is used for a front plate of an image display device, an image display device, a mirror with an image display function, a resistive touch panel, and a capacitive touch panel, the front plate and the like are excellent keystrokes. It is thought to show durability and manufacturing suitability.
- first resin film 1B second resin film 2A: adhesive layer 3A: hard coat layer (HC layer) 4A, 4B: Optical film 1: Conductive film for touch panel 2: Touch panel 4C: Optical film 5: Transparent insulating substrate 6A, 6B: Conductive member 7A, 7B: Protective layer 8: First conductive layer 9: Second conductive layer 11A: 1st dummy electrode 11: 1st electrode 12: 1st peripheral wiring 13: 1st external connection terminal 14: 1st connector part 15: 1st metal fine wire 21: 2nd electrode 22: 2nd peripheral wiring 23: 2nd exterior Connection terminal 24: 2nd connector part 25: 2nd metal fine wire C1: 1st cell C2: 2nd cell D1: 1st direction D2: 2nd direction M1: 1st mesh pattern M2: 2nd mesh pattern S1: Active area S2: peripheral area
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Abstract
Description
ガラス代替材料の樹脂フィルムとしては、例えば、特許文献1には、基材と、基材の少なくとも一方の面に積層されたハードコート層とを備え、面内方向のレターデーションが6000nm以上40000nm以下であるハードコートフィルムが記載されている。また、特許文献2には、熱可塑性樹脂を含むベース層と、このベース層上に形成された硬化性樹脂を含むハードコート層とを備えるハードコート層付樹脂フィルムが、複数枚積層されている積層体が記載されている。
本発明者らが鋭意検討した結果、樹脂フィルムの膜厚を厚くすることで打鍵耐久性を改良できることが分かってきた。その一方、樹脂フィルムの膜厚が厚くなるにつれて、平滑性が低下したり、変形したり、厚膜樹脂フィルム製造の際に担体からの剥離が困難になったりする問題が生じることも分かってきた。また、膜厚の厚い樹脂フィルムを製膜するには相応の時間を要すること、特に溶液製膜の場合には、残留溶媒を除去するための乾燥工程がより長くなることから、製造効率の問題も生じてしまう。このように、樹脂フィルムの打鍵耐久性と、樹脂フィルムの外観ないし製造適性(製造効率)との間には、いわゆるトレードオフの関係が生じることが明らかとなってきた。
本発明はこれらの知見に基づきさらに検討を重ね、完成されるに至ったものである。
(1)
少なくとも、第一の樹脂フィルム(A)と接着層(B)と第二の樹脂フィルム(C)とが、この順で積層されてなり、
上記第一の樹脂フィルム(A)の25℃における引張弾性率EA、上記接着層(B)の25℃における引張弾性率EB及び上記第二の樹脂フィルム(C)の25℃における引張弾性率ECが下記式(1)~(5)を満たし、
上記第一の樹脂フィルム(A)と上記接着層(B)と上記第二の樹脂フィルム(C)の合計厚みが100μmより大きい光学フィルム。
|EA-EB|≦4.0GPa 式(1)
|EC-EB|≦4.0GPa 式(2)
2.0GPa≦EA 式(3)
2.0GPa≦EB 式(4)
2.0GPa≦EC 式(5)
(2)
上記引張弾性率EA及び上記引張弾性率EBが下記式(1-2)を満たす、(1)に記載の光学フィルム。
|EA-EB|≦2.0GPa 式(1-2)
(3)
上記接着層(B)の厚みが10nm以上10μm以下である、(1)または(2)に記載の光学フィルム。
(4)
面内方向のレターデーションが6000nmより小さい、(1)~(3)のいずれか1つに記載の光学フィルム。
(5)
上記第一の樹脂フィルム(A)がセルロースエステル樹脂フィルムである、(1)~(4)のいずれか1つに記載の光学フィルム。
(6)
上記第二の樹脂フィルム(C)がセルロースエステル樹脂フィルムである、(1)~(5)のいずれか1つに記載の光学フィルム。
(7)
上記接着層(B)がポリビニルアルコールからなる、(1)~(6)のいずれか1つに記載の光学フィルム。
(8)
上記第一の樹脂フィルム(A)と第二の樹脂フィルム(C)が同一のフィルムである、(1)~(7)のいずれか1つに記載の光学フィルム。
(9)
上記第一の樹脂フィルム(A)および第二の樹脂フィルム(C)の少なくとも一方が、上記接着層(B)と反対側の面にハードコート層を有する、(1)~(8)のいずれか1つに記載の光学フィルム。
(10)
(1)~(9)のいずれか1つに記載の光学フィルムを有する、画像表示装置の前面板。
(11)
(10)に記載の前面板と、画像表示素子とを有する画像表示装置。
(12)
上記画像表示素子が液晶表示素子である、(11)に記載の画像表示装置。
(13)
上記画像表示素子が有機エレクトロルミネッセンス表示素子である、(11)に記載の画像表示装置。
(14)
上記画像表示素子がインセルタッチパネル表示素子である、(11)~(13)のいずれか1つに記載の画像表示装置。
(15)
上記画像表示素子がオンセルタッチパネル表示素子である、(11)~(13)のいずれか1つに記載の画像表示装置。
(16)
(10)に記載の前面板を有する抵抗膜式タッチパネル。
(17)
(10)に記載の前面板を有する静電容量式タッチパネル。
(18)
(11)に記載の画像表示装置を用いた画像表示機能付きミラー。
本明細書において、単に「アクリル」又は「(メタ)アクリル」と記載するときは、メタアクリル及び/又はアクリルを意味する。また、単に「アクリロイル」又は「(メタ)アクリロイル」と記載するときは、メタアクリロイル及び/又はアクリロイルを意味する。
本明細書において、各層の厚み及び引張弾性率は、実施例記載の方法により測定されるものである。
本発明の光学フィルムは、タッチパネルの前面板等として好適に用いることができ、また、偏光フィルム、位相差フィルム及び液晶表示用の輝度向上フィルム等の光学フィルムとしても好適に用いることができる。
[光学フィルム]
本発明の光学フィルムの好ましい実施形態を図1に示す。図1に示す光学フィルム4Aは、少なくとも、第一の樹脂フィルム(A)と接着層(B)と第二の樹脂フィルム(C)(図1においては、順に符号1A、2A、1Bで示される。)とが、この順で積層されてなる光学フィルムである。光学フィルムにおける、上記第一の樹脂フィルム(A)の25℃における引張弾性率EA、上記接着層(B)の25℃における引張弾性率EB及び上記第二の樹脂フィルム(C)の25℃における引張弾性率ECは、下記式(1)~(5)を満たす。また、光学フィルムの厚み、すなわち、上記第一の樹脂フィルム(A)と上記接着層(B)と上記第二の樹脂フィルム(C)の合計厚みは、100μmより大きい。
|EA-EB|≦4.0GPa 式(1)
|EC-EB|≦4.0GPa 式(2)
2.0GPa≦EA 式(3)
2.0GPa≦EB 式(4)
2.0GPa≦EC 式(5)
本発明の光学フィルムは上記構成を有することにより、優れた打鍵耐久性を実現することができる。これは、樹脂フィルムに打鍵を重ねると引張弾性率に大きな差がある面で歪みが発生するところ、本発明の光学フィルムでは引張弾性率が特定値以上の2層の樹脂フィルムを、これらの樹脂フィルムと引張弾性率の差が特定の値以下にある接着層を介して積層し、さらに光学フィルム全体を一程以上の厚みとすることにより、この歪みの発生を効果的に抑制できるためと推定される。また本発明の光学フィルムは積層体でありながらも、個々のフィルム厚を抑えることができるため、製造適性にも優れている。
樹脂フィルムの引張弾性率は、例えば、樹脂フィルムを構成する樹脂の種類により変えることができ、一般に、樹脂の分子量及び/又は結晶化度を高めることにより引張弾性率は高まる傾向がある。また、樹脂フィルムは、延伸により延伸方向の引張弾性率を高めることができる。樹脂フィルムが多層からなる場合にも、樹脂フィルムとしての引張弾性率を意味する。
第一の樹脂フィルム(A)の25℃における引張弾性率EA及び第二の樹脂フィルム(C)の25℃における引張弾性率ECは、打鍵耐久性をより高める点から、各々独立に、2.5GPa以上が好ましく、3.0GPa以上がより好ましく、3.5GPa以上がさらに好ましく、4.0GPa以上が最も好ましい。上限値は、特に制限はないが、12.0GPa以下が実際的である。
接着層(B)(以下、単に「接着層」とも称す。)の引張弾性率は、例えば、接着層を構成する樹脂の種類により変えることができ、一般に、樹脂の分子量や結晶化度を高めることにより引張弾性率は高まる傾向がある。また、接着層が架橋性基を持つ場合には、架橋剤などの添加によって接着層の架橋度を向上させることにより引張弾性率を高めることができる。さらに、接着層に重合性組成物が含まれる場合は、重合性基を有する化合物の重合性基当量(この化合物の分子量を、この化合物に含まれる重合性基の総数で除した値)の低減、接着層の重合率の向上、接着層への高弾性物質(例えば無機粒子等)の添加、剛直な分子構造(例えばアダマンタン骨格)を含む化合物の添加等により高まる傾向がある。
接着層(B)の25℃における引張弾性率EBは、打鍵耐久性をより高める点から、2.5GPa以上が好ましく、3.0GPa以上がより好ましく、3.5GPa以上がより好ましく、4.0GPa以上がさらに好ましく、4.5GPa以上が特に好ましく、5.0GPa以上が最も好ましい。上限値は、特に制限はないが、12.0GPa以下が実際的である。
上記式(1)で表される、第一の樹脂フィルム(A)の25℃における引張弾性率EAと接着層(B)の25℃における引張弾性率EBとの差の絶対値(|EA-EB|で記載される。以下において、絶対値と記載しない場合にも同様である。)は、打鍵耐久性をより高める点から、3.5GPa以下が好ましく、3.0GPa以下がより好ましく、2.5GPa以下がより好ましく、2.0GPa以下がさらに好ましく、1.5GPa以下が特に好ましく、1.0GPa以下が最も好ましい。
上記式(2)で表される、第二の樹脂フィルム(C)の25℃における引張弾性率ECと接着層(B)の25℃における引張弾性率EBとの差の絶対値(|EC-EB|で記載される。以下において、絶対値と記載しない場合にも同様である。)は、打鍵耐久性をより高める点から、3.5GPa以下が好ましく、3.0GPa以下がより好ましく、2.5GPa以下がより好ましく、2.0GPa以下がさらに好ましく、1.5GPa以下が特に好ましく、1.0GPa以下が最も好ましい。
本発明の光学フィルムの厚みは、打鍵耐久性の点から、120μm以上が好ましく、150μm以上がより好ましく、180μm以上がさらに好ましく、220μm以上がさらに好ましい。上限値は320μm以下であることが実際的である。
樹脂フィルムの厚みは、打鍵耐久性及び製造適性の点から、各々独立に、50~160μmが好ましく、60~160μmがより好ましく、80~160μmがさらに好ましく、100~160μmが特に好ましい。
ここで、第一の樹脂フィルムと第二の樹脂フィルムの厚みの合計は、打鍵耐久性の点から、100~320μmが好ましく、160~320μmがより好ましく、200~320μmがさらに好ましい。
(接着層の厚み)
接着層の厚みは、第一の樹脂フィルムと第二の樹脂フィルムを接着する点から10nm以上が好ましく、さらに干渉ムラも低減する観点から10nm~10μmが好ましく、10nm~5μmがより好ましく、10nm~1μmがさらに好ましい。
光学フィルムの波長550nmにおける面内方向のレターデーションは、干渉ムラを低減する点から、6000nmより小さいことが好ましく、1000nm以下が好ましく、500nm以下がより好ましく、50nm以下がさらに好ましい。
ここで、光学フィルムの面内方向の位相差(レターデーション)は、光学フィルムに直線偏光を入射して、光学フィルムを通過した光を、進相軸および遅相軸に沿った2つの直線偏光に分解したときに、進相軸での屈折率Nxと遅相軸での屈折率Nyおよび光学フィルムの厚さd(単位:nm)とから下記式(A)により示されるR(単位:nm)として定義される。
R=d×(Nx-Ny) (A)
(樹脂フィルムの材質)
本発明に用いられる樹脂フィルムは、光学フィルムを形成した場合に、上記引張弾性率の規定を満たすものであれば、その材質は特に限定されない。
樹脂フィルムは、例えば、アクリル系樹脂フィルム、ポリカーボネート(PC)系樹脂フィルム、トリアセチルセルロース(TAC)系樹脂フィルム等のセルロースエステル系樹脂フィルム、ポリエチレンテレフタラート(PET)系樹脂フィルム、ポリオレフィン系樹脂フィルム、ポリエステル系樹脂フィルム、および、アクリロニトリル-ブタジエン-スチレン共重合体フィルムを挙げることができ、アクリル系樹脂フィルム、セルロースエステル系樹脂フィルム、ポリエチレンテレフタラート系樹脂フィルムおよびポリカーボネート系樹脂フィルムから選択されるフィルムが好ましく、透湿性の点から、セルロースエステル系樹脂フィルムがより好ましい。
尚、アクリル系樹脂フィルムとは、アクリル酸エステルおよびメタクリル酸エステルからなる群から選択される1種以上の化合物から形成される重合体または共重合体の樹脂フィルムをいう。アクリル系樹脂フィルムの例としては、ポリメタクリル酸メチル樹脂(PMMA)フィルムが挙げられる。
樹脂の重量平均分子量は、引張弾性率を高める点から、10,000~1,000,000が好ましく、100,000~1,000,000がより好ましい。
また、樹脂フィルムの構成も限定されず、単層でも、2層以上からなる積層フィルムであってもよいが、2層以上の積層フィルムが好ましい。積層フィルムの積層数は、2~10層が好ましく、2~5層がより好ましく、2層または3層がさらに好ましい。3層以上の場合、外層と外層以外の層(コア層等)とは、異なる組成のフィルムが好ましい。また、外層同士は、同じ組成のフィルムが好ましい。
具体的には、TAC-a/TAC-b/TAC-a、アクリル-a/PC/アクリル-aおよびPET-a/PET-b/PET-aの積層構造を有するフィルム、ならびに、ポリカーボネート系樹脂単層のフィルムが挙げられる。ここで、同じ符号(a又はb)を付けたフィルム(例えば、Tac-a)は、同じ組成のフィルムを示す。
樹脂フィルムは、上述の樹脂の他に添加剤を含有してもよい。添加剤としては、後述のハードコート層で記載する、無機粒子、マット粒子、紫外線吸収剤、含フッ素化合物、表面調整剤、レベリング剤等が挙げられる。
後述の溶融製膜法では、上記添加剤と樹脂とを混合溶融した樹脂溶融物として、また、後述の溶液製膜法では、溶媒(後述のハードコートにおける記載を適用できる。)と樹脂と上記添加剤とを混合したドープ液として、樹脂フィルムの形成に用いることができる。
