WO2018128171A1 - 光学フィルムおよび画像表示装置 - Google Patents
光学フィルムおよび画像表示装置 Download PDFInfo
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- WO2018128171A1 WO2018128171A1 PCT/JP2017/047350 JP2017047350W WO2018128171A1 WO 2018128171 A1 WO2018128171 A1 WO 2018128171A1 JP 2017047350 W JP2017047350 W JP 2017047350W WO 2018128171 A1 WO2018128171 A1 WO 2018128171A1
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- optical film
- resin
- hard coat
- coat layer
- acrylate
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- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
- G02B1/10—Optical coatings produced by application to, or surface treatment of, optical elements
- G02B1/14—Protective coatings, e.g. hard coatings
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
- B32B7/02—Physical, chemical or physicochemical properties
- B32B7/023—Optical properties
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
- B32B27/08—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/28—Layered products comprising a layer of synthetic resin comprising synthetic resins not wholly covered by any one of the sub-groups B32B27/30 - B32B27/42
- B32B27/281—Layered products comprising a layer of synthetic resin comprising synthetic resins not wholly covered by any one of the sub-groups B32B27/30 - B32B27/42 comprising polyimides
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/34—Layered products comprising a layer of synthetic resin comprising polyamides
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
- B32B7/04—Interconnection of layers
- B32B7/12—Interconnection of layers using interposed adhesives or interposed materials with bonding properties
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- G—PHYSICS
- G09—EDUCATION; CRYPTOGRAPHY; DISPLAY; ADVERTISING; SEALS
- G09F—DISPLAYING; ADVERTISING; SIGNS; LABELS OR NAME-PLATES; SEALS
- G09F9/00—Indicating arrangements for variable information in which the information is built-up on a support by selection or combination of individual elements
-
- G—PHYSICS
- G09—EDUCATION; CRYPTOGRAPHY; DISPLAY; ADVERTISING; SEALS
- G09F—DISPLAYING; ADVERTISING; SIGNS; LABELS OR NAME-PLATES; SEALS
- G09F9/00—Indicating arrangements for variable information in which the information is built-up on a support by selection or combination of individual elements
- G09F9/30—Indicating arrangements for variable information in which the information is built-up on a support by selection or combination of individual elements in which the desired character or characters are formed by combining individual elements
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- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05B—ELECTRIC HEATING; ELECTRIC LIGHT SOURCES NOT OTHERWISE PROVIDED FOR; CIRCUIT ARRANGEMENTS FOR ELECTRIC LIGHT SOURCES, IN GENERAL
- H05B33/00—Electroluminescent light sources
- H05B33/02—Details
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K50/00—Organic light-emitting devices
- H10K50/80—Constructional details
- H10K50/84—Passivation; Containers; Encapsulations
- H10K50/844—Encapsulations
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2255/00—Coating on the layer surface
- B32B2255/10—Coating on the layer surface on synthetic resin layer or on natural or synthetic rubber layer
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2307/00—Properties of the layers or laminate
- B32B2307/50—Properties of the layers or laminate having particular mechanical properties
- B32B2307/51—Elastic
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2457/00—Electrical equipment
- B32B2457/20—Displays, e.g. liquid crystal displays, plasma displays
- B32B2457/206—Organic displays, e.g. OLED
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K2102/00—Constructional details relating to the organic devices covered by this subclass
- H10K2102/301—Details of OLEDs
- H10K2102/311—Flexible OLED
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K59/00—Integrated devices, or assemblies of multiple devices, comprising at least one organic light-emitting element covered by group H10K50/00
- H10K59/80—Constructional details
- H10K59/87—Passivation; Containers; Encapsulations
Definitions
- the present invention relates to an optical film and an image display device.
- an optical film used for such a foldable image display device may be subjected to an impact on the surface of the optical film, impact resistance is required.
- the surface of the optical film may be recessed, and a member such as a display panel (for example, an organic light-emitting diode panel) existing inside the optical film in the image display device May be damaged.
- the dent on the surface of the optical film there are a dent caused by the optical film itself and a dent caused by the adhesive layer disposed inside the image display device rather than the optical film.
- the dent caused by the optical film itself means a dent caused by the deformation of the optical film itself due to the impact when the impact is applied to the surface of the optical film. Because the adhesive layer is soft, when an impact is applied to the surface of the optical film, the adhesive layer placed inside the image display device causes plastic deformation rather than the optical film, and the optical film follows the plastic deformation of the adhesive layer. It means a dent caused by doing.
- the present situation is that an optical film having such excellent impact resistance has not yet been obtained.
- an object of the present invention is to provide a foldable optical film having excellent impact resistance and an image display device including the foldable optical film.
- a foldable light transmissive optical film used for an image display device the resin base material and a hard coat provided on the first surface side of the resin base material And a resin layer having a film thickness of 50 ⁇ m or more and 300 ⁇ m or less provided on the second surface side opposite to the first surface of the resin base material, 25 ° C., 500 Hz in the optical film
- the shear storage modulus G ′ in the frequency range of 1000 Hz or less is more than 200 MPa and 1200 MPa or less
- the shear loss modulus G ′′ in the frequency range of 25 ° C. and 500 Hz to 1000 Hz in the optical film is 3 MPa.
- An optical film having a pressure of 150 MPa or less is provided.
- the resin base material may be a base material made of a polyimide resin, a polyamide resin, or a mixture thereof.
- a foldable image display device comprising: a display panel; and the optical film disposed on the viewer side with respect to the display panel, wherein the optical film includes the optical film.
- an image display device in which a hard coat layer is located closer to an observer than the resin base material.
- the image display device may further include an adhesive layer disposed between the optical film and the display panel.
- the display panel may be an organic light emitting diode panel.
- a foldable optical film having excellent impact resistance can be provided.
- an image display apparatus provided with such an optical film can be provided.
- FIG. 1 is a schematic configuration diagram of an optical film according to an embodiment.
- FIG. 2 is a schematic configuration diagram of a solid shearing jig used when measuring the shear storage elastic modulus G ′ and the shear loss elastic modulus G ′′.
- FIGS. 3A to 3C are diagrams schematically showing the state of the continuous folding test.
- 4 (A) and 4 (B) are diagrams schematically showing a state of the folding stationary test.
- FIG. 5 is a schematic configuration diagram of another optical film according to the embodiment.
- 1 is a schematic configuration diagram of an image display device according to an embodiment.
- FIG. 1 is a schematic configuration diagram of an optical film according to the present embodiment
- FIG. 2 is a schematic configuration diagram of a solid shearing jig used when measuring a shear storage elastic modulus G ′ and a shear loss elastic modulus G ′′.
- 3 is a diagram schematically showing the state of the continuous folding test
- FIG. 4 is a diagram schematically showing the state of the folding stationary test
- FIG. 5 is another optical system according to this embodiment. It is a schematic block diagram of a film.
- the optical film 10 shown in FIG. 1 is used for an image display device, is foldable, and has optical transparency.
- the “light transmittance” in the present specification means a property of transmitting light.
- the total light transmittance is 50% or more, preferably 70% or more, more preferably 80% or more, and particularly preferably 90%. Including that.
- the light transmissive property does not necessarily need to be transparent, and may be translucent.
- the optical film 10 is a surface opposite to the resin substrate 11, the hard coat layer 12 provided on the first surface 11 ⁇ / b> A side of the resin substrate 11, and the first surface 11 ⁇ / b> A of the resin substrate 11. And a resin layer 13 provided on the second surface 11B side.
- a release film may be provided on the surface of the resin layer 13 opposite to the surface on the resin base material 11 side.
- the physical properties and the like of the optical film 10 described in the present specification are values in a state where a release film is not provided, and the release film is peeled off during use. The film shall not constitute a part of the optical film.
- the surface 10 ⁇ / b> A of the optical film 10 is the surface 12 ⁇ / b> A of the hard coat layer 12.
- the surface of the optical film is used as meaning the surface of one side of the optical film, so that the surface opposite to the surface of the optical film is distinguished from the back surface in order to distinguish it from the surface of the optical film. Shall be called.
- the back surface 10 ⁇ / b> B of the optical film 10 is a surface 13 ⁇ / b> A opposite to the surface on the resin base material 11 side in the resin layer 13.
- the shear storage modulus G ′ in the frequency range of 25 ° C. and 500 Hz to 1000 Hz is more than 200 MPa and 1200 MPa or less.
- the shear storage modulus G ′ of the film exceeds 200 MPa, when an impact is applied to the surface of the optical film, not only the deformation of the optical film itself but also the adhesive layer is disposed inside the image display device rather than the optical film. Even in this case, plastic deformation of the adhesive layer can be suppressed.
- the crack of the optical film in the case of folding can be suppressed as the shear storage elastic modulus G 'of an optical film is 1200 Mpa or less.
- the lower limit of the shear storage modulus G ′ of the optical film 10 is preferably 400 MPa or more, and more preferably 500 MPa or more. By setting it as such a lower limit, more excellent impact resistance can be obtained.
- the upper limit of the shear storage modulus G ′ of the optical film 10 is preferably less than 800 MPa. By setting it as such an upper limit, when it is folded and left still and opened again, a good restoring property can be obtained.
- the shear loss elastic modulus G ′′ in the frequency range of 25 ° C. and 500 Hz to 1000 Hz is 3 MPa to 150 MPa. If the shear loss elastic modulus G ′′ of the optical film is less than 3 MPa, the impact absorption performance may be reduced. Moreover, when the shear loss elastic modulus G ′′ of the optical film exceeds 150 MPa, the hardness of the resin layer may decrease.
- the lower limit of the shear loss elastic modulus G ′′ of the optical film 10 is preferably 20 MPa or more, and the upper limit of the shear loss elastic modulus G ′′ of the optical film 10 is from the viewpoint of making the optical film 10 thinner.
- the pressure is preferably 130 MPa or less, and more preferably 100 MPa or less.
- the shear storage elastic modulus G ′ and the shear loss elastic modulus G ′′ can be measured by a dynamic viscoelasticity measuring device (DMA).
- DMA dynamic viscoelasticity measuring device
- the optical film 10 is punched into a 10 mm ⁇ 5 mm rectangular shape. Get a sample.
- two samples are prepared and attached to a solid shearing jig which is an option of a dynamic viscoelasticity measuring apparatus (product name “Rheogel-E4000”, manufactured by UBM). Specifically, as shown in FIG.
- the solid shearing jig 20 is arranged on one metal solid shear plate 21 (medium plate) having a thickness of 1 mm and on both sides of the solid shear plate 21.
- Two L-shaped brackets 22 (outer plates), one sample S is sandwiched between the solid shear plate 21 and one L-shaped bracket 22, and the solid shear plate 21 and the other L-shaped bracket 22 are sandwiched. And sandwich the other sample S.
- the sample S is sandwiched so that the resin layer is on the solid shear plate 21 side and the hard coat layer is on the L-shaped metal fitting 22 side. Then, the L-shaped metal fittings are fastened with screws 23 to fix the sample S.
- a solid is placed between the upper chuck and the lower chuck.
- a shearing jig is attached with a distance between chucks of 20 mm.
- the distance between chucks is a distance between the upper chuck and the lower chuck.
- set temperature is 25 degreeC and it heats up at 2 degree-C / min. In this state, the solid viscoelasticity of the solid at 25 ° C.
- the shear storage elastic modulus G ′ and the shear loss elastic modulus G ′′ of the optical film 10 are measured.
- the shear storage elastic modulus G ′ and the shear loss elastic modulus G ′′ in the frequency range of 500 Hz to 1000 Hz in the optical film respectively give longitudinal vibrations of frequencies 500 Hz, 750 Hz, and 950 Hz to the L-shaped brackets, respectively.
- the shear storage elastic modulus G ′ and the shear loss elastic modulus G ′′ of the optical film are measured at the frequency of, and an arithmetic average value of these shear storage elastic modulus G ′ and shear loss elastic modulus G ′′ is obtained.
- the measurement is repeated three times, and the three arithmetic average values obtained are further calculated as arithmetic average values.
- the frequency range of 500 Hz to 1000 Hz is that the frequency of the frequency range is from several microns to several tens of microns when an object is freely dropped from a height of several centimeters. This is because it is a frequency that is deformed and is a frequency that damages the display panel and the like existing inside the image display device from the optical film.
- the other film When another film such as a polarizing plate is provided on one surface side of the optical film 10 via an adhesive layer or an adhesive layer, the other film is peeled off together with the adhesive layer or the adhesive layer, and then stored in shear. It is assumed that the elastic modulus G ′ and the shear loss elastic modulus G ′′ are measured.