本発明の光学フィルムの作製前後で、樹脂フィルムの厚みはほとんど変化しない。
また、本発明に用いられる樹脂フィルムは、易接着層を有していてもよい。易接着層は、特開2015-224267号公報の段落0098~0133に記載された偏光子側易接着層および偏光子側易接着層の製造方法の内容を、本発明にあわせて本明細書に組み込むことができる。
この場合、易接着層は、本発明の光学フィルムにおける樹脂フィルム(A)あるいは(C)を構成する層とし、樹脂フィルム(A)あるいは(C)の引張弾性率は、易接着層を含む樹脂フィルム(A)あるいは(C)の引張弾性率を意味する。
樹脂フィルムは、いずれの方法で製膜してもよく、例えば溶融製膜法および溶液製膜法が挙げられる。
樹脂フィルムを溶融製膜法で製膜する場合、樹脂を押出機で溶融する溶融工程と、溶融した樹脂をダイからシート状に押し出す工程と、フィルム状に成形する工程とを含むことが好ましい。樹脂の材質によっては、溶融工程の後に溶融樹脂のろ過工程を設けてもよく、シート状に押し出す際に冷却してもよい。
以下、具体的な溶膜製膜法を説明するが、本発明はこれに限定されるものではない。
上記樹脂フィルムの製造方法は、樹脂を押出機で溶融する溶融工程と、溶融した樹脂をフィルターが設置されたろ過装置に通してろ過するろ過工程と、ろ過した樹脂をダイからシート状に押し出し、冷却ドラムの上に密着させることにより冷却固化して未延伸の樹脂フィルムを成形するフィルム成形工程と、未延伸の樹脂フィルムを、1軸又は2軸延伸する延伸工程とを有する。
このような構成により、樹脂フィルムを製造することができる。溶融した樹脂のろ過工程で使用されるフィルターの孔径が1μm以下であると、異物を十分に取り除くことができる。その結果、得られる樹脂フィルムのフィルム幅方向の表面粗さを制御することができる。
具体的には、樹脂フィルムの形成方法は下記工程を含むことができる。
上記樹脂フィルムの製造方法は、樹脂を押出機で溶融する溶融工程を含む。
樹脂、または樹脂と添加剤との混合物を含水率200ppm以下に乾燥した後、一軸(単軸)あるいは二軸の押出機に導入し溶融させることが好ましい。この時、樹脂の分解を抑制するために、窒素中あるいは真空中で溶融することも好ましい。詳細な条件は、特許4962661号の<0051>~<0052>(US2013/0100378号公報の<0085>~<0086>)を援用して、これらの公報に従い実施でき、これらの公報に記載された内容は本明細書に組み込まれる。
押出機は、一軸混練押出機が好ましい。
さらに、溶融樹脂(メルト)の送り出し精度を上げるためギアポンプを使用することも好ましい。
上記樹脂フィルムの製造方法は、溶融した樹脂をフィルターが設置されたろ過装置に通してろ過するろ過工程を含み、ろ過装置で使用されるフィルターの孔径は1μm以下が好ましい。
このような孔径の範囲のフィルターを有するろ過装置は、ろ過工程において1セットのみ設置してもよく、2セット以上設置してもよい。
上記樹脂フィルムの製造方法は、ろ過した樹脂をダイからシート状に押し出し、冷却ドラムの上に密着させることにより冷却固化して未延伸の樹脂フィルムを成形するフィルム成形工程を含む。
樹脂フィルムが多層で押出されて製造されてなる場合、得られる樹脂フィルムの好ましい内層の厚み(全層に対する比率)は50%以上95%以下が好ましく、より好ましくは60%以上90%以下、さらに好ましくは70%以上85%以下である。このような積層は、フィードブロックダイやマルチマニホールドダイを用いることで実施できる。
ダイから押し出される樹脂の温度は、放射温度計(林電工製、型番:RT61-2、放射率0.95で使用)により樹脂の表面を非接触で測定することができる。
冷却ドラムの上に密着する際の樹脂の温度は、放射温度計(林電工製、型番:RT61-2、放射率0.95で使用)により樹脂の表面を非接触で測定することができる。
上記樹脂フィルムの製造方法は、未延伸の樹脂フィルムを、1軸又は2軸延伸する延伸工程を含む。
縦延伸工程(フィルムの搬送方向と同じ方向に延伸する工程)では、樹脂フィルムが予熱された後、樹脂フィルムが加熱された状態で、周速差のある(すなわち、搬送速度の異なる)ローラー群で搬送方向に延伸される。
(ThTD-max-ThTD-min)÷ ThTD-av×100 [%]
が幅方向の厚みの変動である。
(ThMD-max-ThMD-min)÷ ThMD-av×100 [%]
が長手方向の厚みの変動である。
樹脂フィルムを溶液製膜法で製膜する場合、ドープ液を流延バンド上に流延し、流延膜を形成する工程と、流延膜に乾燥する工程と、流延膜を延伸する工程とを含むことが好ましい。具体的には、特許第4889335号に記載の方法によって製膜するのが好ましい。
本発明では、以下の方法を採用することが好ましい。
例えば、特開平11-123732号公報に記載の、流延膜の乾燥速度を乾量基準の含有溶媒量で300質量%/min(=5質量%/s)以下とし、緩やかな乾燥を行う方法が挙げられる。また、特開2003-276037号公報に記載の、中間層であるコア層の両表面にスキン層(外層)を有する多層構造の流延膜の共流延法において、コア層を形成するドープ液の粘度を高めて流延膜の強度を確保するとともに外層を形成するドープの粘度を低くする方法が挙げられる。さらに、流延膜を急乾燥して流延膜表面に膜を形成し、形成された膜のレベリング効果により面状を平滑化する方法、及び、流延膜を延伸する方法なども好ましく挙げられる。
ここで「同一のフィルム」とは、樹脂フィルムを構成する樹脂の材質が同じ(例えば、いずれもTACフィルム)であることを意味する。なかでも、樹脂の分子量が同じであることが好ましく、樹脂の分子量及び結晶化度が同じであることがより好ましく、樹脂の分子量、結晶化度及び延伸率が同じであることがさらに好ましい。また、上記に加えて、第一の樹脂フィルム(A)と第二の樹脂フィルム(C)の厚みが同じであることもより好ましい。
なお、「同じ」とは、完全同一に限定されず、実質的に同一であることを含む。具体的には、同一の製造方法(膜厚、延伸等が同じになるような条件)で作製したものであり、この条件で生じる誤差が含まれる。
(接着層を構成し得る成分)
接着層とは、樹脂フィルム同士を貼り合わせる役割を果たす層であり、本発明においては、第一の樹脂フィルムと第二の樹脂フィルムとを接着する。
接着層は、乾燥や反応により接着性を発現する成分(接着剤)を含む組成物を用いて形成することが好ましい。例えば、硬化反応により接着性を発現する成分を含む組成物(以下、「硬化性組成物」と称す。)を用いて形成される接着層は、かかる硬化性組成物を硬化させてなる硬化層である
ここで、セルロース誘導体とは、セルロースを変性したものを意味する。セルロース誘導体に特に制限はなく、公知のセルロース誘導体を使用することができる。例えば、HEC(ヒドロキシエチルセルロース)等を用いることができる。
樹脂の重量平均分子量は、引張弾性率を高める点から、1000以上が好ましく、10、000以上がより好ましい。
ケン化の方法については、特開2007-86748号公報の段落番号<0211>及び段落番号<0212>に記載されている方法を用いることができる。
たとえば、水平方向または鉛直方向に移動する帯状の長尺の樹脂フィルム(A)あるいは(C)の一方の面に、樹脂フィルム(C)あるいは(A)を同じ移動速度で接近させ、上記樹脂フィルム(A)と樹脂フィルム(C)の間に、接着剤層(B)となる接着剤を塗布し、ピンチロールで圧力をかけて樹脂フィルム(A)と樹脂フィルム(C)を貼り合わせることができる。ここで、塗布される接着剤は、接着剤層(B)を構成する材質を塗布できるように溶媒で希釈したものであってもよい。その場合、接着剤層(B)中の溶媒を乾燥させ、樹脂フィルム(A)と樹脂フィルム(C)の接着が完了する。この際の乾燥温度は、接着剤層(B)中の溶媒種および、樹脂フィルム(A)と樹脂フィルム(C)の樹脂種および厚みによるが、例えば接着剤層(B)中の溶媒が水である場合、30~85℃であることが好ましく、さらに好ましくは45~80℃である。
本発明においては、表面硬度の点から、第一の樹脂フィルム(A)及び第二の樹脂フィルム(C)の少なくとも一方が、上記接着層(B)の設けられた側とは反対側の面にハードコート層を有することが好ましく、どちらか一方の樹脂フィルムが有することがより好ましい。この場合、ハードコート層は、本発明の光学フィルムにおける樹脂フィルム(A)あるいは(C)を構成する層とはみなさず、樹脂フィルム(A)あるいは(C)の引張弾性率は、ハードコート層を含まない樹脂フィルム(A)あるいは(C)の引張弾性率を意味する。HC層を有する光学フィルムの一態様として、図2に示すように、第一の樹脂フィルム1A、接着層d2A、第二の樹脂フィルム1Bがこの順に積層され、第一の樹脂フィルム1Aの、接着層2Aを有する面とは反対側の面にハードコート層3Aを有する光学フィルム4Bが挙げられる。HC層は、光学フィルムに所望の鉛筆硬度を付与できれば、いずれの材質から構成されてもよい。
本発明の光学フィルムは、第一の樹脂フィルム(A)及び第二の樹脂フィルム(C)の少なくとも一方にHC層を有している場合にも、本発明の効果を奏する。
以下、HC層の具体的態様を説明するが、本発明は下記態様に限定されるものではない。
本発明に用いられるHC層は、HC層形成用硬化性組成物に活性エネルギー線を照射することにより硬化することで得ることができる。なお本発明および本明細書において、「活性エネルギー線」とは、電離放射線をいい、X線、紫外線、可視光、赤外線、電子線、α線、β線、γ線等が包含される。
本発明に用いられるHC層は、1層構造でも2層以上の積層構造であってもよいが、下記に詳細を記載する1層構造または2層以上の積層構造からなるHC層が好ましい。
1層構造のHC層形成用硬化性組成物の好ましい態様としては、第一の態様として、1分子中に2個以上のエチレン性不飽和基を有する重合性化合物を少なくとも一種含むHC層形成用硬化性組成物を挙げることができる。エチレン性不飽和基とは、エチレン性不飽和二重結合を含有する官能基をいう。また、第二の態様として、少なくとも一種のラジカル重合性化合物と少なくとも一種のカチオン重合性化合物を含むHC層形成用硬化性組成物を挙げることができる。
第一の態様のHC層形成用硬化性組成物に含まれる1分子中に2個以上のエチレン性不飽和基を有する重合性化合物としては、多価アルコールと(メタ)アクリル酸とのエステル〔例えば、エチレングリコールジ(メタ)アクリレート、ブタンジオールジ(メタ)アクリレート、ヘキサンジオールジ(メタ)アクリレート、1,4-シクロヘキサンジアクリレート、ペンタエリスリトールテトラ(メタ)アクリレート、ペンタエリスリトールトリ(メタ)アクリレート、トリメチロールプロパントリ(メタ)アクリレート、トリメチロールエタントリ(メタ)アクリレート、ジペンタエリスリトールテトラ(メタ)アクリレート、ジペンタエリスリトールペンタ(メタ)アクリレート、ジペンタエリスリトールヘキサ(メタ)アクリレート、ペンタエリスリトールヘキサ(メタ)アクリレート、1,2,3-シクロヘキサンテトラメタクリレート、ポリウレタンポリアクリレート、ポリエステルポリアクリレート〕、上記のエステルのエチレンオキサイド変性体、ポリエチレンオキサイド変性体やカプロラクトン変性体、ビニルベンゼンおよびその誘導体〔例、1,4-ジビニルベンゼン、4-ビニル安息香酸-2-アクリロイルエチルエステル、1,4-ジビニルシクロヘキサノン〕、ビニルスルホン(例、ジビニルスルホン)、アクリルアミド(例、メチレンビスアクリルアミド)およびメタクリルアミドが挙げられる。なお本明細書に記載の「(メタ)アクリレート」とは、アクリレートとメタクリレートの一方または両方の意味で用いられる。また、後述の「(メタ)アクリロイル基」は、アクリロイル基とメタクリロイル基の一方または両方の意味で用いられる。「(メタ)アクリル」は、アクリルとメタクリルの一方または両方の意味で用いられる。
上記の重合性化合物としては、一種のみ用いてもよく、構造の異なる二種以上を併用してもよい。なお、同様に、本明細書に記載の各成分は、この成分を、一種のみ用いてもよく、構造の異なる二種以上を併用してもよい。また、各成分の含有量は、構造の異なる二種以上を併用する場合には、それらの合計含有量をいうものとする。
第二の態様のHC層形成用硬化性組成物は、少なくとも一種のラジカル重合性化合物と少なくとも一種のカチオン重合性化合物を含む。好ましい態様としては、
アクリロイル基およびメタクリロイル基からなる群から選ばれるラジカル重合性基を1分子中に2個以上含むラジカル重合性化合物と;
カチオン重合性化合物と;
を含むHC層形成用硬化性組成物を挙げることができる。
アクリロイル基およびメタクリロイル基からなる群から選ばれるラジカル重合性基を1分子中に2個以上含むラジカル重合性化合物と;
カチオン重合性化合物と;
ラジカル光重合開始剤と;
カチオン光重合開始剤と;
を含むHC層形成用硬化性組成物を挙げることができる。以下において、本態様を、第二の態様(1)と記載する。
a)脂環式エポキシ基およびエチレン性不飽和基を含み、1分子中に含まれる脂環式エポキシ基の数が1個であり、かつ1分子中に含まれるエチレン性不飽和基の数が1個であり、分子量が300以下であるカチオン重合性化合物と;
b)1分子中に3個以上のエチレン性不飽和基を含むラジカル重合性化合物と;
c)ラジカル重合開始剤と;
d)カチオン重合開始剤と;
を含むHC層形成用硬化性組成物を挙げることができる。以下において、本態様を、第二の態様(2)と記載する。第二の態様(2)のHC層形成用硬化性組成物を硬化したHC層は、好ましくは、HC層の全固形分を100質量%とした場合に、上記a)由来の構造を15~70質量%、上記b)由来の構造を25~80質量%、上記c)を0.1~10質量%、上記d)を0.1~10質量%含むことができる。また、一態様では、第二の態様(2)のHC層形成用硬化性組成物は、このHC層形成用硬化性組成物の全固形分を100質量%とした場合に、上記a)を15~70質量%含むことが好ましい。なお、「脂環式エポキシ基」とは、エポキシ環と飽和炭化水素環とが縮合した環状構造を有する1価の官能基をいうものとする。
第二の態様のHC層形成用硬化性組成物は、少なくとも一種のラジカル重合性化合物と少なくとも一種のカチオン重合性化合物を含む。第二の態様(1)におけるラジカル重合性化合物は、アクリロイル基およびメタクリロイル基からなる群から選ばれるラジカル重合性基を1分子中に2個以上含む。上記ラジカル重合性化合物は、アクリロイル基およびメタクリロイル基からなる群から選ばれるラジカル重合性基を、1分子中に、好ましくは例えば2~10個含むことができ、より好ましくは2~6個含むことができる。
GPC装置:HLC-8120(東ソー製)
カラム:TSK gel Multipore HXL-M(東ソー製、内径7.8mm×カラム長30.0cm)
溶離液:テトラヒドロフラン
また、第二の態様(1)のHC層形成用硬化性組成物の第一のラジカル重合性化合物の含有量は、組成物全量100質量%に対して、好ましくは30質量%以上であり、より好ましくは50質量%以上であり、更に好ましくは70質量%以上である。一方、第一のラジカル重合性化合物の含有量は、組成物全量100質量%に対して、98質量%以下であることが好ましく、95質量%以下であることがより好ましく、90質量%以下であることが更に好ましい。
第二のラジカル重合性化合物の1分子中に含まれるラジカル重合性基の数は、好ましくは、少なくとも2個であり、より好ましくは3個以上であり、更に好ましくは4個以上である。また、第二のラジカル重合性化合物の1分子中に含まれるラジカル重合性基の数は、一態様では、例えば10個以下であるが、10個超であってもよい。また、第二のラジカル重合性化合物としては、分子量が200以上1000未満のラジカル重合性化合物が好ましい。
第二のラジカル重合性化合物は2種以上併用してもよい。この場合、ジペンタエリスリトールペンタアクリレートとジペンタエリスリトールヘキサアクリレートの混合物“DPHA”(日本化薬製)などを好ましく用いることができる。
b)成分としては、多価アルコールと(メタ)アクリル酸とのエステル、ビニルベンゼンおよびその誘導体、ビニルスルホン、(メタ)アクリルアミド等が挙げられる。中でも、アクリロイル基およびメタクリロイル基からなる群から選ばれるラジカル重合性基を1分子中に3個以上含むラジカル重合性化合物が好ましい。具体例としては、多価アルコールと(メタ)アクリル酸とのエステルであって、1分子中に3個以上のエチレン性不飽和基を有する化合物を挙げることができる。より詳しくは、例えば、(ジ)ペンタエリスリトールテトラ(メタ)アクリレート、(ジ)ペンタエリスリトールトリ(メタ)アクリレート、トリメチロールプロパントリ(メタ)アクリレート、EO変性トリメチロールプロパントリ(メタ)アクリレート、PO変性トリメチロールプロパントリ(メタ)アクリレート、EO変性リン酸トリ(メタ)アクリレート、トリメチロールエタントリ(メタ)アクリレート、ジトリメチロールプロパンテトラ(メタ)アクリレート、ジペンタエリスリトールテトラ(メタ)アクリレート、(ジ)ペンタエリスリトールペンタ(メタ)アクリレート、ジペンタエリスリトールヘキサ(メタ)アクリレート、ペンタエリスリトールヘキサ(メタ)アクリレート、1,2,3-シクロヘキサンテトラメタクリレート、ポリウレタンポリアクリレート、ポリエステルポリアクリレート、カプロラクトン変性トリス(アクリロキシエチル)イソシアヌレート、トリペンタエリスリトールトリアクリレート、トリペンタエリスリトールヘキサトリアクリレート、1,2,4-シクロヘキサンテトラ(メタ)アクリレート、ペンタグリセロールトリアクリレート、等が挙げられる。なお上記の「(ジ)ペンタエリスリトール」とは、ペンタエリスリトールとジペンタエリスリトールの一方または両方の意味で用いられる。
アクリロイル基およびメタクリロイル基からなる群から選ばれるラジカル重合性基を1分子中に3個以上含む樹脂としては、例えば、ポリエステル系樹脂、ポリエーテル系樹脂、アクリル系樹脂、エポキシ系樹脂、ウレタン系樹脂、アルキド系樹脂、スピロアセタール系樹脂、ポリブタジエン系樹脂、ポリチオールポリエン系樹脂、多価アルコール等の多官能化合物等の重合体等も挙げられる。
更に、アクリロイル基およびメタクリロイル基からなる群から選ばれるラジカル重合性基を1分子中に3個以上含むラジカル重合性化合物の具体例としては、日本化薬製KAYARAD DPHA、同DPHA-2C、同PET-30、同TMPTA、同TPA-320、同TPA-330、同RP-1040、同T-1420、同D-310、同DPCA-20、同DPCA-30、同DPCA-60、同GPO-303、大阪有機化学工業製V#400、V#36095D等のポリオールと(メタ)アクリル酸のエステル化物を挙げることができる。また紫光UV-1400B、同UV-1700B、同UV-6300B、同UV-7550B、同UV-7600B、同UV-7605B、同UV-7610B、同UV-7620EA、同UV-7630B、同UV-7640B、同UV-6630B、同UV-7000B、同UV-7510B、同UV-7461TE、同UV-3000B、同UV-3200B、同UV-3210EA、同UV-3310EA、同UV-3310B、同UV-3500BA、同UV-3520TL、同UV-3700B、同UV-6100B、同UV-6640B、同UV-2000B、同UV-2010B、同UV-2250EA、同UV-2750B(日本合成化学製)、UL-503LN(共栄社化学製)、ユニディック17-806、同17-813、同V-4030、同V-4000BA(大日本インキ化学工業製)、EB-1290K、EB-220、EB-5129、EB-1830,EB-4358(ダイセルUCB製)、ハイコープAU-2010、同AU-2020((株)トクシキ製)、アロニックスM-1960(東亜合成製)、アートレジンUN-3320HA、UN-3320HC、UN-3320HS、UN-904、HDP-4T等の3官能以上のウレタンアクリレート化合物、アロニックスM-8100、M-8030、M-9050(東亜合成製)、KBM-8307(ダイセルサイテック製)の3官能以上のポリエステル化合物なども好適に使用することができる。
また、b)成分としては、一種のみ用いてもよく、構造の異なる二種胃需要を併用してもよい。
第二の態様のHC層形成用硬化性組成物は、少なくとも一種のラジカル重合性化合物と少なくとも一種のカチオン重合性化合物を含む。カチオン重合性化合物としては、カチオン重合可能な重合性基(カチオン重合性基)を有するものであれば、何ら制限なく用いることができる。また、1分子中に含まれるカチオン重合性基の数は、少なくとも1個である。カチオン重合性化合物は、カチオン重合性基を1分子中に1個含む単官能化合物であっても、2個以上含む多官能化合物であってもよい。多官能化合物に含まれるカチオン重合性基の数は、特に限定されるものではないが、例えば1分子中に2~6個である。また、多官能化合物の1分子中に2個以上含まれるカチオン重合性基は、同一あってもよく、構造が異なる二種以上であってもよい。
(1)カチオン重合性化合物として、含窒素複素環含有化合物を含む。好ましくは、含窒素複素環含有化合物が有する含窒素複素環は、イソシアヌレート環およびグリコールウリル環からなる群から選択される。含窒素複素環含有化合物は、より好ましくは、イソシアヌレート環含有化合物である。更に好ましくは、イソシアヌレート環含有化合物は、1分子中に1つ以上のエポキシ環を含むエポキシ環含有化合物である。
(2)カチオン重合性化合物として、カチオン重合性基当量が150未満のカチオン重合性化合物を含む。好ましくは、エポキシ基当量が150未満のエポキシ基含有化合物を含む。
(3)カチオン重合性化合物が、エチレン性不飽和基を含む。
(4)カチオン重合性化合物として、1分子中に1個以上のオキセタン環を含むオキセタン環含有化合物を、他のカチオン重合性化合物とともに含む。好ましくは、オキセタン環含有化合物は、含窒素複素環を含まない化合物である。
また、上記HC層形成用硬化性組成物のカチオン重合性化合物の含有量は、第一のラジカル重合性化合物の含有量とカチオン重合性化合物との合計含有量100質量部に対して、好ましくは0.05質量部以上であり、より好ましくは0.1質量部以上であり、更に好ましくは1質量部以上である。一方、カチオン重合性化合物の含有量は、第一のラジカル重合性化合物の含有量とカチオン重合性化合物との合計含有量100質量部に対して、50質量部以下であることが好ましく、40質量部以下であることがより好ましい。
なお本発明および本明細書において、カチオン重合性基とラジカル重合性基をともに有する化合物は、カチオン重合性化合物に分類し、HC層形成用硬化性組成物における含有量を規定するものとする。
HC層形成用硬化性組成物は重合開始剤を含むことが好ましく、光重合開始剤を含むことがより好ましい。ラジカル重合性化合物を含むHC層形成用硬化性組成物は、ラジカル光重合開始剤を含むことが好ましく、カチオン重合性化合物を含むHC層形成用硬化性組成物は、カチオン光重合開始剤を含むことが好ましい。なおラジカル光重合開始剤は一種のみ用いてもよく、構造の異なる二種以上を併用してもよい。この点は、カチオン光重合開始剤についても同様である。
以下、各光重合開始剤について、順次説明する。
ラジカル光重合開始剤としては、光照射により活性種としてラジカルを発生することができるものであればよく、公知のラジカル光重合開始剤を、何ら制限なく用いることができる。具体例としては、例えば、ジエトキシアセトフェノン、2-ヒドロキシ-2-メチル-1-フェニルプロパン-1-オン、ベンジルジメチルケタール、4-(2-ヒドロキシエトキシ)フェニル-(2-ヒドロキシ-2-プロピル)ケトン、1-ヒドロキシシクロヘキシルフェニルケトン、2-メチル-2-モルホリノ(4-チオメチルフェニル)プロパン-1-オン、2-ベンジル-2-ジメチルアミノ-1-(4-モルホリノフェニル)ブタノン、2-ヒドロキシ-2-メチル-1-[4-(1-メチルビニル)フェニル]プロパノンオリゴマー、2-ヒドロキシ-1-{4-[4-(2-ヒドロキシ-2-メチル-プロピオニル)-ベンジル]フェニル}-2-メチル-プロパン-1-オン等のアセトフェノン類;1,2-オクタンジオン、1-[4-(フェニルチオ)-,2-(O-ベンゾイルオキシム)]、エタノン,1-[9-エチル-6-(2-メチルベンゾイル)-9H-カルバゾール-3-イル]-,1-(0-アセチルオキシム)等のオキシムエステル類;ベンゾイン、ベンゾインメチルエーテル、ベンゾインエチルエーテル、ベンゾインイソプロピルエーテル、ベンゾインイソブチルエーテル等のベンゾイン類;ベンゾフェノン、オルト-ベンゾイル安息香酸メチル、4-フェニルベンゾフェノン、4-ベンゾイル-4’-メチル-ジフェニルサルファイド、3,3’,4,4’-テトラ(t-ブチルパーオキシカルボニル)ベンゾフェノン、2,4,6-トリメチルベンゾフェノン、4-ベンゾイル-N,N-ジメチル-N-[2-(1-オキソ-2-プロペニルオキシ)エチル]ベンゼンメタナミニウムブロミド、(4-ベンゾイルベンジル)トリメチルアンモニウムクロリド等のベンゾフェノン類;2-イソプロピルチオキサントン、4-イソプロピルチオキサントン、2,4-ジエチルチオキサントン、2,4-ジクロロチオキサントン、1-クロロ-4-プロポキシチオキサントン、2-(3-ジメチルアミノ-2-ヒドロキシ)-3,4-ジメチル-9H-チオキサントン-9-オンメソクロリド等のチオキサントン類;2,4,6-トリメチルベンゾイル-ジフェニルフォスフィンオキサイド、ビス(2,6-ジメトキシベンゾイル)-2,4,4-トリメチル-ペンチルフォスフィンオキサイド、ビス(2,4,6-トリメチルベンゾイル)-フェニルフォスフィンオキサイド等のアシルフォスフィンオキサイド類;等が挙げられる。また、ラジカル光重合開始剤の助剤として、トリエタノールアミン、トリイソプロパノールアミン、4,4’-ジメチルアミノベンゾフェノン(ミヒラーケトン)、4,4’-ジエチルアミノベンゾフェノン、2-ジメチルアミノエチル安息香酸、4-ジメチルアミノ安息香酸エチル、4-ジメチルアミノ安息香酸(n-ブトキシ)エチル、4-ジメチルアミノ安息香酸イソアミル、4-ジメチルアミノ安息香酸2-エチルヘキシル、2,4-ジエチルチオキサンソン、2,4-ジイソプロピルチオキサンソン等を併用してもよい。
以上のラジカル光重合開始剤および助剤は、公知の方法で合成可能であり、市販品として入手も可能である。市販のラジカル光重合開始剤としては、BASF製のイルガキュア(127,651,184,819,907,1870(CGI-403/Irg184=7/3混合開始剤、500,369,1173,2959,4265,4263など)、OXE01)等、日本化薬製のKAYACURE(DETX-S,BP-100,BDMK,CTX,BMS,2-EAQ,ABQ,CPTX,EPD,ITX,QTX,BTC,MCAなど)、サートマー製のEsacure(KIP100F,KB1,EB3,BP,X33,KT046,KT37,KIP150,TZT)等を好ましい例として挙げられる。
カチオン光重合開始剤としては、光照射により活性種としてカチオンを発生することができるものであればよく、公知のカチオン光重合開始剤を、何ら制限なく用いることができる。具体例としては、公知のスルホニウム塩、アンモニウム塩、ヨードニウム塩(例えばジアリールヨードニウム塩)、トリアリールスルホニウム塩、ジアゾニウム塩、イミニウム塩などが挙げられる。より具体的には、例えば、特開平8-143806号公報段落0050~0053に示されている式(25)~(28)で表されるカチオン光重合開始剤、特開平8-283320号公報段落0020にカチオン重合触媒として例示されているもの等を挙げることができる。また、カチオン光重合開始剤は、公知の方法で合成可能であり、市販品としても入手可能である。市販品としては、例えば、日本曹達製CI-1370、CI-2064、CI-2397、CI-2624、CI-2639、CI-2734、CI-2758、CI-2823、CI-2855およびCI-5102等、ローディア製PHOTOINITIATOR2047等、ユニオンカーバイト製UVI-6974、UVI-6990、サンアプロ製CPI-10Pを用いることができる。
HC層形成用硬化性組成物は、活性エネルギー線の照射により硬化する性質を有する少なくとも一種の成分を含み、任意に少なくとも一種の重合開始剤を含むことができ、含むことが好ましい。それらの詳細は、先に記載した通りである。
次に、HC層形成用硬化性組成物に任意に含まれ得る各種成分について説明する。
HC層形成用硬化性組成物は、平均一次粒径が2μm未満の無機粒子を含むことができる。HC層形成用硬化性組成物を硬化したHC層を有する前面板の硬度向上(更にはこの前面板を有する液晶パネルの硬度向上)の観点からは、HC層形成用硬化性組成物およびこの組成物を硬化したHC層は、平均一次粒径が2μm未満の無機粒子を含むことが好ましい。無機粒子の平均一次粒径は、10nm~1μmの範囲であることが好ましく、10nm~100nmの範囲であることがより好ましく、10nm~50nmの範囲であることが更に好ましい。
無機粒子および後述のマット粒子の平均一次粒径については、透過型電子顕微鏡(倍率50万~200万倍)で粒子の観察を行い、無作為に選択した粒子(一次粒子)100個を観察し、それらの粒径の平均値をもって平均一次粒径とする。
S-1 H2C=C(X)COOC3H6Si(OCH3)3
S-2 H2C=C(X)COOC2H4OTi(OC2H5)3
S-3 H2C=C(X)COOC2H4OCOC5H10OPO(OH)2
S-4 (H2C=C(X)COOC2H4OCOC5H10O)2POOH
S-5 H2C=C(X)COOC2H4OSO3H
S-6 H2C=C(X)COO(C5H10COO)2H
S-7 H2C=C(X)COOC5H10COOH
S-8 CH2CH(O)CH2OC3H6Si(OCH3)3
(Xは、水素原子またはメチル基を表す)
HC層形成用硬化性組成物は、マット粒子を含むこともできる。マット粒子とは、平均一次粒径が2μm以上の粒子をいうものとし、無機粒子であっても有機粒子であってもよく、または無機・有機の複合材料の粒子であってもよい。マット粒子の形状は、球形、非球形を問わない。マット粒子の平均一次粒径は、2~20μmの範囲であることが好ましく、4~14μmの範囲であることがより好ましく、6~10μmの範囲であることが更に好ましい。
HC層形成用硬化性組成物は、紫外線吸収剤を含有することも好ましい。紫外線吸収剤としては、例えば、ベンゾトリアゾール化合物、トリアジン化合物を挙げることができる。ここでベンゾトリアゾール化合物とは、ベンゾトリアゾール環を有する化合物であり、具体例としては、例えば特開2013-111835号公報段落0033に記載されている各種ベンゾトリアゾール系紫外線吸収剤を挙げることができる。トリアジン化合物とは、トリアジン環を有する化合物であり、具体例としては、例えば特開2013-111835号公報段落0033に記載されている各種トリアジン系紫外線吸収剤を挙げることができる。樹脂フィルム中の紫外線吸収剤の含有量は、例えばフィルムに含まれる樹脂100質量部に対して0.1~10質量部程度であるが、特に限定されるものではない。また、紫外線吸収剤については、特開2013-111835号公報段落0032も参照できる。なお本発明および本明細書における紫外線とは200~380nmの波長帯域に発光中心波長を有する光をいうものとする。