- Other films can be peeled as follows, for example. First, the laminate with other films attached to the optical film through an adhesive layer or adhesive layer is heated with a dryer, and the blade edge of the cutter is inserted into the part that appears to be the interface between the optical film and the other film. I will let you. By repeating such heating and peeling, the pressure-sensitive adhesive layer, the adhesive layer, and other films can be peeled off. Even if such a peeling process is performed, the results of the shear storage elastic modulus G ′ and the shear loss elastic modulus G ′′ are not significantly affected.
- the optical film 10 can be folded, specifically, even when the folding test (continuous folding test) described below is repeated 100,000 times on the optical film 10, It is preferable that no cracks or breaks occur, and even when the continuous folding test is repeated 200,000 times, it is more preferable that the optical film 10 is not cracked or broken, and when it is repeated 1 million times. Even more preferably, the optical film does not crack or break.
- a continuous folding test is repeated 100,000 times on the optical film 10, if the optical film 10 is cracked or the like, the folding property of the optical film 10 becomes insufficient.
- the continuous folding test may be performed so that the optical film 10 is folded so that the hard coat layer 12 is on the inner side, or may be performed so that the optical film 10 is folded so that the hard coat layer 12 is on the outer side. In any case, it is preferable that the optical film is not cracked or broken.
- the continuous folding test is performed as follows. As shown in FIG. 3A, in the continuous folding test, first, the side portion 10C of the optical film 10 and the side portion 10D facing the side portion 10C are fixed by the fixing portions 30 arranged in parallel, respectively. .
- the optical film 10 may be arbitrary shapes, it is preferable that the optical film 10 in a continuous folding test is a rectangle (for example, rectangle of 30 mm x 100 mm). Further, as shown in FIG. 3A, the fixing portion 30 is slidable in the horizontal direction.
- the fixing portion 30 is moved so as to be close to each other, thereby deforming the optical film 10 so as to be folded. Further, as shown in FIG. After moving the fixing part 30 to a position where the distance between two opposing side parts fixed by the fixing part 30 of the film 10 is 30 mm, the fixing part 30 is moved in the reverse direction to eliminate the deformation of the optical film 10.
- the optical film 10 can be folded by 180 ° by moving the fixing portion 30.
- a continuous folding test is performed so that the bent portion 10E of the optical film 10 does not protrude from the lower end of the fixed portion 30, and the interval when the fixed portion 30 is closest is controlled to 30 mm.
- the interval between the two opposing sides can be 30 mm.
- the outer diameter of the bent portion 10E is regarded as 30 mm.
- the thickness of the optical film 10 is a sufficiently small value compared with the interval (30 mm) of the fixed portion 30, the result of the continuous folding test of the optical film 10 is not affected by the difference in the thickness of the optical film 10. It can be regarded as not received.
- cracking or breaking does not occur when the test of folding 180 ° is repeated 100,000 times so that the distance between the opposing sides of the optical film 10 is 30 mm. It is more preferable that no cracking or breakage occurs when the continuous folding test is repeated 100,000 times so that the interval between the opposing side portions is 6 mm, and the interval between the opposing side portions of the optical film 10 is 3 mm. It is more preferable that no cracking or breakage occurs when the continuous folding test is repeated 100,000 times so that the distance between the opposing sides of the optical film 10 is 2 mm. Most preferably, no cracks or breaks occur when the folding test is repeated 100,000 times.
- the side portion 10C of the optical film 10 and the side portion 10D facing the side portion 10C are separated by a distance of 30 mm between the side portion 10C and the side portion 10D.
- a folding stationary test is performed in which the optical film 10 is folded at 240 ° C. for 240 hours in a state where the optical film 10 is folded.
- the folding portion is released by removing the fixing portion 35 from the side portion 10D after the folding stationary test, and the opening angle ⁇ that is an angle at which the optical film 10 naturally opens in the optical film 10 is measured after 30 minutes at room temperature.
- the opening angle ⁇ of the optical film 10 is preferably 100 ° or more.
- the folding stationary test may be performed so that the optical film 10 is folded so that the hard coat layer 12 is inside, and is performed so that the optical film 10 is folded so that the hard coat layer 12 is outside.
- the opening angle ⁇ is preferably 100 ° or more.
- the surface 10A of the optical film 10 (the surface 12A of the hard coat layer 12) has a hardness (pencil hardness) of B or higher when measured by a pencil hardness test specified in JIS K5600-5-4: 1999. Is more preferable, and H or more is more preferable.
- the pencil hardness test is performed in a state where a load of 1 kg is applied to the pencil and the moving speed of the pencil is 1 mm / second.
- the pencil hardness is the highest hardness at which the surface of the optical film was not damaged in the pencil hardness test.
- the pencil hardness is measured using a plurality of pencils having different hardnesses.
- the pencil hardness test is performed five times for each pencil, and the surface of the optical film is scratched four times or more out of the five times. If not, it is determined that the surface of the optical film was not scratched with the pencil having this hardness.
- the above-mentioned scratches refer to those that are visually observed through transmission observation of the surface of the optical film subjected to the pencil hardness test under a fluorescent lamp.
- the optical film 10 preferably has a yellow index (YI) of 15 or less. If the YI of the optical film 10 exceeds 15, the yellow color of the optical film is conspicuous and may not be applicable to uses where transparency is required.
- the yellow index (YI) is a value measured using a spectrophotometer (product name “UV-3100PC”, manufactured by Shimadzu Corporation, light source: tungsten lamp and deuterium lamp).
- the upper limit of the yellow index (YI) of the optical film 10 is more preferably 10 or less.
- the yellow index (YI) shall be measured after peeling. Even if there is such a peeling process, there is no significant influence on the measurement of the yellow index (YI).
- the resin base material 11 or the resin layer 13 may contain a blue pigment that is a complementary color of yellow. Even if it is a case where yellowishness becomes a problem by using a polyimide base material as a resin base material, by including a blue pigment
- the blue pigment may be either a pigment or a dye.
- the optical film 10 when used in an organic light emitting diode display device, it is preferable to have both light resistance and heat resistance.
- the above-mentioned blue pigment polycyclic organic pigments, metal complex organic pigments, etc. are used in applications where light resistance is required because the degree of molecular breakage due to ultraviolet rays is small compared to the molecular dispersion of dyes and the light resistance is remarkably superior More specifically, phthalocyanine-based organic pigments and the like are preferable.
- the pigment is particle-dispersed with respect to the solvent, transparency inhibition due to particle scattering exists, and therefore it is preferable to put the particle size of the pigment dispersion in the Rayleigh scattering region.
- the transparency of the optical film is regarded as important, it is preferable to use a dye that is molecularly dispersed in a solvent as the blue pigment.
- the transmittance of light having a wavelength of 380 nm of the optical film 10 is preferably 8% or less.
- the transmittance of the optical film exceeds 8%, when the optical film is used in a mobile terminal, the polarizer may be exposed to ultraviolet rays and may be easily deteriorated.
- the transmittance can be measured using a spectrophotometer (product name “UV-3100PC”, manufactured by Shimadzu Corporation, light source: tungsten lamp and deuterium lamp).
- the transmittance is an arithmetic average value obtained by measuring three times.
- the upper limit of the transmittance of the optical film 10 is more preferably 5%.
- permeability of the optical film 10 can be achieved by adjusting the addition amount of the ultraviolet absorber mentioned later in the resin layer 13.
- the haze value (total haze value) of the optical film 10 is preferably 2.5% or less. If the haze value of the optical film exceeds 2.5%, the image display surface may be whitened when the optical film is used for a mobile terminal.
- the haze value is more preferably 1.5% or less, and more preferably 1.0% or less.
- the haze value can be measured by a method in accordance with JIS K7136: 2000 using a haze meter (product name “HM-150”, manufactured by Murakami Color Research Laboratory).
- HM-150 manufactured by Murakami Color Research Laboratory
- the above haze value is cut out to a size of 50 mm ⁇ 100 mm, and installed so that the surface side of the optical film becomes the non-light source side without curling or wrinkling, and without fingerprints or dust. Is measured three times, and the arithmetic average value of the values obtained by measuring three times is used. In this specification, “measuring three times” means not measuring the same place three times, but measuring three different places.
- the visually observed surface 10A is flat
- the resin layer 12 is also flat
- the variation in film thickness is within ⁇ 10%.
- the average value of the haze value of the approximate whole in-plane of an optical film is obtained by measuring a haze value in three different places of the cut-out optical film.
- the variation in the haze value is within ⁇ 10% regardless of whether the measurement target is as long as 1 m ⁇ 3000 m or the size of a 5-inch smartphone.
- HM-150 has an inlet opening for measurement of 20 mm.phi., So that the sample size needs to be 21 mm or more in diameter. For this reason, you may cut out an optical film suitably in the magnitude
- the measurement points are set to three positions by gradually shifting within a range where the light source spot is not removed or changing the angle.
- a light emitting diode (Light Emitting Diode) has been actively adopted as a light source for a backlight of an image display device such as a personal computer or a tablet terminal.
- the light emitting diode strongly emits light called blue light. .
- This blue light is a light with a wavelength of 380 to 495 nm and has properties close to ultraviolet rays, and has strong energy. Therefore, the blue light reaches the retina without being absorbed by the cornea or the crystalline lens. It is said to cause serious fatigue and adverse effects on sleep. For this reason, when an optical film is applied to an image display device, it is preferable that the optical film has excellent blue light shielding properties without affecting the color of the display screen.
- the optical film 10 has a spectral transmittance of less than 1% at a wavelength of 380 nm, a spectral transmittance of less than 10% at a wavelength of 410 nm, and a spectral transmittance of 70 at a wavelength of 440 nm. % Or more is preferable. If the spectral transmittance at a wavelength of 380 nm is 1% or more or the spectral transmittance at a wavelength of 410 nm is 10% or more, the problem due to blue light may not be solved, and the spectral transmittance at a wavelength of 440 nm is 70%.
- the optical film 10 sufficiently absorbs light in the wavelength region of 410 nm or less of the wavelength of blue light, while sufficiently transmitting light of wavelength 440 nm or more without affecting the color of the display screen. Blue light shielding properties can be improved. Moreover, when the optical film 10 having excellent blue light shielding properties is applied to an organic light emitting diode (OLED) display device as an image display device, it is also effective in suppressing deterioration of the organic light emitting diode element.
- OLED organic light emitting diode
- the light transmittance of the optical film 10 is almost 0% up to a wavelength of 380 nm, it is preferable that the light transmission gradually increases from a wavelength of 410 nm, and the light transmission rapidly increases in the vicinity of a wavelength of 440 nm.
- the spectral transmittance changes between a wavelength of 410 nm and 440 nm so as to draw a sigmoid curve.
- the spectral transmittance at a wavelength of 380 nm is more preferably less than 0.5%, still more preferably less than 0.2%, and the spectral transmittance at a wavelength of 410 nm is more preferably less than 7%, more preferably less than 5%.
- the spectral transmittance at a wavelength of 440 nm is more preferably 75% or more, and still more preferably 80% or more.
- the optical film 10 preferably has a spectral transmittance of less than 50% at a wavelength of 420 nm. By satisfying such a spectral transmittance relationship, the optical film 10 has a sharply improved transmittance around a wavelength of 440 nm, and has an excellent blue light shielding property without affecting the color of the display screen. Can be obtained.
- the spectral transmittance at a wavelength of 380 nm in the optical film 10 is more preferably less than 0.1%, the spectral transmittance at a wavelength of 410 nm is more preferably less than 7%, and the spectral transmittance at a wavelength of 440 nm is 80% or more. It is more preferable that
- the optical film 10 preferably has an inclination a of a transmission spectrum in a wavelength range of 415 to 435 nm obtained by using the least square method such that a> 2.0. If the slope a is 2.0 or less, light cannot be sufficiently cut in the blue light wavelength region, for example, the wavelength region of 415 to 435 nm, and the blue light cut effect may be weakened. Further, there is a possibility that the light wavelength region of blue light (wavelength 415 to 435 nm) is cut too much. In that case, the backlight of the image display device or the light emission wavelength region (for example, light emission from the wavelength 430 nm of the OLED) There is a possibility that a problem such as a problem that the color becomes worse due to interference with the color is increased.
- the slope a is, for example, a transmittance data for at least 5 points between 1 nm before and after using a spectroscope (product name “UVPC-2450”, manufactured by Shimadzu Corporation) that can be measured in 0.5% increments. Can be calculated by measuring between 415 and 435 nm.
- a spectroscope product name “UVPC-2450”, manufactured by Shimadzu Corporation
- the optical film 10 preferably has a blue light shielding rate of 40% or more. If the blue light shielding rate is less than 40%, the above-described problems caused by blue light may not be sufficiently solved.
- the blue light shielding rate is, for example, a value calculated according to JIS T7333: 2005. Such a blue light shielding rate can be achieved, for example, when the resin layer 13 contains a sesamol type benzotriazole-based monomer described later.