HC層形成用硬化性組成物は、レベリング剤および防汚剤等の含フッ素化合物を含有することも好ましい。
レベリング剤としては、含フッ素ポリマーが好ましく用いられる。例えば、特許5175831号に記載されているフルオロ脂肪族基含有ポリマーが挙げられる。またフルオロ脂肪族基含有ポリマーを構成する、一般式(1)で表されるフルオロ脂肪族基含有モノマーの含有量が全重合単位の50質量%以下のフルオロ脂肪族基含有ポリマーをレベリング剤として用いることもできる。
HC層が防汚剤を含むと、指紋や汚れの付着を低減し、また、付着した汚れの拭き取りを容易にすることができる。また、表面のすべり性を向上させる事により耐擦性をより向上させることも可能になる。
防汚剤は、含フッ素化合物を含有することが好ましい。含フッ素化合物は、パーフルオロポリエーテル基および重合性基(好ましくは、ラジカル重合性基)を有することが好ましく、パーフルオロポリエーテル基および重合性基を有し、かつ重合性基を一分子中に複数有することがさらに好ましい。このような構成とすることにより、耐擦性改良という効果をより効果的に発揮させることができる。
尚、本明細書では、防汚剤が、重合性基を有する場合であっても、上記重合性化合物1~3および上記他の重合性化合物には該当しないものとして扱う。
上記含フッ素化合物は、モノマー、オリゴマーおよびポリマーのいずれであってもよいが、オリゴマー(含フッ素オリゴマー)であることが好ましい。
なお、後述の(vi)その他の成分に記載するリベリング剤および防汚剤も、上記に加えて含有することができる。
以上説明した防汚剤としては、公知の方法で合成したものを用いてもよく、市販品を用いてもよい。市販品としては、DIC社製のRS-90、RS-78などを好ましく用いることができる。
HC層形成用硬化性組成物は、防汚剤を、1種のみ含んでいても良いし、2種以上含んでいても良い。2種以上含まれている場合、その合計量が上記範囲となることが好ましい。
また、HC層形成用硬化性組成物は、防汚剤を実質的に含まない構成とすることもできる。
HC層形成用硬化性組成物は、溶媒を含むことも好ましい。溶媒としては、有機溶媒が好ましく、有機溶媒の1種または2種以上を任意の割合で混合して用いることができる。有機溶媒の具体例としては、例えば、メタノール、エタノール、プロパノール、n-ブタノール、i-ブタノール等のアルコール類;アセトン、メチルイソブチルケトン、メチルエチルケトン、シクロヘキサノン等のケトン類;エチルセロソルブ等のセロソルブ類;トルエン、キシレン等の芳香族類;プロピレングリコールモノメチルエーテル等のグリコールエーテル類;酢酸メチル、酢酸エチル、酢酸ブチル等の酢酸エステル類;ジアセトンアルコール等が挙げられる。これらの中でも、シクロヘキサノン、メチルエチルケトン、メチルイソブチルケトンおよび酢酸メチルが好ましく、シクロヘキサノン、メチルエチルケトン、メチルイソブチルケトンおよび酢酸メチルを任意の割合で混合して用いることがより好ましい。このような構成とすることにより、耐擦性、打抜き性および密着性により優れた光学フィルムが得られる。
また、HC形成用硬化性組成物の固形分は、10~90質量%であることが好ましく、50~80質量%であることがより好ましく、65~75質量%であることが特に好ましい。
HC層形成用硬化性組成物は、上記成分に加えて、公知の添加剤の一種以上を任意の量で含むことができる。添加剤としては、表面調整剤、レベリング剤、重合禁止剤、ポリロタキサン等を挙げることができる。それらの詳細については、例えば特開2012-229412号公報の段落0032~0034を参照できる。また、市販の防汚剤または公知の方法で調製可能な防汚剤を含むこともできる。ただし添加剤はこれらに限らず、HC層形成用硬化性組成物に一般に添加され得る各種添加剤を用いることができる。また、HC層形成用硬化性組成物は、公知の溶媒を任意の量で含むこともできる。
本発明の光学フィルムは、図2におけるHC層3Aが、少なくとも、第1のHC層、および第2のHC層を樹脂フィルム1A側から順に有する態様も好ましい。
樹脂フィルム1Aの表面に、第1のHC層が位置していても、間に他の層を有していてもよい。同様に、第1のHC層の表面に、第2のHC層が位置していても、間に他の層を有していても良い。第1のHC層と第2のHC層の密着性を高める観点からは、第1のHC層の表面に第2のHC層が位置する、すなわち、両層は、膜面の少なくとも一部において接している方が好ましい。
さらに、詳細を後述するとおり、本発明の光学フィルムをタッチパネルに用いる場合、上記第2のHC層が画像表示素子の前面側となるように光学フィルムを配置することが好ましいが、光学フィルム表面の耐擦性、打抜き性を優れたものにするためには、上記第2のHC層が光学フィルムの表面側、特に、最表面に配置されることが好ましい。
本発明の第1のHC層は、第1のHC層形成用硬化性組成物から形成される。
第1のHC層形成用硬化性組成物は、ラジカル重合性基を有する重合性化合物1と、同一分子内にカチオン重合性基とラジカル重合性基を有し、かつ重合性化合物1とは異なる重合性化合物2とを含有し、第1のHC層形成用硬化性組成物に含まれる重合性化合物中、重合性化合物2の含有量が51質量%以上である。
重合性化合物1としては、前述のラジカル重合性化合物の記載が好ましく適用され、重合性化合物2としては、前述のカチオン重合性化合物におけるa)成分の記載が好ましく適用される。
また、第1のHC層形成用硬化性組成物は、重合性化合物1とも重合性化合物2とも異なる他の重合性化合物を有していてもよい。
上記他の重合性化合物は、カチオン重合性基を有する重合性化合物であることが好ましい。上記カチオン重合性基としては、重合性化合物2で述べたカチオン重合性基と同義であり、好ましい範囲も同様である。特に、本発明では、他の重合性化合物として、カチオン重合性基を含む、含窒素複素環含有化合物が好ましい。このような化合物を用いることにより、樹脂フィルムと第1のHC層の密着性をより効果的に向上させることができる。含窒素複素環としては、イソシアヌレート環(後述の例示化合物B-1~B-3に含まれる含窒素複素環)およびグリコールウリル環(後述の例示化合物B-10に含まれる含窒素複素環)からなる群から選ばれる含窒素複素環が例示され、イソシアヌレート環がより好ましい。他の重合性化合物が有するカチオン性基の数は、1~10が好ましく、2~5がより好ましい。また、他の重合性化合物として、カチオン重合性基と含窒素複素環構造を有する重合性化合物を用いる場合、樹脂フィルムは、アクリル系樹脂フィルムを含む樹脂フィルムが好ましい。このような構成とすることにより、樹脂フィルムと第1のHC層の密着性がより向上する傾向にある。
他の重合性化合物の具体例としては、前述の例示化合物B-1~B-14が挙げられるが、本発明は前述の具体例に限定されるものではない。
その他、前述の、重合開始剤、無機粒子、マット粒子、紫外線吸収剤、含フッ素化合物、溶媒およびその他の成分の記載を好ましく適用することができる。
特に第1のHC層形成用硬化性組成物は、溶媒を含むことが好ましく、第2のHC層形成用硬化性組成物は、防汚剤を含むことが好ましい。
HC層の厚みは、3μm以上100μm以下が好ましく、5μm以上70μm以下がより好ましく、10μm以上50μm以下がさらに好ましい。
(HC層の鉛筆硬度)
HC層の鉛筆硬度は、硬いほどよく、具体的には5H以上が好ましく、7H以上がより好ましい。
HC層形成用硬化性組成物を、樹脂フィルム上に直接、または易接着層等の他の層を介して、塗布し、活性エネルギー線を照射することにより、HC層を形成することができる。塗布は、ディップコート法、エアーナイフコート法、カーテンコート法、ローラーコート法、ダイコート法、ワイヤーバーコート法、グラビアコート法等の公知の塗布方法により行うことができる。なおHC層は、二種以上の異なる組成の組成物を同時または逐次塗布することにより二層以上(例えば二層~五層程度)の積層構造のHC層として形成することもできる。
本発明の光学フィルムを含む物品としては、家電業界、電気電子業界、自動車業界、住宅業界をはじめとする様々な産業界において打鍵耐久性および製造適正を向上することが求められる各種物品を挙げることができる。具体例としては、タッチセンサ、タッチパネル、液晶表示装置等の画像表示装置、自動車の窓ガラス、住居の窓ガラス、等を挙げることができる。これら物品に、好ましくは表面保護フィルムとして本発明の光学フィルムを設けることにより、優れた打鍵耐久性を示す物品を優れた製造適正で提供することが可能となる。本発明の光学フィルムは、画像表示装置用の前面板に用いられる光学フィルムとして好ましく用いられ、タッチパネルの画像表示素子の前面板に用いられる光学フィルムであることがより好ましい。
本発明の光学フィルムを用いることができるタッチパネルは特に制限はなく、目的に応じて適宜選択することができ、例えば、表面型静電容量式タッチパネル、投影型静電容量式タッチパネル、抵抗膜式タッチパネルなどが挙げられる。詳細については、後述する。
なお、タッチパネルとは、いわゆるタッチセンサを含むものとする。タッチパネルにおけるタッチパネルセンサー電極部の層構成が、2枚の透明電極を貼合する貼合方式、1枚の基板の両面に透明電極を具備する方式、片面ジャンパーあるいはスルーホール方式あるいは片面積層方式のいずれでもよい。
本発明の光学フィルムを有する画像表示装置は、本発明の光学フィルムを有する前面板と、画像表示素子とを有する画像表示装置である。
画像表示装置としては、液晶表示装置(Liquid Crystal Display;LCD)、プラズマディスプレイパネル、エレクトロルミネッセンスディスプレイ、陰極管表示装置およびタッチパネルのような画像表示装置に用いることができる。
液晶表示装置としては、TN(Twisted Nematic)型、STN(Super-Twisted Nematic)型、TSTN(Triple Super Twisted Nematic)型、マルチドメイン型、VA(Vertical Alignment)型、IPS(In Plane Switching)型、OCB(Optically CompensatedBend)型等が挙げられる。
画像表示装置は、脆性が改良されハンドリング性に優れ、表面平滑性やシワによる表示品位を損なう事が無く、湿熱試験時の光漏れを低減できることが好ましい。
すなわち、本発明の光学フィルムを有する画像表示装置は、画像表示素子が液晶表示素子であることが好ましい。液晶表示素子を有する画像表示装置としては、ソニーエリクソン社製、エクスペリアPなどを挙げることができる。
有機エレクトロルミネッセンス表示素子は、公知技術を、何ら制限なく適用することができる。有機エレクトロルミネッセンス表示素子を有する画像表示装置としては、SAMSUNG社製、GALAXY SIIなどを挙げることができる。
インセルタッチパネル表示素子は、例えば、特開2011-76602号公報、特開2011-222009号公報等の公知技術を、何ら制限なく適用することができる。インセルタッチパネル表示素子を有する画像表示装置としては、ソニーエリクソン社製、エクスペリアPなどを挙げることができる。
-Cell)タッチパネル表示素子であることも好ましい。オンセルタッチパネル表示素子とは、タッチパネル機能を画像表示素子セル外に配置したものである。
オンセルタッチパネル表示素子は、例えば、特開2012-88683号公報等の公知技術を、何ら制限なく適用することができる。オンセルタッチパネル表示素子を有する画像表示装置としては、SAMSUNG社製、GALAXY SIIなどを挙げることができる。
本発明の光学フィルムを有するタッチパネルは、本発明の光学フィルムにタッチセンサーフィルムを貼り合わせてタッチセンサを含むタッチパネルである。本発明の光学フィルムがHC層を有する場合には、HC層が配置された面とは反対側の樹脂フィルム面にタッチセンサーフィルムを貼り合わせることが好ましい。
タッチセンサーフィルムとしては特に制限はないが、導電層が形成された導電性フィルムであることが好ましい。
導電性フィルムは、任意の支持体の上に導電層が形成された導電性フィルムであることが好ましい。
導電層は、電極パターンであることが好ましい。また、透明電極パターンであることも好ましい。電極パターンは透明導電材料層をパターニングしたものでもよく、不透明な導電材料の層をパターン形成したものでもよい。
金属細線が銀または銀を含む合金からなることが好ましい。金属細線が銀または銀を含む合金からなる導電層としては特に制限は無く、公知の導電層を用いることができる。例えば、特開2014-168886号公報の段落0040~0041に記載の導電層を用いることが好ましく、この公報の内容は本明細書に組み込まれる。
金属細線が銅または銅を含む合金からなることも好ましい。上記合金は、特に制限は無く、公知の導電層を用いることができる。例えば、特開2015-49852号公報の段落0038~0059に記載の導電層を用いることが好ましく、この公報の内容は本明細書に組み込まれる。
タッチセンサーフィルムは、両面に導電層を有することも好ましい。
本発明の光学フィルムを有する抵抗膜式タッチパネルは、本発明の光学フィルムを有する前面板を有する抵抗膜式タッチパネルである。
抵抗膜式タッチパネルは、導電性膜を有する上下1対の基板の導電性膜同士が対向するようにスペーサーを介して配置された基本構成からなるものである。なお抵抗膜式タッチパネルの構成は公知であり、本発明では公知技術を何ら制限なく適用することができる。
本発明の光学フィルムを有する静電容量式タッチパネルは、本発明の光学フィルムを有する前面板を有する静電容量式タッチパネルである。
静電容量式タッチパネルの方式としては、表面型静電容量式、投影型静電容量式等が挙げられる。投影型の静電容量式タッチパネルは、X軸電極と、X電極と直交するY軸電極とを絶縁体を介して配置した基本構成からなる。具体的態様としては、X電極およびY電極が、1枚の基板上の別々の面に形成される態様、1枚の基板上にX電極、絶縁体層、Y電極を上記順で形成する態様、1枚の基板上にX電極を形成し、別の基板上にY電極を形成する態様(この態様では、2枚の基板を貼り合わせた構成が上記基本構成となる)等が挙げられる。なお静電容量式タッチパネルの構成は公知であり、本発明では公知技術を何ら制限なく適用することができる。
また、図3に示すように、平坦化または、導電部材6Aおよび6Bを保護する目的で、導電部材6Aおよび導電部材6Bを覆うように透明な保護層7Aおよび保護層7Bが配置されていてもよい。
光学フィルム4Cには、後述する周辺領域S2を遮光する加飾層を形成してもよい。
透明絶縁基板5の材質としては、例えば、ガラス、PET(ポリエチレンテレフタレート)、PEN(ポリエチレンナフタレート)、COP(シクロオレフィンポリマー)、COC(シクロオレフィンポリマー)、PC(ポリカーボネート)等が使用できる。また、透明絶縁基板5の厚さは20~200μmが好ましい。
光学フィルム4Cとタッチパネル用導電フィルム1との間には、粘着層(図中で図示しない)を設けてもよく、粘着層としては、光学透明粘着シート(Optical Clear Adhesive)または光学透明粘着樹脂(Optical Clear Resin)が使用できる。粘着層の好ましい厚みは10~100μmである。光学透明粘着シートとしては、一般的には、例えば3M社製の8146シリーズが好ましく使用できる。粘着層の比誘電率の好ましい値は4.0~6.0であり、より好ましくは5.0~6.0である。
保護層7Aおよび保護層7Bとしては、例えば、ゼラチン、アクリル樹脂、ウレタン樹脂等の有機膜、および、二酸化シリコン等の無機膜を使用できる。厚みは、10nm以上100nm以下が好ましい。比誘電率は、2.5~4.5が好ましい。
保護層7Aおよび保護層7B中のハロゲン不純物の濃度は、50ppm以下であることが好ましく、ハロゲン不純物は含有しないことがより好ましい。この態様によれば、導電部材6Aおよび導電部材6Bの腐食を抑制できる。
アクティブエリアS1内には、透明絶縁基板5のおもて面(第1面)上に形成された第1導電層8と透明絶縁基板5の裏面(第2面)上に形成された第2導電層9とが互いに重なるように配置されている。なお、第1導電層8および第2導電層9は、透明絶縁基板5を介して、互いに絶縁された状態で配置されている。
透明絶縁基板5のおもて面上の第1導電層8により、それぞれ第1の方向D1に沿って延び且つ第1の方向D1に直交する第2の方向D2に並列配置された複数の第1電極11が形成され、透明絶縁基板5の裏面上の第2導電層9により、それぞれ第2の方向D2に沿って延び且つ第1の方向D1に並列配置された複数の第2電極21が形成されている。
これら複数の第1電極11および複数の第2電極21は、タッチパネル2の検出電極を構成するものである。第1電極11および第2電極21の電極幅は1~5mmが好ましく、電極間ピッチは3~6mmであることが好ましい。
同様に、周辺領域S2における透明絶縁基板5の裏面上に、複数の第2電極21に接続された複数の第2周辺配線22が形成され、透明絶縁基板5の縁部に複数の第2外部接続端子23が配列形成されると共に、それぞれの第2電極21の両端に第2コネクタ部24が形成されている。第2コネクタ部24に、対応する第2周辺配線22の一端部が接続され、第2周辺配線22の他端部は、対応する第2外部接続端子23に接続されている。
タッチパネル用導電フィルム1は、透明絶縁基板5のおもて面上に第1電極11、第1周辺配線12、第1外部接続端子13および第1コネクタ部14を含む導電部材6Aを有すると共に、透明絶縁基板5の裏面上に第2電極21、第2周辺配線22、第2外部接続端子23および第2コネクタ部24を含む導電部材6Bを有する。
第1コネクタ部14および第2コネクタ部24を設けることで、電極と周辺配線との接続箇所での電気的導通を良くすることができる効果がある。特に、電極と周辺配線の材料が異なる場合は、第1コネクタ部14および第2コネクタ部24を設けることが好ましい。第1コネクタ部14および第2コネクタ部24の幅は、それぞれ接続される電極の幅の1/3以上、電極の幅以下であることが好ましい。第1コネクタ部14および第2コネクタ部24の形状はベタ膜形状でもよいし、国際公開WO2013/089085号公報に示されているような枠形状、またはメッシュ形状でもよい。
第1周辺配線12および第2周辺配線22の配線幅は10μm以上200μm以下であり、最小配線間隔(最小配線間距離)は20μm以上100μm以下であることが好ましい。
各周辺配線は、ウレタン樹脂、アクリル樹脂、エポキシ樹脂等からなる保護絶縁膜で覆ってもよい。保護絶縁膜を設けることにより、周辺配線のマイグレーション、錆び等を防止できる。なお、周辺配線の腐食を引きこす可能性があるので、絶縁膜中にはハロゲン不純物を含有しないことが好ましい。保護絶縁膜の厚みは1~20μmが好ましい。
タッチパネル用導電フィルム1をタッチパネルとして使用する場合、第1外部接続端子13と第2外部接続端子23とは異方性導電フィルム(Anisotropic Conductive Film)を介してフレキブル配線基板(Flexible Printed Circuits)と電気的に接続される。フレキシブル配線基板は、駆動機能と位置検出機能とを有するタッチパネル制御基板に接続される。
第1外部接続端子13と第2外部接続端子23はフレキシブル配線基板との電気接続性を良くする目的で、第1周辺配線12および第2周辺配線22の配線幅より大きい端子幅で形成される。具体的には、第1外部接続端子13と第2外部接続端子23の端子幅は0.1mm以上0.6mm以下が好ましく、端子長さは0.5mm以上2.0mm以下が好ましい。
メッシュパターンの形状としては、図5のような同一のメッシュ(定形セル)が繰り返し配置されたパターンが好ましく、メッシュの形状はひし形が特に好ましいが、平行四辺形、正方形、長方形等の四角形でも良く、正六角形や他の多角形であっても良い。ひし形の場合、そのひし形の狭角角度は20°以上70°以下であることが表示装置の画素とのモアレ低減の観点から好ましい。メッシュの中心間距離(メッシュピッチ)は100~600μmであることが視認性の観点から好ましい。第1金属細線15からなるメッシュパターンM1と第2金属細線25からなるメッシュパターンM2が同一形状であることが好ましい。さらに、図5のように、第1金属細線15からなるメッシュパターンM1と第2金属細線25からなるメッシュパターンM2とを、メッシュピッチ半分相当の距離だけずらして配置し、視認側からはメッシュピッチが半分になるメッシュパターンを形成するように配置することが、視認性の観点から好ましい。別の形態としては、メッシュの形状はランダムなパターン、または特開2013-214545号公報に示されているようなひし形の定形セルのピッチに10%程度のランダム性を付与するような、定形セル形状にある一定のランダム性を付与したセミランダム形状であっても良い。
また、互いに隣り合う第1電極11の間、互いに隣り合う第2電極21の間に、それぞれ第1金属細線15、第2金属細線25で形成された電極と絶縁されたダミーメッシュパターンを有していてもよい。ダミーメッシュパターンは、電極を形成するメッシュパターンと同一のメッシュ形状で形成することが好ましい。
ダイレクトボンディング方式に使用される透明な粘着剤は前述の透明な粘着層と同じく、光学透明粘着シート(Optical Clear Adhesive)または光学透明粘着樹脂(Optical Clear Resin)が使用でき、好ましい厚みは10μm以上100μm以下である。光学透明粘着シートとしては、例えば同じく3M社製の8146シリーズが好ましく使用できる。ダイレクトボンディング方式に使用される透明な粘着剤の比誘電率は、前述の透明な粘着層の比誘電率より小さいものを使用することがタッチパネル2の検出感度を向上させる点で好ましい。ダイレクトボンディング方式に使用される透明な粘着剤の比誘電率の好ましい値は、2.0~3.0である。
上記可視光反射率の測定方法としては、以下のようにして測定する。先ず、日本分光社製紫外可視分光光度計V660(1回反射測定ユニットSLM-721)を使用し、測定波長350nmから800nm、入射角5度で反射スペクトルを測定する。なお、アルミ蒸着平面鏡の正反射光をベースラインとする。得られた反射スペクトルからXYZ表色系D65光源2度視野のY値(等色関数JIS Z9701-1999)を、日本分光社製色彩計算プログラムを用いて計算し、可視光反射率とする。
第1金属細線15を構成する材料で、第1電極11、第1周辺配線12、第1外部接続端子13および第1コネクタ部14を含む導電部材6Aを形成することができる。よって、第1電極11、第1周辺配線12、第1外部接続端子13および第1コネクタ部14を含む導電部材6Aはすべて同じ金属で同じ厚みで形成され、同時形成することができる。
第2電極21、第2周辺配線22、第2外部接続端子23および第2コネクタ部24を含む導電部材6Bに関しても同様である。
なお、第1電極11と隣接する第1ダミー電極11Aとは、連続的な第1メッシュパターンM1に沿って配置された金属細線に幅5μm以上30μm以下の断線を設けることにより、電気的に絶縁している。図6は、第1電極11と隣接する第1ダミー電極11Aとの境界線のみに断線を形成した形状であるが、第1ダミー電極11A内の第1セルC1の辺の全てに、または部分的に断線を形成してもよい。
また、図示しないが、アクティブエリアS1内における透明絶縁基板5の裏面上に配置されている第2導電層9は、複数の第2電極21の間にそれぞれ配置された複数の第2ダミー電極を有していてもよい。これらの第2ダミー電極は、複数の第2電極21から絶縁されており、第2電極21と同様に、多数の第2セルC2で構成された第2メッシュパターンM2を有している。
なお、第2電極21と隣接する第2ダミー電極とは、連続的な第2メッシュパターンM2に沿って配置された金属細線に幅5μm以上30μm以下の断線を設けることにより、電気的に絶縁している。第2電極21と隣接する第1ダミー電極との境界線のみに断線を形成した形状でもよいが、第2ダミー電極内の第2セルC2の辺の全てに、または部分的に断線を形成してもよい。
このとき、第1電極11は、第1メッシュパターンM1に沿って第1金属細線15が配置された第1導電層8からなり、第2電極21は、第2メッシュパターンM2に沿って第2金属細線25が配置された第2導電層9からなり、第1導電層8と第2導電層9とが透明絶縁基板5を挟んで図4のようにアクティブエリアS1内で互いに重なるように配置されるものとする。
これら導電部材6Aおよび導電部材6Bの形成方法は、特に限定されるものではない。例えば、特開2012-185813号公報の<0067>~<0083>、特開2014-209332号公報の<0115>~<0126>、または、特開2015-5495号公報の<0216>~<0215>に記載されているように感光性ハロゲン化銀塩を含有する乳剤層を有する感光材料を露光し、現像処理を施すことによって、導電部材6Aおよび6Bを形成することができる。
例えば、透明絶縁基板5の一方の面側に、導電部材6Aと導電部材6Bが層間絶縁膜を介して配置される構成とすることもできる。
さらに、2枚基板の構成とすることもできる。すなわち、第1透明絶縁基板の表面上に導電部材6Aを配置し、第2透明絶縁基板の表面上に導電部材6Bを配置し、これら第1透明絶縁基板および第2透明絶縁基板を、光学透明粘着シート(Optical Clear Adhesive)を用いて貼り合わせて使用することもできる。
さらに、透明絶縁基板5を用いずに、図3に示した光学フィルム4Cの表面上に導電部材6Aと導電部材6Bが層間絶縁膜を介して配置される構成としてもよい。
また、US2012/0262414号公報等に開示されている交差部がない電極構成のように検出電極が基板の片側にしかない構成のタッチパネルにも適用できる。
さらに、タッチパネルは他の機能フィルムとの組合せとの使用も可能である、特開2014-13264号公報に開示されている高レタレーション値を有する基板を用いたニジムラを防止する画像品位向上用機能フィルム、特開2014-142462号公報に開示されているタッチパネルの電極の視認性改善の為の円偏光板との組合せ等も可能である。
本発明の光学フィルムは、一方の樹脂フィルムの、接着層を有する面とは反対側の面に、反射層(直線偏光反射層または円偏光反射層)を有してもよい。かかる光学フィルムは、画像表示素子と組み合わせることにより、画像表示機能付きミラーの前面板に用いられる光学フィルムとして好ましく用いられる。本発明の光学フィルムと反射層との間には、粘着層を設けてもよく、粘着層としては、光学透明粘着シート(Optical Clear Adhesive)または光学透明粘着樹脂(Optical Clear Resin)が使用できる。
本明細書において、画像表示機能付きミラーの前面板に用いられる、直線偏光反射層または円偏光反射層を有する光学フィルムを「ハーフミラー」と称することがある。
湾曲は、上下方向、左右方向、または上下方向および左右方向にあればよい。また、湾曲は、曲率半径が500~3000mmであればよく、1000~2500mmであることがより好ましい。曲率半径は、断面で湾曲部分の外接円を仮定した場合の、この外接円の半径である。
反射層としては、半透過半反射層として機能できる反射層を用いればよい。すなわち、反射層は、画像表示時には、画像表示素子が備える光源からの出射光を透過させることにより、画像表示機能付きミラーの前面に画像が表示されるように機能し、一方で、画像非表示時には、反射層は、前面方向からの入射光の少なくとも一部を反射するとともに、画像表示素子からの反射光を透過させ、画像表示機能付きミラーの前面がミラーとなるように機能するものであればよい。
反射層としては、偏光反射層が用いられる。偏光反射層は、直線偏光反射層または円偏光反射層であればよい。
直線偏光反射層としては、例えば、(i)多層構造の直線偏光反射板、(ii)複屈折の異なる薄膜を積層してなる偏光子、(iii)ワイヤーグリッド型偏光子、(iv)偏光プリズムおよび(v)散乱異方性型偏光板が挙げられる。
誘電体薄膜の成膜方法としては、特に制限はなく、目的に応じて適宜選択することができ、例えば、イオンプレーティングおよびイオンビーム等の真空蒸着法、スパッタリング等の物理的気相成長法(PVD法)ならびに化学的気相成長法(CVD法)が挙げられる。これらの中でも、真空蒸着法またはスパッタリング法が好ましく、スパッタリング法が特に好ましい。
複屈折の異なる薄膜を積層した偏光子としては、市販品を用いることができ、市販品としては、例えば、DBEF(登録商標)(3M社製)が挙げられる。
ワイヤーグリッド偏光子は、金属ワイヤーを周期的に配列したもので、テラヘルツ波帯域で主に偏光子として用いられる。ワイヤーグリッドが偏光子として機能するためには、ワイヤー間隔が入射電磁波の波長よりも十分小さいことが必要となる。
ワイヤーグリッド偏光子では、金属ワイヤーが等間隔に配列されている。金属ワイヤーの長手方向と平行な偏光方向の偏光成分はワイヤーグリッド偏光子において反射され、垂直な偏光方向の偏光成分はワイヤーグリッド偏光子を透過する。
ハーフミラーに円偏光反射層を用いることにより、前面側からの入射光を円偏光として反射させ、画像表示素子からの入射光を円偏光として透過させることができる。そのため、円偏光反射層を用いた画像表示機能付きミラーでは、偏光サングラスを介しても、画像表示機能付きミラーの方向に依存せずに、表示画像およびミラー反射像の観察を行うことができる。
Polλ/4円偏光反射層において、直線偏光反射板と1/4波長板とは直線偏光反射板の偏光反射軸に対しλ/4波長板の遅相軸が45°となるように配置されていればよい。また、1/4波長板と直線偏光反射板とは、例えば、接着層により接着されていればよい。
Polλ/4円偏光反射層において、直線偏光反射板が画像表示素子に近い面となるように配置して使用する、つまり、光学フィルムに対し1/4波長板および直線偏光反射板をこの順に配置して使用することで、画像表示素子からの画像表示のための光を効率よく円偏光に変換して、画像表示機能付きミラー前面から出射させることができる。画像表示素子からの画像表示のための光が直線偏光であるとき、この直線偏光を透過するように直線偏光反射板の偏光反射軸を調整すればよい。
Polλ/4円偏光反射層の厚みは2.0μm~300μmの範囲が好ましく、8.0μm~200μmの範囲がより好ましい。
直線偏光反射板としては、上記で直線偏光反射層として説明したものを用いることができる。
1/4波長板としては、後述する1/4波長板を用いることができる。
コレステリック円偏光反射層は、コレステリック液晶層を少なくとも1層含む。コレステリック円偏光反射層に含まれるコレステリック液晶層は可視光領域で選択反射を示すものであればよい。
円偏光反射層は2層以上のコレステリック液晶層を含んでいてもよく、配向層などの他の層を含んでいてもよい。円偏光反射層はコレステリック液晶層のみからなることが好ましい。また、円偏光反射層が複数のコレステリック液晶層を含むときは、それらは隣接するコレステリック液晶層と直接接していることが好ましい。円偏光反射層は、3層および4層など、3層以上のコレステリック液晶層を含んでいることが好ましい。
コレステリック円偏光反射層の厚みは、2.0μm~300μmの範囲が好ましく、8.0~200μmの範囲がより好ましい。