- the use of the optical film 10 is not particularly limited. Examples of the use of the optical film 10 include image display devices such as smartphones, tablet terminals, personal computers (PCs), wearable terminals, digital signage, televisions, and car navigation systems. Can be mentioned.
- the optical film 10 is also suitable for in-vehicle use.
- the form of each image display device is also preferable for applications that require flexibility such as foldable and rollable.
- the optical film 10 may be cut into a desired size, but may be in a roll shape.
- the size of the optical film is not particularly limited, and is appropriately determined according to the size of the display surface of the image display device.
- the size of the optical film 10 may be, for example, not less than 2.8 inches and not more than 500 inches.
- “inch” means the length of a diagonal line when the optical film has a quadrangular shape, means the diameter when the optical film is circular, and has the short diameter when it is elliptical. And the average value of the sum of the major axes.
- the aspect ratio of the optical film when obtaining the inch is not particularly limited as long as there is no problem as a display screen of the image display device.
- length: width 1: 1, 4: 3, 16:10, 16: 9, 2: 1, and the like.
- the aspect ratio is not particularly limited in in-vehicle applications and digital signage that are rich in design.
- size of the optical film 10 is large, after cutting out to A5 size (148 mm x 210 mm) from arbitrary positions, it shall cut out to the magnitude
- the location of the optical film 10 in the image display device may be inside the image display device, but is preferably near the surface of the image display device.
- the optical film 10 When used near the surface of the image display device, the optical film 10 functions as a cover film used instead of the cover glass.
- the resin base material 11 is a base material made of a resin having optical transparency.
- the thickness of the resin substrate 11 is preferably 10 ⁇ m or more and 100 ⁇ m or less. If the thickness of the resin base material is less than 10 ⁇ m, the curl of the optical film may be increased and the hardness may be insufficient. Further, when the optical film is produced by Roll to Roll, wrinkles are likely to occur. Therefore, the appearance may be deteriorated. On the other hand, if the thickness of the resin substrate exceeds 100 ⁇ m, the folding performance of the optical film becomes insufficient, and the requirements for the continuous folding test may not be satisfied, and the optical film becomes heavy, which is not preferable in terms of weight reduction. .
- the thickness of the resin base material is obtained by photographing a cross section of the resin base material using a scanning electron microscope (SEM), measuring 20 film thicknesses of the resin base material in the image of the cross section, and measuring the film thickness at the 20 locations.
- the arithmetic average value of The method for taking a cross-sectional photograph of the resin substrate is the same as the method for taking a cross-sectional photograph of the hard coat layer.
- the lower limit of the resin base material 11 is more preferably 25 ⁇ m or more, and the upper limit of the resin base material 11 is more preferably 80 ⁇ m or less.
- the resin constituting the resin substrate 11 examples include polyimide resin, polyamideimide resin, polyamide resin, polyester resin (for example, polyethylene terephthalate resin and polyethylene naphthalate resin), or a mixture of two or more of these resins. Can be mentioned. Among these, not only is cracking or breaking difficult to occur in the continuous folding test, it also has excellent hardness and transparency, and also has excellent heat resistance, and further improved hardness and transparency by firing. From the viewpoint of imparting a high molecular weight, a polyimide resin, a polyamide resin, or a mixture thereof is preferable.
- the polyimide resin is obtained by reacting a tetracarboxylic acid component and a diamine component. It is preferable to obtain imidization by obtaining a polyamic acid by polymerization of a tetracarboxylic acid component and a diamine component.
- the imidization may be performed by thermal imidization or chemical imidization. Moreover, it can also manufacture by the method which used thermal imidation and chemical imidization together.
- the polyimide resin may be an aliphatic polyimide resin, but is preferably an aromatic polyimide resin containing an aromatic ring.
- the aromatic polyimide resin contains an aromatic ring in at least one of the tetracarboxylic acid component and the diamine component.
- tetracarboxylic dianhydride is preferably used as specific examples of the tetracarboxylic acid component.
- diamine component examples include p-phenylenediamine, m-phenylenediamine, o-phenylenediamine, 3,3′-diaminodiphenyl ether, 3,4′-diaminodiphenyl ether, 4,4′-diaminodiphenyl ether, 3,3 '-Diaminodiphenyl sulfide, 3,4'-diaminodiphenyl sulfide, 4,4'-diaminodiphenyl sulfide, 3,3'-diaminodiphenyl sulfone, 3,4'-diaminodiphenyl sulfone, 4,4'-diaminodiphenyl sulfone 3,3′-diaminobenzophenone, 4,4′-diaminobenzophenone, 3,4′-diaminobenzophenone, 4,4′-diaminobenzanilide, 3,3′
- the polyimide-based resin includes an aromatic ring, and (i) a fluorine atom, (ii) an aliphatic ring, and (iii) an aromatic ring. It is preferable that it is a polyimide resin containing at least one selected from the group consisting of a linking group that cleaves the electron conjugation between each other, and it is a polyimide resin containing at least one of (i) and (iii). More preferred.
- the polyimide resin contains an aromatic ring, the orientation is improved and the rigidity is improved, but the transmittance tends to be lowered depending on the absorption wavelength of the aromatic ring.
- the light transmittance is improved because the electronic state in the polyimide skeleton can be hardly transferred.
- the polyimide resin contains (ii) an aliphatic ring
- light transmittance is improved because the transfer of charges in the skeleton can be inhibited by breaking the ⁇ electron conjugation in the polyimide skeleton.
- the polyimide resin includes (iii) a linking group that cleaves the electron conjugation between aromatic rings, the transfer of charge in the skeleton may be inhibited by breaking the ⁇ electron conjugation in the polyimide skeleton.
- the light transmittance is improved from the point where it can be done.
- linking group that cleaves the electron conjugation between aromatic rings include, for example, ether bond, thioether bond, carbonyl bond, thiocarbonyl bond, amide bond, sulfonyl bond, sulfinyl bond, and fluorine-substituted.
- a divalent linking group such as an alkylene group.
- a polyimide resin containing an aromatic ring and containing a fluorine atom is preferably used from the viewpoint of improving light transmittance and improving rigidity.
- the content ratio of fluorine atoms in the polyimide resin containing fluorine atoms is the ratio (F / C) of the number of fluorine atoms (F) and the number of carbon atoms (C) measured on the surface of the polyimide resin by X-ray photoelectron spectroscopy. , 0.01 or more, and more preferably 0.05 or more.
- the said ratio by the measurement of X-ray photoelectron spectroscopy (XPS) can be calculated
- polyimide resin in which 70% or more of the hydrogen atoms bonded to the carbon atoms contained in the polyimide resin are hydrogen atoms directly bonded to the aromatic ring. It is preferably used from the point of improving.
- the proportion of hydrogen atoms (number) directly bonded to the aromatic ring in the total hydrogen atoms (number) bonded to the carbon atoms contained in the polyimide resin is preferably 80% or more, more preferably 85% or more. It is more preferable that When 70% or more of the hydrogen atoms bonded to the carbon atoms contained in the polyimide are polyimide atoms that are bonded directly to the aromatic ring, the film is stretched at, for example, 200 ° C.
- polyimide which is a hydrogen atom bonded directly to an aromatic ring
- YI total light transmittance and yellow index
- a substrate made of a polyimide resin utilizes its high heat resistance, and is often used for devices that require a heating process, but 70% of the hydrogen atoms bonded to the carbon atoms contained in the polyimide resin.
- the ratio of the hydrogen atoms (number) directly bonded to the aromatic ring in the total hydrogen atoms (number) bonded to the carbon atoms contained in the polyimide resin is determined by high-performance liquid chromatography, gas chromatography It can be determined using a tomograph mass spectrometer and NMR.
- a sample is decomposed with an alkaline aqueous solution or supercritical methanol, and the resulting decomposition product is separated by high performance liquid chromatography, and a qualitative analysis of each separated peak is performed using a gas chromatograph mass spectrometer and NMR.
- the ratio of hydrogen atoms (numbers) directly bonded to the aromatic ring in the total hydrogen atoms (numbers) contained in the polyimide can be determined by performing determination using high performance liquid chromatography.
- polyimide-type resin As a polyimide-type resin, it is chosen from the group which consists of a structure represented by the following general formula (1) and the following general formula (3) especially. It preferably has at least one structure.
- R 1 is a tetravalent group which is a tetracarboxylic acid residue
- R 2 is a trans-cyclohexanediamine residue, a trans-1,4-bismethylenecyclohexanediamine residue
- 4,4 It represents at least one divalent group selected from the group consisting of a '-diaminodiphenylsulfone residue, a 3,4'-diaminodiphenylsulfone residue, and a divalent group represented by the following general formula (2).
- n represents the number of repeating units and is 1 or more.
- tetracarboxylic acid residue means a residue obtained by removing four carboxyl groups from tetracarboxylic acid, and a residue obtained by removing an acid dianhydride structure from tetracarboxylic dianhydride; Represents the same structure.
- diamine residue refers to a residue obtained by removing two amino groups from a diamine.
- R 3 and R 4 each independently represent a hydrogen atom, an alkyl group, or a perfluoroalkyl group.
- R 5 represents a cyclohexanetetracarboxylic acid residue, a cyclopentanetetracarboxylic acid residue, a dicyclohexane-3,4,3 ′, 4′-tetracarboxylic acid residue, and 4,4 ′.
- At least one tetravalent group selected from the group consisting of-(hexafluoroisopropylidene) diphthalic acid residues R 6 represents a divalent group that is a diamine residue.
- n ′ represents the number of repeating units and is 1 or more.
- R 1 is a tetracarboxylic acid residue, and can be a residue obtained by removing the acid dianhydride structure from the tetracarboxylic dianhydride as exemplified above.
- R 1 in the general formula (1) is, among others, 4,4 ′-(hexafluoroisopropylidene) diphthalic acid residue, 3,3 ′, from the viewpoint of improving light transmittance and improving rigidity.
- these suitable residues are preferably contained in a total amount of 50 mol% or more, more preferably 70 mol% or more, and still more preferably 90 mol% or more.
- R 1 is selected from the group consisting of 3,3 ′, 4,4′-biphenyltetracarboxylic acid residue, 3,3 ′, 4,4′-benzophenonetetracarboxylic acid residue, and pyromellitic acid residue.
- a group of tetracarboxylic acid residues (group A) suitable for improving rigidity such as at least one selected from 4,4 ′-(hexafluoroisopropylidene) diphthalic acid residues, 2,3 ′ , 3,4′-biphenyltetracarboxylic acid residue, 3,3 ′, 4,4′-diphenylsulfonetetracarboxylic acid residue, 4,4′-oxydiphthalic acid residue, cyclohexanetetracarboxylic acid residue, and cyclohexane
- group B suitable for improving transparency, such as at least one selected from the group consisting of pentanetetracarboxylic acid residues.
- the content ratio of the tetracarboxylic acid residue group (group A) suitable for improving the rigidity and the tetracarboxylic acid residue group (group B) suitable for improving transparency is, 0.05 mol of the tetracarboxylic acid residue group (group A) suitable for improving the rigidity is 1 mol per 1 mol of the tetracarboxylic acid residue group (group B) suitable for improving the transparency. It is preferably 9 mol or less, more preferably 0.1 mol or more and 5 mol or less, still more preferably 0.3 mol or more and 4 mol or less.
- R 2 in the general formula (1) is, among others, 4,4′-diaminodiphenylsulfone residue, 3,4′-diaminodiphenylsulfone residue from the viewpoint of improving light transmittance and improving rigidity.
- at least one divalent group selected from the group consisting of a divalent group represented by the general formula (2) and is preferably a 4,4′-diaminodiphenylsulfone residue, 3 , 4′-diaminodiphenylsulfone residue, and at least one divalent group selected from the group consisting of a divalent group represented by the general formula (2) wherein R 3 and R 4 are perfluoroalkyl groups
- the group is preferably.
- R 5 in the general formula (3) is, among others, 4,4 ′-(hexafluoroisopropylidene) diphthalic acid residue, 3,3 ′, from the viewpoint of improving light transmittance and improving rigidity. It preferably contains a 4,4′-diphenylsulfone tetracarboxylic acid residue and an oxydiphthalic acid residue.
- these suitable residues are preferably contained in an amount of 50 mol% or more, more preferably 70 mol% or more, and even more preferably 90 mol% or more.
- R 6 in the general formula (3) is a diamine residue, and can be a residue obtained by removing two amino groups from the diamine as exemplified above.
- R 6 in the general formula (3) is, among others, a 2,2′-bis (trifluoromethyl) benzidine residue, bis [4- (4) from the viewpoint of improving light transmittance and improving rigidity.
- these suitable residues are preferably contained in a total amount of 50 mol% or more, more preferably 70 mol% or more, and still more preferably 90 mol% or more.
- R 6 is a bis [4- (4-aminophenoxy) phenyl] sulfone residue, 4,4′-diaminobenzanilide residue, N, N′-bis (4-aminophenyl) terephthalamide residue, A group of diamine residues suitable for improving the rigidity such as at least one selected from the group consisting of a paraphenylenediamine residue, a metaphenylenediamine residue, and a 4,4′-diaminodiphenylmethane residue (group) C), 2,2′-bis (trifluoromethyl) benzidine residue, 4,4′-diaminodiphenylsulfone residue, 2,2-bis [4- (4-aminophenoxy) phenyl] hexafluoropropane residue Group, bis [4- (3-aminophenoxy) phenyl] sulfone residue, 4,4′-diamino-2,2′-bis (trifluoromethyl) diphen
- the content ratio of the diamine residue group (group C) suitable for improving the rigidity and the diamine residue group (group D) suitable for improving transparency improves transparency.
- the diamine residue group (group C) suitable for improving the rigidity is 0.05 mol or more and 9 mol or less with respect to 1 mol of the diamine residue group (group D) suitable for the treatment. More preferably, it is preferably 0.1 mol or more and 5 mol or less, and more preferably 0.3 mol or more and 4 mol or less.
- the number of repeating units n in the polyimide is not particularly limited as long as it is appropriately selected depending on the structure so as to exhibit a preferable glass transition temperature described later.
- the average number of repeating units is usually 10 to 2000, and more preferably 15 to 1000.
- the polyimide resin may contain a polyamide structure in a part thereof.
- the polyamide structure examples include a polyamideimide structure containing a tricarboxylic acid residue such as trimellitic anhydride and a polyamide structure containing a dicarboxylic acid residue such as terephthalic acid.
- the polyimide resin preferably has a glass transition temperature of 250 ° C. or higher, and more preferably 270 ° C. or higher, from the viewpoint of heat resistance.
- the glass transition temperature is preferably 400 ° C. or lower, and more preferably 380 ° C. or lower, from the viewpoint of easy stretching and reduction of the baking temperature.
- examples of the polyimide resin include compounds having a structure represented by the following formula.
- n is a repeating unit and represents an integer of 2 or more.
- Polyamide resin is a concept including not only aliphatic polyamide but also aromatic polyamide (aramid).
- the polyamide resin generally has a skeleton represented by the following formulas (21) and (22).
- Examples of the polyamide resin include compounds represented by the following formula (23). .
- n is a repeating unit and represents an integer of 2 or more.
- Examples of the commercially available base material made of the polyimide resin include, for example, Neoprim manufactured by Mitsubishi Gas Chemical Co., Ltd., and examples of the commercially available base material made of the aramid resin include, for example, Mikutron manufactured by Toray Industries, Inc. It is done.
- the polyimide resin or polyamide resin represented by the above formulas (4) to (20) and (23) may be synthesized by a known method.
- a method for synthesizing a polyimide resin represented by the above formula (4) is described in Japanese Patent Application Laid-Open No. 2009-132091, and specifically, 4,4′-hexafluoro represented by the following formula (24): It can be obtained by reacting propylidenebisphthalic dianhydride (FPA) with 2,2′-bis (trifluoromethyl) -4,4′-diaminobiphenyl (TFDB).
- FPA propylidenebisphthalic dianhydride
- TFDB 2,2′-bis (trifluoromethyl) -4,4′-diaminobiphenyl
- the weight average molecular weight of the polyimide resin or polyamide resin is preferably in the range of 3,000 to 500,000, more preferably in the range of 5,000 to 300,000, and in the range of 10,000 to 200,000. Further preferred. When the weight average molecular weight is less than 3000, sufficient strength may not be obtained. When the weight average molecular weight exceeds 500,000, the viscosity increases and the solubility decreases, so that a substrate having a smooth surface and a uniform film thickness can be obtained. It may not be obtained.
- the “weight average molecular weight” is a polystyrene conversion value measured by gel permeation chromatography (GPC).
- a polyimide resin or an aramid resin having a structure in which charge transfer within a molecule or between molecules hardly occurs is preferable because it has excellent transparency.
- polyimide resins having an alicyclic structure such as the above formulas (13) to (15)
- polyamide resins having a halogen group such as the above formula (23).
- the fluorinated polyimide resins of the above formulas (4) to (11) have a fluorinated structure and thus have high heat resistance, and are colored by the heat during the production of the substrate made of the polyimide resin. Therefore, it has excellent transparency.
- the resin base material 11 is made of a fluorinated polyimide resin represented by the above formulas (4) to (11) or an aramid resin having a halogen group such as the above formula (23) from the viewpoint of improving the hardness. It is preferable to use a substrate. Especially, it is more preferable to use the base material which consists of a polyimide resin represented by the said Formula (4) from a viewpoint which can improve hardness more.
- polyester resin examples include resins containing at least one of polyethylene terephthalate, polypropylene terephthalate, polybutylene terephthalate, and polyethylene naphthalate as constituent components.
- the hard coat layer 12 means a layer having a Martens hardness at the center of the cross section of the hard coat layer 12 of 375 MPa or more.
- the “Martens hardness” is the hardness when the indenter is pushed in by 500 nm by the hardness measurement by the nanoindentation method.
- the measurement of the Martens hardness by the nanoindentation method is performed using “TI950 TriboIndenter” manufactured by HYSITRON. That is, under the following measurement conditions, a Berkovich indenter (triangular pyramid) as the above indenter was pushed into the center of the cross section of the hard coat layer by 500 nm and held for a certain period of time to relieve the residual stress.
- the maximum load is measured, and the Martens hardness is calculated by P max / A using the maximum load P max ( ⁇ N) and the indentation area A (nm 2 ) having a depth of 500 nm.
- the Martens hardness is the arithmetic average value of the values obtained by measuring 10 locations. (Measurement condition) ⁇ Loading speed: 10 nm / second ⁇ Retention time: 5 seconds ⁇ Load unloading speed: 10 nm / second ⁇ Measurement temperature: 25 ° C.
- the film thickness of the hard coat layer 12 is preferably 1 ⁇ m or more and 20 ⁇ m or less. If the thickness of the hard coat layer 12 is less than 1 ⁇ m, the hardness of the hard coat layer may be reduced, and if it exceeds 20 ⁇ m, the workability may be deteriorated due to the thickness being too thick. .
- the “film thickness of the hard coat layer” means the total film thickness (total thickness) of the hard coat layers when the hard coat layer has a multilayer structure. To do.
- the upper limit of the hard coat layer 12 is more preferably 15 ⁇ m or less, and further preferably 10 ⁇ m or less.
- the film thickness of the hard coat layer is obtained by photographing a cross section of the hard coat layer using a scanning electron microscope (SEM), measuring 20 film thicknesses of the hard coat layer in the image of the cross section, The arithmetic average value of thickness.
- SEM scanning electron microscope
- a specific method for taking a cross-sectional photograph is described below.
- a block is prepared by embedding an optical film cut into 1 mm ⁇ 10 mm with an embedding resin, and a uniform section having a thickness of 70 nm or more and 100 nm or less without holes is cut out from this block by a general section preparation method. .
- “Ultra Microtome EM UC7” Leica Microsystems Co., Ltd.
- the remaining block from which a uniform section without holes or the like is cut out is taken as a measurement sample. Thereafter, a cross-sectional photograph of the measurement sample is taken using a scanning electron microscope (SEM) (product name “S-4800”, manufactured by Hitachi High-Technologies Corporation).
- SEM scanning electron microscope
- the cross-section is observed with the detector set to “SE”, the acceleration voltage set to “5 kV”, and the emission current set to “10 ⁇ A”.
- the magnification is appropriately adjusted from 100 to 100,000 times while adjusting the focus and observing whether each layer can be distinguished.
- the aperture is set to “beam monitor aperture 3”
- the objective lens aperture is set to “3”
- D. May be set to “8 mm”.
- the interface contrast between the hard coat layer and another layer for example, a resin substrate
- a dyeing process such as osmium tetroxide, ruthenium tetroxide, or phosphotungstic acid can be used to easily see the interface between the organic layers.
- the interface contrast may be difficult to understand when the magnification is high. In that case, the low magnification is also observed at the same time. For example, it is observed at two magnifications, such as 25,000 times and 50,000 times, and 50,000 times and 100,000 times, and the above-mentioned arithmetic average value is obtained at both magnifications. The value of the film thickness.
- the hard coat layer may have a single layer structure, but is preferably a multilayer structure of two or more layers from the viewpoint of improving folding performance.
- FIG. 1 shows an example in which the hard coat layer 12 is composed of a first hard coat layer 12B and a second hard coat layer 12C laminated on the first hard coat layer 12B. Yes.
- the first hard coat layer 12B is a layer mainly for imparting hardness to the optical film.
- the first hard coat layer 12B preferably has a Martens hardness of 500 MPa to 2000 MPa in the center of the cross section of the first hard coat layer 12B. If it is less than 500 MPa, the hardness of the hard coat layer may be insufficient, and if it exceeds 2000 MPa, the folding performance of the optical film may be insufficient.
- the lower limit of the Martens hardness at the center of the cross section of the first hard coat layer 12B is preferably 600 MPa or more, and the upper limit is preferably 1500 MPa or less.
- the Martens hardness of the first hard coat layer 12B is preferably larger than the Martens hardness of the second hard coat layer 12C.
- the optical film 10 has particularly good pencil hardness. This is because when the pencil hardness test is performed on the optical film 10 and the pencil is loaded with a load, the deformation of the optical film 10 is suppressed and the scratches and the dent deformation are reduced.
- the Martens hardness of the first hard coat layer 12B larger than the Martens hardness of the second hard coat layer 12C for example, the content of inorganic particles described later is more contained on the first hard coat layer 12B side. And a method of controlling to do so.
- the inorganic particles are unevenly distributed on the substrate film side in the hard coat layer, that is, the proportion of the inorganic particles in the hard coat layer is on the resin substrate side. It is preferable to be inclined so as to be larger and smaller toward the surface side of the optical film.
- the first hard coat layer 12B contains a resin.
- the first hard coat layer 12B preferably further contains inorganic particles dispersed in the resin.
- the resin contains a polymer (cured product) of a polymerizable compound (curable compound).
- the polymerizable compound has at least one polymerizable functional group in the molecule.
- the polymerizable functional group include ethylenically unsaturated groups such as a (meth) acryloyl group, a vinyl group, and an allyl group.
- the “(meth) acryloyl group” means to include both “acryloyl group” and “methacryloyl group”.
- polyfunctional (meth) acrylate is preferable.
- the polyfunctional (meth) acrylate include trimethylolpropane tri (meth) acrylate, tripropylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, dipropylene glycol di (meth) acrylate, pentaerythritol tri ( (Meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate, 1,6-hexanediol di (meth) acrylate, neopentyl glycol di (meth) acrylate, trimethylolpropane tri (meth) acrylate , Ditrimethylolpropane tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, tripentaerythr
- those having 3 to 6 functional groups are preferable because they can satisfy the above-mentioned Martens hardness, and examples thereof include pentaerythritol triacrylate (PETA), dipentaerythritol hexaacrylate (DPHA), and pentaerythritol tetraacrylate (PETTA). Dipentaerythritol pentaacrylate (DPPA), trimethylolpropane tri (meth) acrylate, tripentaerythritol octa (meth) acrylate, tetrapentaerythritol deca (meth) acrylate, and the like are preferable.
- (meth) acrylate means acrylate and methacrylate.
- a monofunctional (meth) acrylate monomer may be further included for adjusting the hardness, the viscosity of the composition, improving the adhesion, and the like.
- the monofunctional (meth) acrylate monomer include hydroxyethyl acrylate (HEA), glycidyl methacrylate, methoxypolyethylene glycol (meth) acrylate, isostearyl (meth) acrylate, 2-acryloyloxyethyl succinate, acryloylmorpholine, N -Acryloyloxyethyl hexahydrophthalimide, cyclohexyl acrylate, tetrahydrofuryl acrylate, isobornyl acrylate, phenoxyethyl acrylate, adamantyl acrylate and the like.
- HOA hydroxyethyl acrylate
- glycidyl methacrylate methoxypolyethylene glycol (meth) acrylate
- the weight average molecular weight of the monomer is preferably less than 1000, more preferably 200 or more and 800 or less, from the viewpoint of improving the hardness of the resin layer.
- the weight average molecular weight of the polymerizable oligomer is preferably 1000 or more and 20,000 or less, more preferably 1000 or more and 10,000 or less, and further preferably 2000 or more and 7000 or less.
- the inorganic particles are not particularly limited as long as the hardness can be improved, but silica particles are preferable from the viewpoint of obtaining excellent hardness.
- silica particles are preferred.