コレステリック液晶相は、特定の波長域において右円偏光または左円偏光のいずれか一方のセンスの円偏光を選択的に反射させるとともに他方のセンスの円偏光を選択的に透過する円偏光選択反射を示すことが知られている。本明細書において、円偏光選択反射を単に選択反射ということもある。
分光光度計UV3150(島津製作所社製、商品名)を用いて反射層の透過スペクトル(コレステリック液晶層の法線方向から測定したもの)を測定すると、選択反射領域に透過率の低下ピークがみられる。この最も大きいピーク高さの1/2の高さの透過率となる2つの波長のうち、短波長側の波長の値をλ1(nm)、長波長側の波長の値をλ2(nm)とすると、選択反射の中心波長と半値幅は下記式で表すことができる。
選択反射の中心波長=(λ1+λ2)/2
半値幅=(λ2-λ1)
上記のように求められる、コレステリック液晶層が有する選択反射の中心波長λは、コレステリック液晶層の法線方向から測定した円偏光反射スペクトルの反射ピークの重心位置にある波長と通常一致する。なお、本明細書において、「選択反射の中心波長」はコレステリック液晶層の法線方向から測定した時の中心波長を意味する。
上記式から分かるように、螺旋構造のピッチを調節することによって、選択反射の中心波長を調整できる。n値とP値を調節することにより、所望の波長の光に対して右円偏光または左円偏光のいずれか一方を選択的に反射させるための、中心波長λを調節することができる。
λd=n2×P×cosθ2
赤外光領域に選択反射の中心波長を有するコレステリック液晶層を設ける場合は、可視光領域に選択反射の中心波長をそれぞれ有するコレステリック液晶層すべてに対し、最も画像表示素子側にあることが好ましい。
選択反射の中心波長が同一の1種のコレステリック液晶層の形成のために、周期Pが同じで、同じ螺旋のセンスのコレステリック液晶層を複数積層してもよい。周期Pが同じで、同じ螺旋のセンスのコレステリック液晶層を積層することによっては、特定の波長での円偏光選択性を高くすることができる。
コレステリック円偏光反射層を用いた画像表示機能付きミラーにおいて、ハーフミラーはさらに1/4波長板を含んでいてもよく、高Re(面内レタデーション)位相差膜と、コレステリック円偏光反射層と、1/4波長板とをこの順に含むことが好ましい。
画像表示素子とコレステリック円偏光反射層との間に1/4波長板を含むことによって、特に、直線偏光により画像表示している画像表示素子からの光を円偏光に変換してコレステリック円偏光反射層に入射させることが可能となる。そのため、円偏光反射層において反射されて画像表示素子側に戻る光を大幅に減らすことができ、明るい画像の表示が可能となる。また、1/4波長板の利用によりコレステリック円偏光反射層において画像表示素子側に反射するセンスの円偏光を生じさせない構成が可能であるため、画像表示素子およびハーフミラーの間の多重反射による画像表示品質の低下が生じにくい。
すなわち、例えば、コレステリック円偏光反射層に含まれるコレステリック液晶層の選択反射の中心波長が、画像表示素子の白表示時の発光スペクトルにおける青色光の発光ピーク波長と略同一(例えば差異が5nm未満)であったとしても、円偏光反射層において画像表示側に反射するセンスの円偏光を生じさせることなく、画像表示素子の出射光を前面側に透過させることができる。
前者の1/4波長板の正面位相差は、画像表示素子の発光波長の1/4の長さであればよい。それゆえ、例えば画像表示素子の発光波長が450nm、530nmおよび640nmの場合は、450nmの波長で112.5nm±10nm、好ましくは112.5nm±5nm、より好ましくは112.5nm、530nmの波長で132.5nm±10nm、好ましくは132.5nm±5nm、より好ましくは132.5nm、640nmの波長で160nm±10nm、好ましくは160nm±5nm、より好ましくは160nmの位相差であるような逆分散性の位相差層が、1/4波長板として最も好ましいが、位相差の波長分散性の小さい位相差板や順分散性の位相差板も用いることができる。なお、「逆分散性」とは長波長になるほど位相差の絶対値が大きくなる性質を意味し、「順分散性」とは短波長になるほど位相差の絶対値が大きくなる性質を意味する。
λ/4波長板としては、市販品を用いることもでき、市販品としては、例えば、ピュアエース(登録商標) WR(帝人株式会社製ポリカーボネートフィルム)が挙げられる。
λ/4波長板はコレステリック円偏光反射層と、直接接していてもよく、接着層により接着されていてもよく、直接接していることが好ましい。
以下、コレステリック液晶層および液晶組成物から形成される1/4波長板の作製材料および作製方法について説明する。
上記1/4波長板の形成に用いる材料としては、重合性液晶化合物を含む液晶組成物などが挙げられる。上記コレステリック液晶層の形成に用いる材料としては、重合性液晶化合物と、さらにキラル剤(光学活性化合物)とを含む液晶組成物などが挙げられる。必要に応じてさらに界面活性剤や重合開始剤などと混合して溶媒などに溶解した上記液晶組成物を、仮支持体、支持体、配向膜、高Re位相差膜、下層となるコレステリック液晶層、または1/4波長板などに塗布し、配向熟成後、液晶組成物の硬化により固定化してコレステリック液晶層および/または1/4波長板を形成することができる。
重合性液晶化合物としては、重合性の棒状液晶化合物を用いればよい。
重合性の棒状液晶化合物の例としては、棒状ネマチック液晶化合物が挙げられる。棒状ネマチック液晶化合物としては、アゾメチン類、アゾキシ類、シアノビフェニル類、シアノフェニルエステル類、安息香酸エステル類、シクロヘキサンカルボン酸フェニルエステル類、シアノフェニルシクロヘキサン類、シアノ置換フェニルピリミジン類、アルコキシ置換フェニルピリミジン類、フェニルジオキサン類、トラン類およびアルケニルシクロヘキシルベンゾニトリル類が好ましく用いられる。低分子液晶化合物だけではなく、高分子液晶化合物も用いることができる。
コレステリック液晶層の形成に用いる材料はキラル剤を含んでいることが好ましい。キラル剤はコレステリック液晶相の螺旋構造を誘起する機能を有する。キラル剤は、化合物によって誘起する螺旋のセンスまたは螺旋ピッチが異なるため、目的に応じて選択すればよい。
キラル剤としては、特に制限はなく、通常用いられる化合物(例えば、液晶デバイスハンドブック、第3章4-3項、TN、STN用カイラル剤、199頁、日本学術振興会第142委員会編、1989に記載)、イソソルビドおよびイソマンニド誘導体を用いることができる。
キラル剤は、一般に不斉炭素原子を含むが、不斉炭素原子を含まない軸性不斉化合物あるいは面性不斉化合物もキラル剤として用いることができる。軸性不斉化合物または面性不斉化合物の例には、ビナフチル、ヘリセン、パラシクロファンおよびこれらの誘導体が含まれる。キラル剤は、重合性基を有していてもよい。キラル剤と液晶化合物とがいずれも重合性基を有する場合は、重合性キラル剤と重合性液晶化合物との重合反応により、重合性液晶化合物から誘導される繰り返し単位と、キラル剤から誘導される繰り返し単位とを有するポリマーを形成することができる。この態様では、重合性キラル剤が有する重合性基は、重合性液晶化合物が有する重合性基と、同種の基であることが好ましい。従って、キラル剤の重合性基も、不飽和重合性基、エポキシ基またはアジリジニル基であることが好ましく、不飽和重合性基であることがさらに好ましく、エチレン性不飽和重合性基であることが特に好ましい。
また、キラル剤は、液晶化合物であってもよい。
本発明に用いられる液晶組成物は、重合開始剤を含有していることが好ましい。紫外線照射により重合反応を進行させる態様では、使用する重合開始剤は、紫外線照射によって重合反応を開始可能な光重合開始剤であることが好ましい。光重合開始剤の例には、α-カルボニル化合物(米国特許第2367661号、米国特許第2367670号の各明細書記載)、アシロインエーテル(米国特許第2448828号明細書記載)、α-炭化水素置換芳香族アシロイン化合物(米国特許第2722512号明細書記載)、多核キノン化合物(米国特許第3046127号、米国特許第2951758号の各明細書記載)、トリアリールイミダゾールダイマーとp-アミノフェニルケトンとの組み合わせ(米国特許第3549367号明細書記載)、アクリジンおよびフェナジン化合物(特開昭60-105667号公報、米国特許第4239850号明細書記載)、アシルフォスフィンオキシド化合物(特公昭63-40799号公報、特公平5-29234号公報、特開平10-95788号公報、特開平10-29997号公報記載)、オキシム化合物(特開2000-66385号公報、日本特許第4454067号明細書記載)、ならびにオキサジアゾール化合物(米国特許第4212970号明細書記載)等が挙げられる。
液晶組成物中の光重合開始剤の含有量は、重合性液晶化合物量に対して0.1~20質量%であることが好ましく、0.5質量%~5質量%であることがさらに好ましい。
液晶組成物は、硬化後の膜強度向上、耐久性向上のため、任意に架橋剤を含有していてもよい。架橋剤としては、紫外線、熱、湿気等で硬化するものが好適に使用できる。
架橋剤としては、特に制限はなく、目的に応じて適宜選択することができ、例えばトリメチロールプロパントリ(メタ)アクリレートおよびペンタエリスリトールトリ(メタ)アクリレート等の多官能アクリレート化合物;グリシジル(メタ)アクリレートおよびエチレングリコールジグリシジルエーテル等のエポキシ化合物;2,2-ビスヒドロキシメチルブタノール-トリス[3-(1-アジリジニル)プロピオネート]および4,4-ビス(エチレンイミノカルボニルアミノ)ジフェニルメタン等のアジリジン化合物;ヘキサメチレンジイソシアネートおよびビウレット型イソシアネート等のイソシアネート化合物;オキサゾリン基を側鎖に有するポリオキサゾリン化合物;ならびにビニルトリメトキシシランおよびN-(2-アミノエチル)3-アミノプロピルトリメトキシシラン等のアルコキシシラン化合物が挙げられる。また、架橋剤の反応性に応じて通常用いられる触媒を用いることができ、膜強度および耐久性向上に加えて生産性を向上させることができる。これらは、1種単独で使用してもよいし、2種以上を併用してもよい。
液晶組成物における架橋剤の含有量は3質量%~20質量%が好ましく、5質量%~15質量%がより好ましい。架橋剤の含有量が、上記下限値以上であることにより、架橋密度向上の効果を得ることができる。また、上記上限値以下とすることにより、形成される層の安定性を維持することができる。
液晶組成物中には、安定的にまたは迅速にプレーナー配向とするために寄与する配向制御剤を添加してもよい。配向制御剤の例としては特開2007-272185号公報の段落〔0018〕~〔0043〕等に記載のフッ素(メタ)アクリレート系ポリマーならびに特開2012-203237号公報の段落〔0031〕~〔0034〕等に記載の式(I)~(IV)で表される化合物などが挙げられる。
なお、配向制御剤としては1種を単独で用いてもよいし、2種以上を併用してもよい。
その他、液晶組成物は、塗膜の表面張力を調整し厚みを均一にするための界面活性剤、および重合性モノマー等の種々の添加剤から選ばれる少なくとも1種を含有していてもよい。また、液晶組成物中には、必要に応じて、さらに重合禁止剤、酸化防止剤、紫外線吸収剤、光安定化剤、色材、金属酸化物微粒子等を、光学的性能を低下させない範囲で添加することができる。
液晶組成物の調製に使用する溶媒としては、特に制限はなく、目的に応じて適宜選択することができるが、有機溶媒が好ましく用いられる。
有機溶媒としては、特に制限はなく、目的に応じて適宜選択することができ、例えばケトン類、アルキルハライド類、アミド類、スルホキシド類、ヘテロ環化合物、炭化水素類、エステル類およびエーテル類が挙げられる。これらは、1種単独で使用してもよいし、2種以上を併用してもよい。これらの中でも、環境への負荷を考慮した場合にはケトン類が特に好ましい。
仮支持体、配向膜、高Re位相差膜、1/4波長板、及び/又は下層となるコレステリック液晶層などへの液晶組成物の塗布方法は、特に制限はなく、目的に応じて適宜選択することができ、例えば、ワイヤーバーコーティング法、カーテンコーティング法、押し出しコーティング法、ダイレクトグラビアコーティング法、リバースグラビアコーティング法、ダイコーティング法、スピンコーティング法、ディップコーティング法、スプレーコーティング法およびスライドコーティング法などが挙げられる。また、別途支持体上に塗設した液晶組成物を転写することによっても実施できる。塗布した液晶組成物を加熱することにより、液晶分子を配向させる。コレステリック液晶層形成の際はコレステリック配向させればよく、1/4波長板形成の際は、ネマチック配向させることが好ましい。コレステリック配向の際、加熱温度は、200℃以下が好ましく、130℃以下がより好ましい。この配向処理により、重合性液晶化合物が、フィルム面に対して実質的に垂直な方向に螺旋軸を有するように捩れ配向している光学薄膜が得られる。ネマチック配向の際、加熱温度は、25℃~120℃が好ましく、30℃~100℃がより好ましい。
<1.樹脂フィルムの作製>
(1)コア層セルロースアシレートドープ液の調製
下記の組成物をミキシングタンクに投入して撹拌し、コア層セルロースアシレートドープ溶液を調製した。
コア層セルロースアシレートドープ液
・アセチル置換度2.88、重量平均分子量260,000のセルロースアセテート 100質量部
・下記構造のフタル酸エステルオリゴマーA 10質量部
・下記式Iで表される化合物(A-1) 4質量部
・下記式IIで表される紫外線吸収剤(BASF社製) 2.7質量部
・光安定剤(BASF社製、商品名:TINUVIN123) 0.18質量部
・N-アルケニルプロピレンジアミン3酢酸(ナガセケムテックス社製、商品名:テークランDO) 0.02質量部
・メチレンクロライド(第1溶媒) 430質量部
・メタノール(第2溶媒) 64質量部
フタル酸エステルオリゴマーA(重量平均分子量:750)
式I:
式II:
上記のコア層セルロースアシレートドープ液90質量部に下記の無機粒子含有組成物を10質量部加え、外層セルロースアシレートドープ液を調製した。
無機粒子含有組成物
・平均一次粒径20nmのシリカ粒子(日本アエロジル社製、商品名:AEROSIL R972) 2質量部
・メチレンクロライド(第1溶媒) 76質量部
・メタノール(第2溶媒) 11質量部
・コア層セルロースアシレートドープ液 1質量部
外層セルロースアシレートドープ液がコア層セルロースアシレートドープ液の両側に配されるように、外層セルロースアシレートドープ液、コア層セルロースアシレートドープ液、および外層セルロースアシレートドープ液の3種を、流延口から表面温度20℃の流延バンド上に同時に流延した。
流延バンドとして幅2.1mで長さが70mのステンレス製のエンドレスバンドを利用した。流延バンドは、厚みが1.5mm、表面粗さが0.05μm以下になるように研磨した。その材質はSUS316製であり、十分な耐腐食性と強度を有する流延バンドを用いた。流延バンドの全体の厚みムラは0.5%以下であった。
得られた流延膜に、風速が8m/s、ガス濃度が16%、温度が60℃の急速乾燥風を流延膜表面に当てて初期膜を形成した。その後、流延バンド上部の上流側からは140℃の乾燥風を送風した。また下流側からは120℃の乾燥風および60℃の乾燥風を送風した。
残留溶媒量を約33質量%にした後、バンドから剥ぎ取った。次いで、得られたフィルムの幅方向の両端をテンタークリップで固定し、溶媒残留量が3~15質量%のフィルムを、横方向に1.06倍延伸しつつ乾燥した。その後、熱処理装置のロール間を搬送することにより、更に乾燥し、厚みが100μm(外層/コア層/外層=3μm/94μm/3μm)である第一の樹脂フィルム(A)を作製した。