- the reactive silica particles are silica particles that can form a crosslinked structure with the polyfunctional (meth) acrylate. By containing the reactive silica particles, the first hard coat layer 12B. Can be sufficiently increased in hardness.
- the reactive silica particles preferably have a reactive functional group on the surface, and for example, the polymerizable functional group is preferably used as the reactive functional group.
- the reactive silica particles are not particularly limited, and conventionally known reactive silica particles can be used, and examples thereof include reactive silica particles described in JP-A-2008-165040.
- Examples of commercially available reactive silica particles include, for example, Nissan Chemical Industries, Ltd .; MIBK-SD, MIBK-SDMS, MIBK-SDL, MIBK-SDZL, JGC Catalysts &Chemicals; V8802, V8803, and the like. .
- the silica particles may be spherical silica particles, but are preferably irregular silica particles. Spherical silica particles and irregular-shaped silica particles may be mixed.
- spherical silica particles means, for example, silica particles such as spherical and elliptical spheres, and “deformed silica particles” are potato-shaped (with an aspect ratio of 1 during cross-sectional observation). .2 or more and 40 or less) means a silica particle having a shape having random irregularities on the surface.
- the irregular-shaped silica particles have a surface area larger than that of the spherical silica particles, the inclusion of such irregular-shaped silica particles increases the contact area with the polyfunctional (meth) acrylate and the hard coat.
- the hardness of the layer can be improved. Whether or not the silica particles contained in the hard coat layer are irregularly shaped silica particles is confirmed by observing the cross section of the hard coat layer with a transmission electron microscope (TEM) or a scanning transmission electron microscope (STEM). be able to.
- TEM transmission electron microscope
- STEM scanning transmission electron microscope
- the average particle size of the silica particles is preferably 5 nm or more and 200 nm or less. If the thickness is less than 5 nm, it may be difficult to produce the particles themselves, the particles may aggregate together, and it may be extremely difficult to deform the ink. In some stages, the dispersible silica particles may be poorly dispersed and may aggregate. On the other hand, when the average particle size of the irregular shaped silica particles exceeds 200 nm, large irregularities may be formed in the hard coat layer, and problems such as an increase in haze may occur.
- the average particle diameter of the silica particles is 20 particles from the cross-sectional image of the particles taken using a transmission electron microscope (TEM) or a scanning transmission electron microscope (STEM). The particle diameter is measured to obtain the arithmetic average value of the particle diameters of 20 particles.
- the average particle diameter of the silica particles is an image of a cross section of the hard coat layer taken using a transmission electron microscope (TEM) or a scanning transmission electron microscope (STEM).
- the maximum value (major axis) and the minimum value (minor axis) of the distance between two points on the outer periphery of the particle are measured and averaged to obtain the particle size, which is the arithmetic average value of the particle size of 20 particles.
- the hardness (Martens hardness) of the first hard coat layer 12B can be controlled by controlling the size and blending amount of the inorganic particles.
- the silica particles when forming the first hard coat layer 12B, have a diameter of 5 nm or more and 200 nm or less, and preferably 25 to 60 parts by mass with respect to 100 parts by mass of the polymerizable compound.
- the second hard coat layer 12C is a layer for satisfying the above-described continuous folding test.
- the second hard coat layer 12C preferably has a Martens hardness of 375 MPa or more and 1500 MPa or less at the center of the cross section of the second hard coat layer 12C. If it is less than 375 MPa, the scratch resistance of the hard coat layer may be insufficient. If it exceeds 1500 MPa, the folding performance of the optical film may be insufficient and the above-described continuous folding test may not be satisfied.
- the lower limit of the Martens hardness at the center of the cross section of the second hard coat layer 12C is more preferably 450 MPa or more, and the upper limit is more preferably 575 MPa or less.
- the second hard coat layer 12C contains a resin.
- the second hard coat layer 12C may further include inorganic particles dispersed in the resin.
- the resin contains a polymer (cured product) of a polymerizable compound (curable compound).
- a polymerizable compound curable compound
- polyfunctional (meth) acrylate is preferable.
- the thing similar to the polyfunctional (meth) acrylate of the column of the 1st hard-coat layer 12B is mentioned.
- the second hard coat layer 12C may include polyfunctional urethane (meth) acrylate and / or polyfunctional epoxy (meth) acrylate.
- inorganic particles examples include those similar to the inorganic particles in the column of the first hard coat layer 12B.
- the content of the inorganic particles in the second hard coat layer 12C is not particularly limited, but for example, it is preferably 0 to 50% by mass with respect to the second hard coat layer 12C.
- At least one of the first hard coat layer 12B and the second hard coat layer 12C may contain a material other than the above-described materials as long as the above-described Martens hardness is satisfied. As above, it may contain a polymerizable monomer or a polymerizable oligomer that forms a cured product by irradiation with ionizing radiation.
- the polymerizable monomer or polymerizable oligomer include a (meth) acrylate monomer having a radically polymerizable unsaturated group in the molecule, or a (meth) acrylate oligomer having a radically polymerizable unsaturated group in the molecule. It is done.
- Examples of the (meth) acrylate monomer having a radically polymerizable unsaturated group in the molecule or the (meth) acrylate oligomer having a radically polymerizable unsaturated group in the molecule include urethane (meth) acrylate and polyester (meth) ) Acrylates, epoxy (meth) acrylates, melamine (meth) acrylates, polyfluoroalkyl (meth) acrylates, and silicone (meth) acrylate monomers or oligomers. These polymerizable monomers or polymerizable oligomers may be used alone or in combination of two or more. Among these, urethane (meth) acrylate having polyfunctionality (6 functionalities or more) and having a weight average molecular weight of 1,000 to 10,000 is preferable.
- the hard coat layer 12 (at least one of the first hard coat layer 12B and the second hard coat layer 12C) may further contain an ultraviolet absorber, a spectral transmittance adjusting agent, and / or an antifouling agent. .
- the optical film is particularly preferably used for a mobile terminal such as a foldable smartphone or tablet terminal.
- a mobile terminal is often used outdoors, and therefore, the optical film is disposed closer to the display element than the optical film.
- the polarizer is easily deteriorated by being exposed to ultraviolet rays.
- the resin layer is arranged on the display screen side of the polarizer, when the ultraviolet absorber is contained in the resin layer, deterioration due to exposure of the polarizer to ultraviolet rays can be suitably prevented.
- the ultraviolet absorber (UVA) may be contained in the resin base material 11 and / or the resin layer 13. In this case, the ultraviolet absorber (UVA) may not be contained in the hard coat layer 12.
- ultraviolet absorbers examples include triazine-based ultraviolet absorbers, benzophenone-based ultraviolet absorbers, and benzotriazole-based ultraviolet absorbers.
- Examples of the triazine ultraviolet absorber include 2- (2-hydroxy-4- [1-octyloxycarbonylethoxy] phenyl) -4,6-bis (4-phenylphenyl) -1,3,5-triazine.
- benzophenone ultraviolet absorber examples include 2-hydroxybenzophenone, 2,4-dihydroxybenzophenone, 2,2′-dihydroxy-4,4′-dimethoxybenzophenone, 2,2 ′, 4,4′-tetrahydroxy. Examples thereof include benzophenone, 2-hydroxy-4-methoxybenzophenone, hydroxymethoxybenzophenone sulfonic acid and its trihydrate, hydroxymethoxybenzophenone sulfonate sodium, and the like. Examples of commercially available benzophenone ultraviolet absorbers include CHMASSORB81 / FL (manufactured by BASF).
- benzotriazole ultraviolet absorber examples include 2-ethylhexyl-3- [3-tert-butyl-4-hydroxy-5- (5-chloro-2H-benzotriazol-2-yl) phenyl] propionate, 2 -(2H-benzotriazol-2-yl) -6- (linear and side chain dodecyl) -4-methylphenol, 2- [5-chloro (2H) -benzotriazol-2-yl] -4-methyl- 6- (tert-butyl) phenol, 2- (2H-benzotriazol-2-yl) -4,6-di-tert-pentylphenol, 2- (2′-hydroxy-5′-methylphenyl) benzotriazole, 2- (2′-hydroxy-3 ′, 5′-di-tert-butylphenyl) benzotriazole, 2- (2′-hydroxy-3) -Tert-butyl-5'-methylphenyl) benzotriazole, 2- (2'-
- benzotriazole ultraviolet absorbers examples include KEMISORB71D, KEMISORB79 (all manufactured by Chemipro Kasei Co., Ltd.), JF-80, JAST-500 (all manufactured by Johoku Chemical Co., Ltd.), ULS-1933D (one side) And RUVA-93 (manufactured by Otsuka Chemical Co., Ltd.).
- triazine ultraviolet absorbers and benzotriazole ultraviolet absorbers are preferably used as the ultraviolet absorber. It is preferable that the ultraviolet absorber has high solubility with the resin component constituting the hard coat layer, and it is preferable that the bleed-out after the continuous folding test described above is small.
- the ultraviolet absorber is preferably polymerized or oligomerized.
- a polymer or oligomer having a benzotriazole, triazine, or benzophenone skeleton is preferable. Specifically, (meth) acrylate having a benzotriazole or benzophenone skeleton and methyl methacrylate (MMA) at an arbitrary ratio. It is preferable that it has been heat copolymerized.
- the ultraviolet absorber can also serve to protect the OLED from ultraviolet rays.
- a ultraviolet absorber Although it does not specifically limit as content of a ultraviolet absorber, It is preferable that they are 1 mass part or more and 6 mass parts or less with respect to 100 mass parts of solid content of the composition for hard-coat layers. If the amount is less than 1 part by mass, the effect of containing the above-described ultraviolet absorber in the hard coat layer may not be obtained sufficiently. Sometimes.
- the minimum with more preferable content of the said ultraviolet absorber is 2 mass parts or more, and a more preferable upper limit is 5 mass parts or less.
- the spectral transmittance adjusting agent adjusts the spectral transmittance of the optical film.
- the hard coat layer 12 contains a sesamol type benzotriazole monomer represented by the following general formula (25)
- the above-described spectral transmittance can be preferably satisfied.
- R 7 represents a hydrogen atom or a methyl group.
- R 8 represents a linear or branched alkylene group having 1 to 6 carbon atoms or a linear or branched oxyalkylene group having 1 to 6 carbon atoms.
- the sesamol type benzotriazole monomer is not particularly limited, but specific substance names include 2- [2- (6-hydroxybenzo [1,3] dioxol-5-yl) -2H-benzo Triazol-5-yl] ethyl methacrylate, 2- [2- (6-hydroxybenzo [1,3] dioxol-5-yl) -2H-benzotriazol-5-yl] ethyl acrylate, 3- [2- (6 -Hydroxybenzo [1,3] dioxol-5-yl) -2H-benzotriazol-5-yl] propyl methacrylate, 3- [2- (6-hydroxybenzo [1,3] dioxol-5-yl) -2H -Benzotriazol-5-yl] propyl acrylate, 4- [2- (6-hydroxybenzo [1,3] dioxol-5-yl -2H-benzotriazol-5-yl] butyl methacrylate, 4- [2- (6-
- the sesamol type benzotriazole-based monomer may be contained in the resin layer 13, but when the resin layer has a multilayer structure of two or more, it is contained in one or more resin layers, and The transmittance requirement may be met.
- the sesamol type benzotriazole-based monomer is contained in one of the resin layers so that only the spectral transmittance at a wavelength of 380 nm can be achieved, and the spectral transmittance conditions at a wavelength of 410 nm and a wavelength of 440 nm are set in the other resin layers.
- the structure etc. which contain the said sesamol type benzotriazole type monomer so that it may be achieved are mentioned.
- the resin layer may be composed of three or more layers, and each resin layer may contain the sesamol type benzotriazole monomer so as to satisfy the above-described spectral transmittance requirement.
- the sesamol type benzotriazole monomer When the sesamol type benzotriazole monomer is contained in the resin layer 13, for example, the sesamol type benzotriazole monomer may be contained in 15 to 30% by mass in the 13 resin layers. preferable. When the sesamol type benzotriazole monomer is contained in such a range, the above-described spectral transmittance can be satisfied.
- the sesamol type benzotriazole-based monomer may be contained in the resin layer 13 by reacting with the resin component constituting the resin layer 13 and reacting with the resin component constituting the resin layer 13. It may be contained alone without doing.
- the antifouling agent may be uniformly dispersed in the hard coat layer. However, from the viewpoint of obtaining sufficient antifouling properties with a small addition amount and suppressing the strength reduction of the hard coat layer. It is preferable that it is unevenly distributed on the surface side. When the hard coat layer has a single layer structure, the antifouling agent is unevenly distributed on the surface side of the hard coat layer. For example, when the hard coat layer is formed, a coating formed using the composition for the hard coat layer is used.
- the antifouling agent Before drying and curing the film, heating the coating film to increase the fluidity by lowering the viscosity of the resin component contained in the coating film, so that the antifouling agent is unevenly distributed on the surface side of the hard coat layer Or, select and use an antifouling agent with a low surface tension, float the antifouling agent on the surface of the paint film without applying heat when drying the paint film, and then cure the paint film. Examples thereof include a method of uneven distribution on the outermost surface side of the hard coat layer. When the hard coat layer has a multilayer structure like the hard coat layer 12, the antifouling agent can be unevenly distributed on the surface side of the hard coat layer by containing the antifouling agent in the hard coat layer on the surface side. it can.
- the antifouling agent is not particularly limited, and examples thereof include silicone antifouling agents, fluorine antifouling agents, silicone and fluorine antifouling agents, which may be used alone or in combination. May be.
- the antifouling agent may be an acrylic antifouling agent.
- the content of the antifouling agent is preferably 0.01 to 3.0 parts by mass with respect to 100 parts by mass of the resin component described above. If it is less than 0.01 part by mass, sufficient antifouling performance may not be imparted to the resin layer, and if it exceeds 3.0 parts by mass, the hardness of the hard coat layer may be reduced.
- the antifouling agent preferably has a weight average molecular weight of 5000 or less, and is a compound having preferably 1 or more, more preferably 2 or more reactive functional groups in order to improve the durability of the antifouling performance. Among them, excellent scratch resistance can be imparted by using an antifouling agent having two or more reactive functional groups.
- the antifouling agent does not have a reactive functional group
- the antifouling agent is transferred to the back surface of the optical film when it is stacked, whether it is a roll or a sheet.
- the other layer may be peeled off and may be easily peeled off by performing a plurality of continuous folding tests.
- the antifouling agent having the reactive functional group has good performance (durability) of antifouling performance, and in particular, the hard coat layer containing the above-described fluorine antifouling agent is difficult to have fingerprints. (Not easily noticeable) and good wipeability. Furthermore, since the surface tension at the time of coating of the composition for hard coat layers can be lowered, the leveling property is good, and the appearance of the hard coat layer to be formed is good.
- the hard coat layer containing a silicone antifouling agent has good sliding properties and good steel wool resistance.
- a touch sensor in which an optical film containing such a silicone antifouling agent is mounted on a hard coat layer has a good tactile sensation because of good sliding when touched with a finger or a pen.
- fingerprints are hardly attached to the hard coat layer (not easily noticeable), and the wiping property is improved.
- the surface tension at the time of coating of the composition for hard coat layers can be lowered, the leveling property is good, and the appearance of the hard coat layer to be formed is good.
- silicone antifouling agents examples include SUA1900L10 (manufactured by Shin-Nakamura Chemical Co., Ltd.), SUA1900L6 (manufactured by Shin-Nakamura Chemical Co., Ltd.), Ebecryl 1360 (manufactured by Daicel Cytec Co., Ltd.), UT3971 (manufactured by Nippon Gosei Co., Ltd.), and BYKUV3500 (BIC Chemie).
- SUA1900L10 manufactured by Shin-Nakamura Chemical Co., Ltd.
- SUA1900L6 manufactured by Shin-Nakamura Chemical Co., Ltd.
- Ebecryl 1360 manufactured by Daicel Cytec Co., Ltd.
- UT3971 manufactured by Nippon Gosei Co., Ltd.
- BYKUV3500 BIC Chemie
- BYKUV3510 by Big Chemie
- BYKUV3570 by Big Chemie
- X22-164E X22-174BX
- X22-2426 KBM503, KBM5103
- TEGO-RAD2250 TEGO-RAD2300
- TEGO-RAD2200N TEGO-RAD2010
- TEGO-RAD2500 TEGO-RAD2600
- TEGO-RAD2700 manufactured by Evonik Japan
- Megafuck RS854 (DIC) Ltd. and the like.
- fluorine-based antifouling agents include, for example, OPTOOL DAC, OPTOOL DSX (manufactured by Daikin Industries, Ltd.), Megafuck RS71, Megafuck RS74 (manufactured by DIC), LINC152EPA, LINC151EPA, and LINC182UA (manufactured by Kyoeisha Chemical Co., Ltd.)
- the solvent include 650A, 601ENT, 602, and 602.
- Examples of commercially available antifouling agents having fluorine-based and silicone-based reactive functional groups include, for example, MegaFac RS851, MegaFac RS852, MegaFac RS853, MegaFac RS854 (manufactured by DIC), Opstar TU2225, Opstar TU2224 ( JSR), X71-1203M (Shin-Etsu Chemical Co., Ltd.) and the like.
- the resin layer 13 is a layer made of a resin having optical transparency.
- the resin layer 13 is a layer having shock absorption.
- the resin layer may have a multilayer structure including two or more resin layers.
- the film thickness of the resin layer 13 is 50 ⁇ m or more and 300 ⁇ m or less. If the thickness of the resin layer 13 is less than 50 ⁇ m, the hardness of the resin layer may be reduced, and if it exceeds 300 ⁇ m, the film thickness is too thick, so that it is not suitable for thinning and the workability deteriorates. There is a fear.
- the film thickness of the resin layer is obtained by photographing a cross section of the resin layer using a scanning electron microscope (SEM), measuring 20 film thicknesses of the resin layer in the image of the cross section, and calculating the film thickness of the 20 positions. Average value.
- the method for taking a cross-sectional photo of the resin layer is the same as the method for taking a cross-sectional photo of the hard coat layer.
- the lower limit of the resin layer 13 is more preferably 60 ⁇ m or more, the upper limit of the resin layer 13 is more preferably 150 ⁇ m or less, and further preferably 100 ⁇ m or less.
- the resin constituting the resin layer 13 is a resin in which the shear storage elastic modulus G ′ and the shear loss elastic modulus G ′′ in the frequency range of 25 ° C. and 500 Hz Hz to 1000 Hz in the optical film 10 are within the above ranges.
- resins include acrylic gels, urethane gels, silicone gels, urethane resins, and epoxy resins. Among these, acrylic gel is preferable.
- “Gel” generally refers to a dispersion having high viscosity and loss of fluidity.
- the resin layer 13 may contain rubber
- acrylic gel As the acrylic gel, various polymers can be used as long as they are polymers obtained by polymerizing a monomer containing an acrylate ester used for an adhesive or the like. Specifically, examples of acrylic gels include ethyl (meth) acrylate, n-propyl (meth) acrylate, i-propyl (meth) acrylate, n-butyl (meth) acrylate, and i-butyl (meth) acrylate.
- the urethane-based resin is a resin having a urethane bond.
- the urethane resin include a cured product of an ionizing radiation curable urethane resin composition and a cured product of a thermosetting urethane resin composition.
- a cured product of an ionizing radiation-curable urethane resin composition is preferable from the viewpoint of obtaining high hardness, high curing speed, and excellent mass productivity.
- the ionizing radiation curable urethane-based resin composition includes urethane (meth) acrylate, and the thermosetting urethane-based resin includes a polyol compound and an isocyanate compound.
- the urethane (meth) acrylate, polyol compound, and isocyanate compound may be any of a monomer, an oligomer, and a prepolymer.
- the number of (meth) acryloyl groups (the number of functional groups) in the urethane (meth) acrylate is preferably 2 or more and 4 or less. If the number of (meth) acryloyl groups in the urethane (meth) acrylate is less than 2, the pencil hardness may be lowered, and if it exceeds 4, the curing shrinkage increases and the optical film curls. In addition, there is a risk of cracks in the resin layer during bending.
- the upper limit of the number of (meth) acryloyl groups in the urethane (meth) acrylate is more preferably 3 or less.
- the “(meth) acryloyl group” means to include both “acryloyl group” and “methacryloyl group”.
- the weight average molecular weight of urethane (meth) acrylate is preferably 1500 or more and 20000 or less. If the weight average molecular weight of the urethane (meth) acrylate is less than 1500, the impact resistance may be lowered. If it exceeds 20000, the viscosity of the ionizing radiation-curable urethane resin composition increases, and the coating is applied. May deteriorate.
- the lower limit of the weight average molecular weight of the urethane (meth) acrylate is more preferably 2000 or more, and the upper limit is more preferably 15000 or less.
- R 9 represents a branched alkyl group
- R 10 represents a branched alkyl group or a saturated cycloaliphatic group
- R 11 represents a hydrogen atom or a methyl group
- R 12 represents ,
- m represents an integer of 0 or more
- x represents an integer of 0 to 3.
- R 9 represents a branched chain alkyl group
- R 10 represents a branched alkyl group or a saturated cyclic aliphatic group
- R 11 represents a hydrogen atom or a methyl group
- R 12 is , Represents a hydrogen atom, a methyl group or an ethyl group
- n represents an integer of 1 or more
- x represents an integer of 0 to 3.
- R 9 represents a branched alkyl group
- R 10 represents a branched alkyl group or a saturated cycloaliphatic group
- R 11 represents a hydrogen atom or a methyl group
- R 12 represents ,
- m represents an integer of 0 or more
- x represents an integer of 0 to 3.
- R 9 represents a branched alkyl group
- R 10 represents a branched alkyl group or a saturated cycloaliphatic group
- R 11 represents a hydrogen atom or a methyl group
- R 12 represents , Represents a hydrogen atom, a methyl group or an ethyl group
- n represents an integer of 1 or more
- x represents an integer of 0 to 3.
- the structure of the resin constituting the resin layer 13 is formed by a polymer chain (repeating unit) by analyzing the resin layer 13 by pyrolysis GC-MS and FT-IR, for example. Judgment is possible.
- pyrolysis GC-MS is useful because it can detect monomer units contained in the resin layer 13 as monomer components.
- the resin layer 13 is a UV absorber, spectral transmission A rate adjusting agent, an antifouling agent, inorganic particles and / or organic particles may be included.
- the ultraviolet absorber and the like those similar to the ultraviolet absorber and the like described in the column of the hard coat layer 12 can be used, and therefore description thereof is omitted here.
- the resin layer 13 is directly provided on the second surface 11B of the resin base material 11, but as the optical film, the resin layer is formed on the resin base material via the adhesive layer.
- a pasted optical film may be used.
- the optical film 40 shown in FIG. 5 includes the resin base material 11, the hard coat layer 12 provided on the first surface 11 ⁇ / b> A side of the resin base material 11, and the first base of the resin base material 11.
- the resin layer 13 provided in the 2nd surface 11B side which is a surface on the opposite side to the surface 11A, and the adhesion layer 41 interposed between the resin base material 11 and the resin layer 13 are provided.
- the resin layer 13 is affixed to the resin base material 11 via the adhesive layer 41.
- members having the same reference numerals as those in FIG. 1 are the same as the members shown in FIG.
- the surface 40 ⁇ / b> A of the optical film 40 is the surface 12 ⁇ / b> A of the hard coat layer 12.
- the back surface 40 ⁇ / b> B of the optical film 40 is a surface 13 ⁇ / b> A opposite to the surface on the resin base material 11 side in the resin layer 13.
- the shear storage modulus G ′ in the frequency range of 25 ° C. and 500 Hz to 1000 Hz is more than 200 MPa and not more than 1200 MPa, and the shear loss in the frequency range of 25 ° C. and 500 Hz to 1000 Hz.
- the elastic modulus G ′′ is 3 MPa or more and 150 MPa or less.
- the shear storage elastic modulus G ′ and the shear loss elastic modulus G ′′ in the optical film 40 are measured by the same method as the shear storage elastic modulus G ′ and the shear loss elastic modulus G ′′ in the optical film 10. Since the other physical properties of the optical film 40 are the same as those of the optical film 10, the description thereof is omitted here.
- the adhesive layer 41 may be an adhesive film. Although it does not specifically limit as the adhesion layer 41, For example, OCA (Optical Clear Adhesive) can be used.
- the thickness of the adhesive layer 41 is preferably 5 ⁇ m or more. When the film thickness of the adhesive layer 41 is 5 ⁇ m or more, the resin layer 13 can be reliably attached to the resin base material 11.
- the lower limit of the thickness of the adhesive layer 41 is preferably 50 ⁇ m or less from the viewpoint of reducing the thickness.
- the optical film 10 can be produced by various methods depending on the type of resin constituting the resin layer 13.
- the resin layer 13 is a layer made of an acrylic gel
- it can be produced as follows, for example. First, on the first surface 11A of the resin substrate 11, the first hard coat layer composition is applied by a coating device such as a bar coater, and the first hard coat layer composition coating is applied. Form.
- the first hard coat layer composition contains a polymerizable compound for forming the first hard coat layer 12B.
- the first hard coat layer composition may further contain an ultraviolet absorber, a spectral transmittance adjusting agent, an antifouling agent, inorganic particles, a leveling agent, a solvent, and a polymerization initiator, if necessary.