第一の樹脂フィルム(A)と同様の作製方法で、厚みが100μmである第二の樹脂フィルム(C)を作製した。
作製した樹脂フィルム(A)および(C)を、液温55℃に保った1.5mol/LのNaOH水溶液(ケン化液)に2分間浸漬した後、フィルムを水洗し、その後、液温25℃の0.05mol/Lの硫酸水溶液に30秒浸漬した後、更に30秒流水下に通して水洗し、フィルムを中性の状態にした。そして、エアナイフによる水切りを3回繰り返し、水を落とした後に雰囲気温度70℃の乾燥ゾーンに15秒間滞留させて乾燥し、ケン化処理した樹脂フィルム(A)および(C)を作製した。
以降、光学フィルムの作製においては、ケン化処理した樹脂フィルム(A)および(C)を単に樹脂フィルム(A)および(C)と称す。
<3.接着層形成用液の調整>
下記表1に示す、接着層(B)形成用液A-1~A-11を使用し、以下に示す方法での樹脂フィルム(A)および(C)を貼り合わせた。
貼り合わせにおける各工程の詳細と、使用した化合物の説明を以下に示す。
表1に記載した各化合物の詳細を以下に示す。
PVA-117H:クラレポバールPVA-117H(商品名、クラレ社製)、ポリビニルアルコール
ゴーセネックス Z410:商品名(日本合成化学社製)、アセトアセチル変性ポリビニルアルコール
HEC:ヒドロキシエチルセルロース、重量平均分子量74,000
SPM-01:Safelink SPM-01(商品名、日本合成化学社製)、架橋剤
上記表1に示す組成で各成分を混合し、孔径10μmのポリプロピレン製フィルターでろ過して、接着層形成用液A-1~A-11を調製した。
樹脂フィルム(A)のバンド側と接していた面に、上記で作製した接着層形成用液A-1を乾燥後の接着層(B)の厚みが1μmとなるように塗布した。次いで、樹脂フィルム(C)のバンド側と接していた面と上述の接着層(B)とを、ロール機で圧力3MPa、速度900rpmの条件で貼り合わせ、雰囲気温度70℃で10分以上乾燥して、樹脂フィルム(A)および(C)が接着層(B)で貼り合わされた積層体を作製した。
<ハードコート層の付与>
ハードコート層付き積層体の作製における各工程の詳細と、使用した化合物の説明を以下に示す。
表2に記載した各化合物の詳細を以下に示す。
DPHA:ジペンタエリスリトールペンタアクリレートとジペンタエリスリトールヘキサアクリレートの混合物(日本化薬社製、商品名:KAYARAD DPHA)
サイクロマーM100:3,4-エポキシシクロヘキシルメチルメタクリレート(ダイセル社製、商品名)
Irg184:1-ヒドロキシ-シクロヘキシル-フェニル-ケトン(α-ヒドロキシアルキルフェノン系のラジカル光重合開始剤、BASF社製、商品名:IRGACURE184)
PAG-1:以下に示すヨードニウム塩化合物であるカチオン光重合開始剤
RS-90:防汚剤、DIC社製、ラジカル重合性基を有する含フッ素オリゴマー
P-112:レベリング剤、特許5175831号の段落0053に記載の化合物P-112
MEK:メチルエチルケトン
MIBK:メチルイソブチルケトン
上記表2に示す組成で各成分を混合し、孔径10μmのポリプロピレン製フィルターでろ過して、HC層形成用硬化性組成物HC-1およびHC-2を調製した。
作製した積層体の、接着層(B)とは逆側の樹脂フィルム(A)の表面上に、HC層形成用硬化性組成物HC-1を塗布し、硬化させてハードコート層を形成した。
塗布および硬化の方法は、具体的には、次の通りとした。特開2006-122889号公報の実施例1記載のスロットダイを用いたダイコート法で、搬送速度30m/分の条件でHC層形成用硬化性組成物を塗布し、雰囲気温度60℃で150秒間乾燥した。その後、更に窒素パージ下、酸素濃度約0.1体積%で160W/cmの空冷メタルハライドランプ(アイグラフィックス社製)を用いて、照度20mW/cm2、照射量30mJ/cm2の紫外線を照射して、塗布したHC層形成用硬化性組成物を硬化させてハードコート層HC-1を形成した後、巻き取りを行った。
接着層形成用液A-1に代えて接着層形成用液A-2~A-8を使用した以外は実施例1と同様にして、実施例2~8の光学フィルムを作製した。
樹脂フィルム(A)および(C)に代えて、下記のように作製したPET系樹脂フィルムを使用した以外、実施例2と同様の方法で、実施例9の光学フィルムを作製した。
<PET系樹脂フィルムの作製>
(1)易接着層形成用組成物の調製
(1-1)ポリエステル系樹脂の調製
下記組成の重合性化合物を共重合したポリエステル系樹脂のスルホン酸系水分散体を得た。
(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/ジエチレングリコール=44/46/10//84/16(モル比)
撹拌器、温度計、還流冷却管、窒素吹き込み管を取り付けた4ツ口フラスコ(反応器)内を窒素雰囲気にし、ここに、HDI(ヘキサメチレンジイソシアネート)1000質量部、3価アルコールであるトリメチロールプロパン(分子量134)22質量部を仕込み、反応器内の反応液温度を90℃に保持しながら1時間撹拌し、ウレタン化を行った。その後、反応液温度を60℃に保持し、イソシアヌレート化触媒であるトリメチルベンジルアンモニウム・ハイドロオキサイドを加え、イソシアヌレートへの転化率が48%になった時点でリン酸を添加し反応を停止した。次いで、反応液を濾過した後、未反応のHDIを薄膜蒸留装置により除去し、イソシアネート系化合物aを得た。
得られたイソシアネート系化合物aの25℃における粘度は25,000mPa・s、イソシアネート基含有量は19.9質量%、数平均分子量は1080、イソシアネート基平均数は5.1であった。NMR(Nuclear Magnetic Resonance)測定により、ウレタン結合、アロファネート結合、イソシアヌレート結合の存在を確認した。
撹拌器、温度計、還流冷却管、窒素吹き込み管、滴下ロートを取り付けた4ツ口フラスコ(反応器)内を窒素雰囲気にし、ここに、上記で得られたイソシアネート系化合物a 100質量部、数平均分子量400のメトキシポリエチレングリコール42.3質量部、ジプロピレングリコールジメチルエーテル76.6質量部を仕込み、反応液温度80℃で6時間保持した。その後、反応液温度を60℃に冷却し、マロン酸ジエチル72質量部、ナトリウムメチラートの28質量%メタノール溶液0.88質量部を添加し、4時間保持した後、2-エチルヘキシルアシッドホスフェート0.86質量部を添加した。次いで、ジイソプロピルアミン43.3質量部を添加し、反応液温度70℃で5時間保持した。この反応液をガスクロマトグラフで分析し、ジイソプロピルアミンの反応率が70%であることを確認し、イソシアネート系化合物Aを得た(固形分濃度70質量%、有効NCO基質量5.3質量%)。
ケン化度77%、重合度600のカルボン酸変性ポリビニルアルコール樹脂(クラレ社製)57.6質量部、上記で作製したポリエステル系樹脂28.8質量部(固形分)、上記で作製したイソシアネート系化合物A 4.0質量部、有機スズ系化合物(第1工業製薬製エラストロンCat・21)0.7質量部、平均一次粒径80nmのシリカゾル8.1質量部を混合し、固形分が8.9質量部になるよう水で希釈し、易接着層形成用組成物を調製した。
(2-1)原料ポリエステル1の調製
以下に示すように、テレフタル酸およびエチレングリコールを直接反応させて水を留去し、エステル化した後、減圧下で重縮合を行う直接エステル化法を用いて、連続重合装置により原料ポリエステル1(Sb触媒系PET)を得た。
(2-1-1)エステル化反応
高純度テレフタル酸4.7トンとエチレングリコール1.8トンを90分かけて混合してスラリー形成させ、3800kg/hの流量で連続的に第1エステル化反応槽に供給した。更に3酸化アンチモンのエチレングリコール溶液を連続的に供給し、撹拌下、反応槽内温度250℃、平均滞留時間約4.3時間で反応を行なった。このとき、3酸化アンチモンはSb添加量が元素換算値で150質量ppm(mass parts per million)となるように連続的に添加した。
この反応物を第2エステル化反応槽に移送し、撹拌下、反応槽内温度250℃で、平均滞留時間で1.2時間反応させた。第2エステル化反応槽には、酢酸マグネシウムのエチレングリコール溶液と、リン酸トリメチルのエチレングリコール溶液を、Mg添加量およびP添加量が元素換算値でそれぞれ65質量ppm、35質量ppmになるように連続的に供給した。
(2-1-2)重縮合反応
上記で得られたエステル化反応生成物を連続的に第1重縮合反応槽に供給し、撹拌下、反応温度270℃、反応槽内圧力20torr(2.67×10-4MPa、1Torrは約133.3224Pa)で、平均滞留時間約1.8時間で重縮合させた。
更に、第2重縮合反応槽に移送し、撹拌下、反応槽内温度276℃、反応槽内圧力5torr(6.67×10-4MPa)で滞留時間約1.2時間の条件で反応(重縮合)させた。
次いで、更に第3重縮合反応槽に移送し、反応槽内温度278℃、反応槽内圧力1.5torr(2.0×10-4MPa)で、滞留時間1.5時間の条件で反応(重縮合)させ、反応物(ポリエチレンテレフタラート(PET))を得た。
(2-1-3)原料ポリエステル1の調製
次に、得られた反応物を、冷水にストランド状に吐出し、直ちにカッティングしてポリエステルのペレット<断面:長径約4mm、短径約2mm、長さ:約3mm>を作製した。得られたポリマーは、IV(Intrinsic Viscosity;固有粘度)=0.63dL/gであった。このポリマーを原料ポリエステル1とした。
乾燥させた紫外線吸収剤(2,2’-(1,4-フェニレン)ビス(4H-3,1-ベンズオキサジン-4-オン))10質量部、原料ポリエステル1(IV=0.63dL/g)90質量部を混合し、混練押出機を用い、原料ポリエステル1の作製と同様にしてペレット化して、紫外線吸収剤を含有する原料ポリエステル2を得た。
(2-3)PETフィルムの作製
3層構成(第I層/第II層/第III層)のポリエステル系樹脂フィルム(積層フィルム)を、以下の方法で作製した。
以下に示す第II層用組成物を、含水率が20質量ppm以下となるまで乾燥させた後、直径50mmの1軸混練押出機のホッパーに投入し、押出機で300℃に溶融することにより、第I層と第III層との間に位置する第II層を形成するための樹脂溶融物を調製した。
第II層用組成物
・原料ポリエステル1 90質量部
・紫外線吸収剤(2,2’-(1,4-フェニレン)ビス(4H-3,1-ベンズオキサジン-4-オン))10質量部を含有した原料ポリエステル2 10質量部
原料ポリエステル1を、含水率が20質量ppm以下となるまで乾燥させた後、直径30mmの1軸混練押出機のホッパーに投入し、押出機で300℃に溶融することにより、第I層および第III層を形成するための樹脂溶融物を調製した。
これらの2種の樹脂溶融物を、それぞれギアポンプ、濾過器(孔径20μm)に通した後、2種3層合流ブロックにて、第II層用押出機から押出された樹脂溶融物が内部の層に、第I層用および第III層用押出機から押出された樹脂溶融物が外層になるように積層し、幅120mmのダイよりシート状に押し出した。
ダイから押出した溶融樹脂シートを、表面温度25℃に設定された冷却キャストドラム上に押出し、静電印加法を用い冷却キャストドラムに密着させた。冷却キャストドラムに対向配置された剥ぎ取りロールを用いて、冷却後のフィルムをドラムから剥離し、未延伸フィルムを得た。このとき、第I層、第II層、第III層の厚みの比は10:80:10となるように各押出機の吐出量を調整した。
未延伸フィルムを、加熱されたロール群および赤外線ヒーターを用いて、フィルム表面温度が95℃になるように加熱し、その後周速差のあるロール群でフィルムの搬送方向から垂直方向に4.0倍延伸して、厚さが100μmである樹脂フィルムを得た。
上記で作製した樹脂フィルムの片面に、500J/m2の処理量でコロナ放電処理を実施した。その後、リバースロール法にて、コロナ放電処理面に上記で作製した易接着層形成用組成物を乾燥後の厚さが0.1μmになるように調整しながら塗布し、易接着層付き樹脂フィルムを作製した。得られた易接着層付き樹脂フィルムをPET系樹脂フィルムとし、下記表3にPETと記載した。
樹脂フィルム(A)および(C)に代えて、特許第3325560号公報[実施例3]を参考に作製した、厚み100μmのポリカーボネートフィルム(550nmにおける面内レターデーションは140nmだった。)を使用した以外、実施例2と同様の方法で、実施例10の光学フィルムを作製した。下記表3において、ポリカーボネートフィルムをPCと記載した。
樹脂フィルム(A)および(C)を、下記のように作製したアクリル系樹脂フィルムを使用した以外、実施例2と同様の方法で、実施例11の光学フィルムを作製した。
<アクリル系樹脂フィルムの作製>
住友化学社製のアクリル系樹脂(商品名:スミペックスEX)のペレットを押出径65mmの1軸押出機に投入して溶融し、マルチマニホールド方式にて溶融積層一体化させ、乾燥後の各層の膜厚が5μm/90μm/5μmとなるよう制御して、設定温度260℃のT型ダイスを介して押出した。得られたフィルム状物を1対の金属製ロールの間に挟み込んで成形することにより、厚さが100μmである、アクリル系樹脂フィルムを作製した。下記表3において、アクリル系樹脂フィルムをPMMAと記載した。
樹脂フィルム(A)および(C)の厚みをいずれも50μm(外層/コア層/外層=3μm/44μm/3μm)とした以外は実施例2と同様にして、実施例12の光学フィルムを作製した。
[実施例13]
樹脂フィルム(A)および(C)の厚みをいずれも80μm(外層/コア層/外層=3μm/74μm/3μm)とした以外は実施例2と同様にして、実施例13の光学フィルムを作製した。
[実施例14]
樹脂フィルム(C)の厚みを60μm(外層/コア層/外層=3μm/54μm/3μm)とした以外は実施例2と同様にして、実施例14の光学フィルムを作製した。
[実施例15~18]
乾燥後の接着層(B)の厚みが、下記表3記載の厚みとなるように塗布した以外は実施例2と同様にして、実施例15~18の光学フィルムを作製した。
[実施例19~20]
接着層形成用液A-2に代えて接着層形成用液A-10~A-11を使用した以外は実施例16と同様にして、実施例19~20の光学フィルムを作製した。
[比較例1]
樹脂フィルム(A)を、厚み100μmのノルボルネン系樹脂フィルム(日本ゼオン(株)製商品名「ゼオノアZF14」)に変更した以外は、実施例3と同様にして、比較例1の光学フィルムを作製した。下記表3において、ゼオノアZF14をZF14と記載した。
[比較例2]
接着層形成用液A-9を使用した以外は実施例1と同様にして、比較例2の光学フィルムを作製した。
[比較例3]
樹脂フィルム(C)を、厚み100μmのノルボルネン系樹脂フィルム(日本ゼオン(株)製商品名「ゼオノアZF14」)に変更した以外は、実施例3と同様にして、比較例3の光学フィルムを作製した。
[比較例4]
樹脂フィルム(C)を実施例1に記載の樹脂フィルムに変更し、接着層形成用液A-7を使用した以外は実施例11と同様にして、比較例4の光学フィルムを作製した。
[比較例5]
樹脂フィルム(A)を実施例1に記載の樹脂フィルムに変更し、接着層形成用液A-7を使用した以外は実施例11と同様にして、比較例5の光学フィルムを作製した。
[比較例6]
樹脂フィルム(A)および(C)の厚みをいずれも40μm(外層/コア層/外層=3μm/34μm/3μm)とした以外は実施例2と同様にして比較例6の光学フィルムを作製した。
上記で作製した光学フィルムについて、以下の試験を行った。試験結果を下記表3にまとめて記載する。なお、表3中、引張弾性率は、弾性率と略して記載する。