- solvent examples include alcohols (eg, methanol, ethanol, propanol, isopropanol, n-butanol, s-butanol, t-butanol, benzyl alcohol, PGME, ethylene glycol, diacetone alcohol), ketones (eg, acetone, methyl ethyl ketone, Methyl isobutyl ketone, cyclopentanone, cyclohexanone, heptanone, diisobutyl ketone, diethyl ketone, diacetone alcohol), ester (methyl acetate, ethyl acetate, butyl acetate, n-propyl acetate, isopropyl acetate, methyl formate, PGMEA), aliphatic Hydrocarbons (eg, hexane, cyclohexane), halogenated hydrocarbons (eg, methylene chloride, chloroform,
- alcohols
- solvents may be used alone or two or more of them may be used in combination.
- methyl isobutyl ketone can be suitably applied to the first hard coat layer composition by dissolving or dispersing components such as urethane (meth) acrylate and other additives. Methyl ethyl ketone is preferred.
- the polymerization initiator is a component that is decomposed by irradiation with ionizing radiation to generate radicals to initiate or advance polymerization (crosslinking) of the polymerizable compound.
- the polymerization initiator is not particularly limited as long as it can release a substance that initiates radical polymerization by irradiation with ionizing radiation.
- the polymerization initiator is not particularly limited, and known ones can be used. Specific examples include, for example, acetophenones, benzophenones, Michler benzoylbenzoate, ⁇ -amyloxime ester, thioxanthones, propiophenone. , Benzyls, benzoins, acylphosphine oxides. Further, it is preferable to use a mixture of photosensitizers, and specific examples thereof include n-butylamine, triethylamine, poly-n-butylphosphine and the like.
- the coating film of the first hard coat layer composition After forming the coating film of the first hard coat layer composition, the coating film is dried by, for example, heating at a temperature of 30 ° C. to 120 ° C. for 10 seconds to 120 seconds by various known methods, Evaporate.
- the coating film is irradiated with ionizing radiation such as ultraviolet rays, and the coating film is semi-cured.
- ionizing radiation such as ultraviolet rays
- the term “semi-curing” in the present specification means that the curing proceeds substantially upon further irradiation with ionizing radiation. However, at this stage, the coating film may be completely cured (full cure). “Complete curing” in the present specification means that curing does not substantially proceed even when ionizing radiation is further applied.
- a second hard coat layer composition for forming the second hard coat layer 12C is applied on the coating film by a coating device such as a bar coater. A coating film of the hard coat layer composition is formed.
- the second hard coat layer composition contains a polymerizable compound for forming the second hard coat layer 12C.
- the 2nd composition for hard-coat layers may contain the ultraviolet absorber, the solvent, and the polymerization initiator as needed.
- the second hard coat layer composition preferably has a total solid content of 25 to 55%. Since the solvent and the polymerization initiator are the same as the solvent and the polymerization initiator described in the first hard coat layer composition, the description thereof will be omitted here.
- the coating film of the second hard coat layer composition After forming the coating film of the second hard coat layer composition, the coating film is dried by heating at a temperature of, for example, 30 ° C. to 120 ° C. for 10 seconds to 120 seconds by various known methods, and the solvent is removed. Evaporate.
- the coating film of the second hard coat layer composition is irradiated with ionizing radiation such as ultraviolet rays to form the first hard coat layer composition coating film and the second hard coat layer.
- the hard coat layer 12 is obtained by completely curing (full curing) the coating film of the composition for forming the first hard coat layer 12B and the second hard coat layer 12C. Then, the composition for resin layers is apply
- composition for resin layer contains urethane (meth) acrylate etc., for example.
- the resin layer composition may contain an ultraviolet absorber, a spectral transmittance adjusting agent, a leveling agent, a solvent, and a polymerization initiator as necessary.
- the solvent and the polymerization initiator the same solvents and polymerization initiators as described in the column of the first hard coat layer composition can be used.
- the coating film of the resin composition After forming the coating film of the resin composition, it is dried and then irradiated with ionizing radiation to cure the coating film of the resin layer composition to form the resin layer 13. Thereby, the optical film 10 shown in FIG. 1 is obtained.
- the hard coat layer 12 is formed on the first surface 11A of the resin base material 11 in the same manner as described above.
- a resin layer composition is applied to form a coating film, then dried, and then irradiated with ionizing radiation. The coating film is cured to form the resin layer 13.
- the release film After forming the resin layer 13 on the release film, the release film is peeled off from the resin layer 13 to obtain the resin layer 13 alone. And the obtained resin layer 13 is affixed on the 2nd surface 11B of the resin base material 11 through the adhesion layer 41. FIG. Thereby, the optical film 40 shown in FIG. 5 is obtained.
- FIG. 6 is a schematic configuration diagram of the image display apparatus according to the present embodiment.
- the image display device 50 mainly has a casing 51 in which a battery or the like is stored, a protective film 52, a display panel 53, a touch sensor 54, and a circularly polarizing plate 55 toward the viewer.
- the optical film 10 are laminated in this order.
- a light-transmitting adhesive layer 56 is disposed between the display panel 53 and the touch sensor 54, between the touch sensor 54 and the circularly polarizing plate 55, and between the circularly polarizing plate 55 and the optical film 10.
- a black layer 57 is provided on a part of the back surface 10 ⁇ / b> B of the optical film 10.
- the adhesive layer 56 is disposed between the display panel 53 and the touch sensor 54, between the touch sensor 54 and the circularly polarizing plate 55, and between the circularly polarizing plate 55 and the optical film 10.
- the arrangement location of is not particularly limited as long as it is between the optical film and the display panel.
- the optical film 10 is disposed so that the hard coat layer 12 is closer to the viewer side than the resin base material 11.
- the surface 12A of the hard coat layer 12 of the optical film 10 (the surface of the second hard coat layer 12C) forms the surface 50A of the image display device 50.
- the display panel 53 is an organic light emitting diode panel including an organic light emitting diode or the like.
- the touch sensor 54 is disposed closer to the display panel 53 than the circularly polarizing plate 55, but may be disposed between the circularly polarizing plate 55 and the optical film 10.
- the touch sensor 54 may be an on-cell method or an in-cell method.
- the adhesive layer 56 for example, OCA (Optical Clear Adhesive) can be used, but from the viewpoint of improving the impact resistance and preventing the display panel 53 from being damaged, the adhesive layer made of the acrylic gel is used. Is preferred.
- the adhesive layer made of the acrylic gel is used as the adhesive layer 56, the display panel 53 and the touch sensor 54, the touch sensor 54 and the circularly polarizing plate 55, the circularly polarizing plate 55 and the optical film 10 are used. What is necessary is just to arrange
- the acrylic gel is sticky, when the resin layer 13 is made of the acrylic gel, the circularly polarizing plate can be provided without providing the adhesive layer 56 between the circularly polarizing plate 55 and the optical film 10. By attaching the resin layer 13 directly to 55, the circularly polarizing plate 55 and the optical film 10 can be fixed.
- the shear loss tangent tan ⁇ is known as an index representing the impact absorption performance. Therefore, the impact resistance in an optical film having a structure having a hard coat layer on one surface side of the resin substrate and a resin layer on the other surface side may be expressed as a shear loss tangent tan ⁇ .
- the shear loss tangent tan ⁇ is a ratio (G ′′ / G ′) between the shear loss elastic modulus G ′′ and the shear storage elastic modulus G ′.
- the surface dent caused by the optical film itself and the surface dent caused by the adhesive layer when an impact is applied to the surface of the optical film, and the image display rather than the optical film In order to suppress damage to members located inside the apparatus, it has been found that the balance of the resin layer thickness, the shear storage elastic modulus G ′, and the shear loss elastic modulus G ′′ is important.
- the film of the resin layer 13 is provided.
- the thickness is as thin as 50 ⁇ m or more and 300 ⁇ m or less, the shear storage elastic modulus G ′ in the optical films 10 and 40 is more than 200 MPa and 1000 MPa or less, and the shear loss elastic modulus G in the optical films 10 and 40 is Since ′′ is 3 MPa or more and 150 MPa or less, when the impact is applied to the surface 10A of the optical film 10 while being foldable, the depressions on the surfaces 10A and 40A caused by the optical films 10 and 40 themselves and The surface 1 of the optical films 10 and 40 caused by the adhesive layer 56 existing inside the image display device 50 rather than the optical film 10.
- the depressions of 0A and 40A can be suppressed, and damage to members such as the display panel 53 located inside the image display device 50 can be suppressed. Thereby, the outstanding impact resistance can be obtained.
- 100% solid content conversion value is a value when the solid content in the solvent diluted product is 100%.
- composition for hard coat layer First, each component was mix
- composition 1 for hard coat layer -Mixture of dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate (product name "M403", manufactured by Toa Gosei Co., Ltd.): 25 parts by mass-Dipentaerythritol EO-modified hexaacrylate (product name "A-DPH-6E", new Nakamura Chemical Co., Ltd.): 25 parts by mass, deformed silica particles (average particle size 25 nm, manufactured by JGC Catalysts & Chemicals Co., Ltd.): 50 parts by mass (converted to 100% solid content)
- Photopolymerization initiator (1-hydroxycyclohexyl phenyl ketone, product name “Irgacure (registered trademark) 184”, manufactured by BASF Japan): 4 parts by mass Fluorine leveling agent (product name “F568”, manufactured by DIC): 0.2 parts by mass (converted to 100%
- composition 2 for hard coat layer -Urethane acrylate (product name "UX5000", Nippon Kayaku Co., Ltd.): 25 parts by mass-Mixture of dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate (product name "M403", manufactured by Toa Gosei Co., Ltd.): 50 parts by mass ⁇ Polyfunctional acrylate polymer (Product name “Acryt 8KX-012C”, manufactured by Taisei Fine Chemical Co., Ltd.): 25 parts by mass (converted to 100% solid content)
- Antifouling agent product name “BYKUV3500”, manufactured by Big Chemie
- Photopolymerization initiator (1-hydroxycyclohexyl phenyl ketone, product name “Irgacure (registered trademark) 184” manufactured by BASF Japan Ltd.): 4 parts by mass Methyl isobutyl ket
- composition 1 for resin layer ⁇ Urethane acrylate (product name “UV3310B”, manufactured by Nippon Synthetic Chemical Co., Ltd., bifunctional): 85 parts by mass • Phenoxyethyl acrylate (product name “Biscoat # 192”, manufactured by Osaka Organic Chemical Industry Co., Ltd.): 5 parts by mass Mixture of erythritol acrylate, mono and dipentaerythritol acrylate, and polymentaerythritol acrylate (product name “Biscoat # 802”, manufactured by Osaka Organic Chemical Industry Co., Ltd.): 10 parts by mass / polymerization initiator (1-hydroxycyclohexyl phenyl ketone, product) Name “Irgacure (registered trademark) 184” manufactured by BASF Japan Ltd.): 5 parts by mass
- composition 2 for resin layer -Urethane acrylate (product name "UV3310B", manufactured by Nippon Synthetic Chemical Co., Ltd., bifunctional): 85 parts by mass-Phenoxyethyl acrylate (product name "Biscoat # 192", manufactured by Osaka Organic Chemical Industry Co., Ltd.): 15 parts by mass Agent (1-hydroxycyclohexyl phenyl ketone, product name “Irgacure (registered trademark) 184”, manufactured by BASF Japan Ltd.): 5 parts by mass / methyl isobutyl ketone: 10 parts by mass
- composition 3 for resin layer ⁇ Urethane acrylate (product name “UV3310B”, manufactured by Nippon Synthetic Chemical Co., Ltd., bifunctional): 80 parts by mass ⁇ Phenoxyethyl acrylate (product name “Biscoat # 192”, manufactured by Osaka Organic Chemical Industry Co., Ltd.): 5 parts by mass Mixture of erythritol acrylate, mono and dipentaerythritol acrylate, and polymentaerythritol acrylate (product name “Biscoat # 802”, manufactured by Osaka Organic Chemical Industry Co., Ltd.): 10 parts by mass of dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate Mixture (product name “KAYARAD DPHA”, manufactured by Nippon Kayaku Co., Ltd.): 5 parts by mass / polymerization initiator (1-hydroxycyclohexyl phenyl ketone, product name “Irga
- composition 4 for resin layer ⁇ Urethane acrylate (product name “UV3310B”, manufactured by Nippon Synthetic Chemical Co., Ltd., bifunctional): 95 parts by mass ⁇ Phenoxyethyl acrylate (product name “Biscoat # 192”, manufactured by Osaka Organic Chemical Industry Co., Ltd.): 5 parts by mass Agent (1-hydroxycyclohexyl phenyl ketone, product name “Irgacure (registered trademark) 184”, manufactured by BASF Japan Ltd.): 5 parts by mass / methyl isobutyl ketone: 10 parts by mass
- a resin substrate As a resin substrate, a polyimide substrate having a thickness of 50 ⁇ m (product name “Neoprim”, manufactured by Mitsubishi Gas Chemical Co., Ltd.) is prepared, and a hard coat layer is applied to the first surface, which is one surface of the polyimide substrate, with a bar coater.