ガラス板(Corning社製、商品名:イーグル XG、厚み1mm)と、上記で作製した光学フィルム(HC層付き積層体)とを、ガラス板と樹脂フィルム(C)側が向かい合うようにして、厚み20μmの粘着剤(綜研化学社製、商品名:SK-2057)を介して、ゴムローラーで2kgの荷重を掛けながら貼り合わせて、温度25℃、相対湿度60%で2時間調湿した。次いで、打鍵試験機(株式会社YSC製)を用いて、HC層の上方から入力ペン(ペン先材料はポリアセタール、半径R=0.8mm、ワコム株式会社製)を押し当て(打鍵速度:2回/分、荷重:250g)、光学フィルムの正面から三波長蛍光灯(ナショナルパルック蛍光灯FL20SS・EX-D/18)で照らしながら目視で観察し、以下の基準で評価した。
<評価基準>
A:50000回打鍵しても凹みが発生しなかった
B:10001回~50000回打鍵する間に凹みが発生した。
C:1001回~10000回打鍵する間に凹みが発生した。
D:101回~1000回打鍵する間に凹みが発生した。
E:100回打鍵する間に凹みが発生した。
各樹脂フィルムの「引張弾性率」は、JIS K7127に記載の方法に従って、以下の方法により試験し、算出した。
上記で作製した樹脂フィルムについて、測定方向に15cmの長さで、幅1cm、の樹脂フィルムを測定用試料として切り出した。切り出した測定用試料を、引張試験機(東洋精機社製、商品名「ストログラフ-R2」)に、測定方向のチャック間隔が10cmとなるように設置し、測定温度25℃の条件下、延伸速度10mm/分でチャック間隔が広がるように延伸し、応力-ひずみ曲線を得た。規定された2点のひずみε1=0.0005及びε2=0.0025の間の曲線の線形回帰により、25℃における引張弾性率を算出した。
なお、樹脂フィルムが異方性を有する場合は、樹脂フィルムの厚み方向に垂直な面において、配向度の最も大きい配向方向を長辺とする測定用試料の引張弾性率と、この配向方向と直行する方向を長辺とする測定用試料の引張弾性率との平均を、樹脂フィルムの引張弾性率とした。
接着層の引張弾性率については、上記で使用した各接着層形成用液について、ガラス板(厚み1mm)上にアプリケーターを用いて乾燥後の膜厚が20μmとなるように流延し、雰囲気温度80℃で10分以上乾燥したのち、ガラス板から剥離した。得られた接着層の試料を用いて、上記樹脂フィルムの引張弾性率と同様の方法により試験し、算出した。
「厚み」は、以下の方法により、走査型電子顕微鏡(Scanning Electron microscope;SEM)により観察して測定した。
各構成部材(樹脂フィルム、接着層及びHC層)または各構成部材を含む部材(例えば液晶パネルやその一部)の断面を、イオンビーム、ミクロトーム等の常法により露出させた後、露出した断面においてSEMによる断面観察を行った。断面観察において、部材の幅方向を4等分した際の、両端を除く3つの等分点における厚みの算術平均として、各種厚みを求めた。
また、光学フィルムの厚みとは、樹脂フィルム(A)と接着層(B)と樹脂フィルム(C)の合計厚みを意味する。
これに対して、樹脂フィルム(A)、接着層(B)及び樹脂フィルム(C)の引張弾性率が式(1)~(5)を満たし、光学フィルムの厚みが100μmより大きい実施例1~18の光学フィルムは、いずれも、100回打鍵しても凹みが発生せず(評価A~D)、打鍵耐久性に優れていた。
また、本発明の光学フィルムにおいては、同じ樹脂種の接着層(B)で比べた場合、接着層(B)の引張弾性率EBが3.3GPaである実施例3、2.3GPaである実施例4に対して、5.5GPaと高い実施例1はより優れた打鍵耐久性を示した。接着層(B)と樹脂フィルム(A)、(C)との引張弾性率の差が1.7GPaである実施例5に対して、0.7GPaと小さい実施例1、および、2.8GPaである実施例6、3.4GBである実施例7に対して、0.8GPaと小さい実施例2はより優れた打鍵耐久性を示した。
さらに、光学フィルムの厚みが101μmである実施例12、161μmである実施例13及び実施例14に対して、201μmと大きい実施例2はより優れた打鍵耐久性を示した。
1B:第二の樹脂フィルム
2A:接着層
3A:ハードコート層(HC層)
4A、4B:光学フィルム
1:タッチパネル用導電フィルム
2:タッチパネル
4C:光学フィルム
5:透明絶縁基板
6A、6B:導電部材
7A、7B:保護層
8:第1導電層
9:第2導電層
11A:第1ダミー電極
11:第1電極
12:第1周辺配線
13:第1外部接続端子
14:第1コネクタ部
15:第1金属細線
21:第2電極
22:第2周辺配線
23:第2外部接続端子
24:第2コネクタ部
25:第2金属細線
C1:第1セル
C2:第2セル
D1:第1の方向
D2:第2の方向
M1:第1メッシュパターン
M2:第2メッシュパターン
S1:アクティブエリア
S2:周辺領域
Claims (18)
- 少なくとも、第一の樹脂フィルム(A)と接着層(B)と第二の樹脂フィルム(C)とが、この順で積層されてなり、
前記第一の樹脂フィルム(A)の25℃における引張弾性率EA、前記接着層(B)の25℃における引張弾性率EB及び前記第二の樹脂フィルム(C)の25℃における引張弾性率ECが下記式(1)~(5)を満たし、
前記第一の樹脂フィルム(A)と前記接着層(B)と前記第二の樹脂フィルム(C)の合計厚みが100μmより大きい光学フィルム。
|EA-EB|≦4.0GPa 式(1)
|EC-EB|≦4.0GPa 式(2)
2.0GPa≦EA 式(3)
2.0GPa≦EB 式(4)
2.0GPa≦EC 式(5) - 前記引張弾性率EA及び前記引張弾性率EBが下記式(1-2)を満たす、請求項1に記載の光学フィルム。
|EA-EB|≦2.0GPa 式(1-2) - 前記接着層(B)の厚みが10nm以上10μm以下である、請求項1または2に記載の光学フィルム。
- 面内方向のレターデーションが6000nmより小さい、請求項1~3のいずれか1項に記載の光学フィルム。
- 前記第一の樹脂フィルム(A)がセルロースエステル樹脂フィルムである、請求項1~4のいずれか1項に記載の光学フィルム。
- 前記第二の樹脂フィルム(C)がセルロースエステル樹脂フィルムである、請求項1~5のいずれか1項に記載の光学フィルム。
- 前記接着層(B)がポリビニルアルコールを含む、請求項1~6のいずれか1項に記載の光学フィルム。
- 前記第一の樹脂フィルム(A)と第二の樹脂フィルム(C)が同一のフィルムである、請求項1~7のいずれか1項に記載の光学フィルム。
- 前記第一の樹脂フィルム(A)および第二の樹脂フィルム(C)の少なくとも一方が、前記接着層(B)と反対側の面にハードコート層を有する、請求項1~8のいずれか1項に記載の光学フィルム。
- 請求項1~9のいずれか1項に記載の光学フィルムを有する、画像表示装置の前面板。
- 請求項10に記載の前面板と、画像表示素子とを有する画像表示装置。
- 前記画像表示素子が液晶表示素子である、請求項11に記載の画像表示装置。
- 前記画像表示素子が有機エレクトロルミネッセンス表示素子である、請求項11に記載の画像表示装置。
- 前記画像表示素子がインセルタッチパネル表示素子である、請求項11~13のいずれか1項に記載の画像表示装置。
- 前記画像表示素子がオンセルタッチパネル表示素子である、請求項11~13のいずれか1項に記載の画像表示装置。
- 請求項10に記載の前面板を有する抵抗膜式タッチパネル。
- 請求項10に記載の前面板を有する静電容量式タッチパネル。
- 請求項11に記載の画像表示装置を用いた画像表示機能付きミラー。
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| JPWO2018180746A1 (ja) * | 2017-03-30 | 2019-11-07 | 富士フイルム株式会社 | 光学フィルムならびにこれを有する画像表示装置の前面板、画像表示装置、画像表示機能付きミラ−、抵抗膜式タッチパネルおよび静電容量式タッチパネル |
| CN111312739A (zh) * | 2020-02-26 | 2020-06-19 | 云谷(固安)科技有限公司 | 显示面板以及显示装置 |
| JPWO2022244355A1 (ja) * | 2021-05-19 | 2022-11-24 |
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|---|---|---|---|---|
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| CN117015821A (zh) * | 2021-03-26 | 2023-11-07 | 迪睿合株式会社 | 显示装置的制造方法 |
| CN119684917A (zh) * | 2023-09-22 | 2025-03-25 | 华为技术有限公司 | 复合叠层结构、柔性显示模组和电子设备 |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2006192658A (ja) * | 2005-01-12 | 2006-07-27 | Nitto Denko Corp | ガラス板割れ防止フィルム、光学フィルムおよびディスプレイ |
| JP2007233215A (ja) * | 2006-03-03 | 2007-09-13 | Nippon Zeon Co Ltd | 偏光板 |
| JP2012215812A (ja) * | 2011-03-31 | 2012-11-08 | Fujifilm Corp | 光学フィルム、偏光板、及び画像表示装置 |
| JP2013140390A (ja) * | 2006-03-31 | 2013-07-18 | Nippon Zeon Co Ltd | 偏光板、液晶表示装置及びタッチパネル |
| JP2014199363A (ja) * | 2013-03-29 | 2014-10-23 | 富士フイルム株式会社 | フィルムミラー |
| JP2016184180A (ja) * | 2016-06-30 | 2016-10-20 | 日東電工株式会社 | 表示装置用保護基板 |
Family Cites Families (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP3710368B2 (ja) * | 2000-09-25 | 2005-10-26 | シャープ株式会社 | 積層フィルムの製造方法 |
| JP5073927B2 (ja) * | 2005-05-30 | 2012-11-14 | 富士フイルム株式会社 | セルロースアシレートフィルムの製造方法及び装置 |
| JP2008063536A (ja) * | 2006-09-11 | 2008-03-21 | Fujifilm Corp | 環状オレフィン系樹脂フィルム |
| JP5141074B2 (ja) * | 2007-03-30 | 2013-02-13 | Jsr株式会社 | 耐衝撃粘着層、耐衝撃粘着積層体、及び表示装置 |
| JP6236200B2 (ja) | 2012-12-06 | 2017-11-22 | 日東電工株式会社 | 積層体および該積層体を用いた透明導電性フィルム |
| JP2016071246A (ja) * | 2014-09-30 | 2016-05-09 | 富士フイルム株式会社 | 表示パネル基板の製造方法、表示パネル基板、及び、タッチパネル表示装置 |
| JP2016164641A (ja) | 2015-03-06 | 2016-09-08 | リンテック株式会社 | ハードコートフィルムおよび画像表示装置 |
| KR101579710B1 (ko) * | 2015-11-12 | 2015-12-22 | 동우 화인켐 주식회사 | 광학적층체 및 이를 포함하는 화상표시장치 |
-
2017
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- 2017-11-16 KR KR1020197013782A patent/KR102233185B1/ko active Active
- 2017-11-16 JP JP2018554896A patent/JP6782305B2/ja active Active
-
2019
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Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2006192658A (ja) * | 2005-01-12 | 2006-07-27 | Nitto Denko Corp | ガラス板割れ防止フィルム、光学フィルムおよびディスプレイ |
| JP2007233215A (ja) * | 2006-03-03 | 2007-09-13 | Nippon Zeon Co Ltd | 偏光板 |
| JP2013140390A (ja) * | 2006-03-31 | 2013-07-18 | Nippon Zeon Co Ltd | 偏光板、液晶表示装置及びタッチパネル |
| JP2012215812A (ja) * | 2011-03-31 | 2012-11-08 | Fujifilm Corp | 光学フィルム、偏光板、及び画像表示装置 |
| JP2014199363A (ja) * | 2013-03-29 | 2014-10-23 | 富士フイルム株式会社 | フィルムミラー |
| JP2016184180A (ja) * | 2016-06-30 | 2016-10-20 | 日東電工株式会社 | 表示装置用保護基板 |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPWO2018180746A1 (ja) * | 2017-03-30 | 2019-11-07 | 富士フイルム株式会社 | 光学フィルムならびにこれを有する画像表示装置の前面板、画像表示装置、画像表示機能付きミラ−、抵抗膜式タッチパネルおよび静電容量式タッチパネル |
| CN111312739A (zh) * | 2020-02-26 | 2020-06-19 | 云谷(固安)科技有限公司 | 显示面板以及显示装置 |
| CN111312739B (zh) * | 2020-02-26 | 2022-10-21 | 云谷(固安)科技有限公司 | 显示面板以及显示装置 |
| JPWO2022244355A1 (ja) * | 2021-05-19 | 2022-11-24 | ||
| JP7724454B2 (ja) | 2021-05-19 | 2025-08-18 | パナソニックIpマネジメント株式会社 | タッチセンサ |
Also Published As
| Publication number | Publication date |
|---|---|
| KR20190073435A (ko) | 2019-06-26 |
| CN110023084A (zh) | 2019-07-16 |
| JPWO2018105352A1 (ja) | 2019-10-24 |
| JP6782305B2 (ja) | 2020-11-11 |
| CN110023084B (zh) | 2021-03-09 |
| US20190255818A1 (en) | 2019-08-22 |
| KR102233185B1 (ko) | 2021-03-30 |
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