- the composition 1 for an application was apply
- the solvent in the coating film is evaporated by heating the formed coating film at 70 ° C. for 1 minute, and ultraviolet rays are removed from the air using an ultraviolet irradiation device (Fusion UV System Japan, light source H bulb).
- the coating film was semi-cured by irradiation so that the accumulated light amount was 100 mJ / cm 2 .
- the hard coat layer composition 2 was applied to the surface of the semi-cured hard coat layer composition 1 with a bar coater to form a coating film.
- the formed coating film is heated at 70 ° C. for 1 minute to evaporate the solvent in the coating film, and using an ultraviolet irradiation device (Fusion UV System Japan, light source H bulb), the ultraviolet ray has oxygen concentration. Irradiation was performed so that the integrated light amount was 200 mJ / cm 2 under conditions of 200 ppm or less, and the coating film was completely cured (full cure).
- a hard coat layer comprising a first hard coat layer having a thickness of 10 ⁇ m on the polyimide substrate and a second hard coat layer having a thickness of 5 ⁇ m laminated on the first hard coat layer. Formed.
- the resin layer composition 1 was applied with a bar coater to the second surface opposite to the first surface of the polyimide base material to form a coating film.
- the solvent in a coating film is evaporated by heating at 70 degreeC with respect to the formed coating film for 1 minute, and ultraviolet rays are air-released using an ultraviolet irradiation device (Fusion UV System Japan company make, light source H bulb).
- the coating film was cured by irradiation so that the integrated light amount was 1200 mJ / cm 2 to form a resin layer made of urethane resin having a film thickness of 200 ⁇ m to obtain an optical film.
- the film thickness of each layer is obtained by photographing a cross section of each layer using a scanning electron microscope (SEM), measuring the film thickness of each layer at 20 points in the image of the cross section, and calculating the arithmetic average value of the film thicknesses at the 20 points. It was.
- the specific cross-sectional photography method was as follows. First, a block is prepared by embedding an optical film cut into 1 mm ⁇ 10 mm with an embedding resin, and a uniform section having a thickness of 70 nm or more and 100 nm or less without holes is cut out from this block by a general section preparation method. .
- the aperture is set to “beam monitor aperture 3”, the objective lens aperture is set to “3”, and D. was set to “8 mm”.
- the thickness of the polyimide base material was also measured by the same method as the film thickness of each layer. In Examples 2 to 6 and Comparative Examples 1 to 5, the thickness of the substrate, the thickness of the hard coat layer, and the resin layer were measured by the same method as in Example 1.
- Example 2 An optical film was obtained in the same manner as in Example 1 except that the thickness of the resin layer was 50 ⁇ m.
- Example 3 An optical film was obtained in the same manner as Example 1 except that the thickness of the resin layer was 300 ⁇ m.
- Example 4 an optical film was obtained in the same manner as in Example 1 except that the resin layer composition 2 was used instead of the resin layer composition 1.
- Example 5 an optical film was obtained in the same manner as in Example 1 except that the resin layer composition 3 was used instead of the resin layer composition 1.
- a resin base material As a resin base material, a polyimide base material having a thickness of 50 ⁇ m (product name “Neoprim”, manufactured by Mitsubishi Gas Chemical Co., Ltd.) is prepared, and the hard coat layer composition 1 is applied to the first surface of the polyimide base material with a bar coater. It was applied to form a coating film. Then, the solvent in the coating film is evaporated by heating the formed coating film at 70 ° C. for 1 minute, and ultraviolet rays are removed from the air using an ultraviolet irradiation device (Fusion UV System Japan, light source H bulb). The coating film was semi-cured by irradiation so that the accumulated light amount was 100 mJ / cm 2 .
- an ultraviolet irradiation device Fusion UV System Japan, light source H bulb
- the hard coat layer composition 2 was applied to the surface of the semi-cured hard coat layer composition 1 with a bar coater to form a coating film.
- the formed coating film is heated at 70 ° C. for 1 minute to evaporate the solvent in the coating film, and using an ultraviolet irradiation device (Fusion UV System Japan, light source H bulb), the ultraviolet ray has oxygen concentration. Irradiation was performed so that the integrated light amount was 200 mJ / cm 2 under conditions of 200 ppm or less, and the coating film was completely cured (full cure).
- a hard coat layer comprising a first hard coat layer having a thickness of 10 ⁇ m on the polyimide substrate and a second hard coat layer having a thickness of 5 ⁇ m laminated on the first hard coat layer. Formed.
- the resin layer composition 1 was applied with a bar coater to the untreated surface of a 100 ⁇ m-thick polyethylene terephthalate film (product name “Cosmo Shine A4100”, manufactured by Toyobo Co., Ltd.) as a release film. A film was formed. And the solvent in a coating film is evaporated by heating at 70 degreeC with respect to the formed coating film for 1 minute, and ultraviolet rays are air-released using an ultraviolet irradiation device (Fusion UV System Japan company make, light source H bulb).
- the coating was cured by irradiating it so that the integrated light amount was 1200 mJ / cm 2 , thereby forming a resin layer made of a urethane-based resin having a film thickness of 200 ⁇ m.
- the polyethylene terephthalate film was peeled from the resin to obtain a resin layer alone.
- a resin layer is applied to the second surface opposite to the first surface of the polyimide base material via a 5 ⁇ m thick adhesive layer (product name “Panaclean PD-S1”, manufactured by Panac Corporation).
- An optical film was obtained by pasting.
- Comparative Example 1 An optical film was obtained in the same manner as in Example 1 except that the thickness of the resin layer was 350 ⁇ m.
- Comparative example 2 In Comparative Example 2, an optical film was obtained in the same manner as in Example 1 except that the thickness of the resin layer was 30 ⁇ m.
- Comparative Example 3 An optical film was obtained in the same manner as in Example 1 except that the resin layer composition 4 was used instead of the resin layer composition 1.
- the solid shearing jig includes a single metal solid shearing plate having a thickness of 1 mm and two L-shaped fittings arranged on both sides of the solid shearing plate. And one L-shaped metal fitting, and one sample was sandwiched between the solid shear plate and the other L-shaped metal fitting. In this case, the sample was sandwiched so that the resin layer was on the solid shear plate side and the hard coat layer was on the L-shaped bracket side. Then, the L-shaped brackets were tightened with screws to fix the sample.
- a solid is placed between the upper chuck and the lower chuck.
- a shearing jig was installed at a chuck distance of 20 mm.
- set temperature was 25 degreeC and it heated up at 2 degree-C / min. In this state, while measuring the solid viscoelasticity of the solid at 25 ° C.
- the shear storage modulus G ′, shear loss modulus G ′′ and shear loss tangent tan ⁇ of the film were measured.
- the shear storage elastic modulus G ′, the shear loss elastic modulus G ′′, and the shear loss tangent tan ⁇ in the frequency range of 500 Hz to 1000 Hz in the optical film are the longitudinal vibrations of frequencies 500 Hz, 750 Hz, and 950 Hz applied to the L-shaped bracket.
- the shear storage elastic modulus G ′, the shear loss elastic modulus G ′′ and the shear loss tangent tan ⁇ of the optical film are measured at the respective frequencies, and the shear storage elastic modulus G ′ and the shear loss elastic modulus G ′′ are measured. And the arithmetic average value of the shear loss tangent tan ⁇ was obtained, and this measurement was repeated three times, and the three arithmetic average values obtained were further arithmetically averaged.
- the optical film according to the example and the comparative example is directly placed on the surface of the soda glass having a thickness of 0.7 mm so that the soda glass side becomes the resin layer side, and the iron ball having a weight of 100 g and a diameter of 30 mm from a position of 30 cm in height.
- the impact resistance test A was dropped three times each on the surface of the hard coat layer of the optical film.
- the optical films according to Examples and Comparative Examples were placed so that the soda glass side would be the resin layer side, and a 200 ⁇ m thick adhesive sheet (product name “Highly Transparent Double-Sided Tape 8146- 2 ”, manufactured by 3M Co., Ltd.), an impact resistance test B in which an iron ball having a weight of 100 g and a diameter of 30 mm was dropped from the position of 30 cm onto the surface of the hard coat layer of the optical film was performed three times. . In the impact resistance tests A and B, the position where the iron ball was dropped was changed each time.
- a new sample produced in the same manner as described above with the optical films according to Examples and Comparative Examples is attached to the above durability tester in the same manner as described above, and the continuous folding test (hard coat) in which the resin side surface of the sample is folded 180 °.
- the test of folding the resin layer so that the resin layer is on the outside and the resin layer is on the inside was performed 100,000 times to examine whether the bent portion was cracked or broken.
- the results of the continuous folding test were evaluated according to the following criteria. ⁇ : In any continuous folding test, no crack or break occurred in the bent portion.
- X In any one of the continuous folding tests, the bent portion was cracked or broken.
- ⁇ Pencil hardness> The pencil hardness on the surface of the optical film according to the example and the comparative example (the surface of the hard coat layer) was measured based on JIS K5600-5-4: 1999. In measuring the pencil hardness, the pencil was moved at a speed of 1 mm / sec while applying a load of 1 kg to the pencil. The pencil hardness is the highest hardness at which the surface of the optical film was not damaged in the pencil hardness test. The pencil hardness is measured using a plurality of pencils having different hardnesses. The pencil hardness test is performed five times for each pencil, and the surface of the optical film is measured under a fluorescent lamp four times or more out of five times. In the case where no scratch is visually recognized on the surface of the optical film during the transmission observation, it is determined that the surface of the optical film is not scratched with the pencil having this hardness.
- a sample produced by cutting the optical film according to Examples 1 to 6 into a rectangle of 30 mm ⁇ 100 mm was used as an endurance tester (product name “DLDMMLH-FS”, Yuasa System Equipment). (Manufactured by the company), the short side (30 mm) side of the sample is fixed by the fixing part, respectively, and attached so that the minimum interval between the two opposing side parts is 2 mm as shown in FIG.
- a continuous folding test (a test in which the hard coat layer is on the inside and the resin layer is on the outside) is performed 100,000 times to fold the surface of the sample on the hard coat layer side, and no cracks or breaks occur in the bent portion. As a result, no cracks or breaks occurred in the bent portion.
- a new sample produced in the same manner as described above with the optical films according to Examples 1 to 6 is attached to the durability test machine so that the minimum distance between two opposing side portions is 2 mm as in the above.
- a continuous folding test (a test in which the hard coat layer is on the outside and the resin layer is on the inside) is performed 100,000 times to fold the surface on the resin layer side of the sample, and the bent portion is not cracked or broken. As a result, no cracks or breaks occurred in the bent portion.
- the short side (30 mm) side of the sample prepared by cutting into a rectangle of 30 mm ⁇ 100 mm is parallel so that the distance between the opposing side portions of the sample is 30 mm.
- a folding stationary test was performed in which the optical film was folded and fixed at 70 ° C. for 240 hours while being fixed to the respective fixed portions. Then, by removing the fixing part from one side after the folding stationary test, the folded state is released, and the opening angle is an angle at which the optical film naturally opens after 30 minutes at room temperature (see FIG. 4B).
- the opening angle of the optical films according to Examples 1 to 4 was 100 ° or more, which was larger than the opening angle of the optical film according to Example 5.
- the shear storage modulus G ′ is less than 800 MPa, the recoverability is improved.
- the folding stationary test was carried out both when the hard coat layer was folded so that it was on the inside and when the hard coat layer was folded so that it was on the outside, and the one with the smaller angle was adopted.
- the Martens hardness of the first hard coat layer was 830 MPa
- the hard coat layer 2 had a Martens hardness of 500 MPa.
- the Martens hardness is determined by using a Berkovich indenter (triangular pyramid) at the center of the cross section of each of the first hard coat layer and the second hard coat layer under the following measurement conditions using a “TI950 TriboIndenter” manufactured by HYSITRON (Heiditron).
- the Martens hardness was an arithmetic average value of values obtained by measuring 10 locations. (Measurement condition) ⁇ Loading speed: 10 nm / second ⁇ Retention time: 5 seconds ⁇ Load unloading speed: 10 nm / second ⁇ Measurement temperature: 25 ° C.
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Abstract
Description
図1に示される光学フィルム10は、画像表示装置に用いられるものであり、折り畳み可能であり、かつ光透過性を有するものである。本明細書における「光透過性」とは、光を透過させる性質を意味し、例えば、全光線透過率が50%以上、好ましくは70%以上、より好ましくは80%以上、特に好ましくは90%以上であることを含む。光透過性とは、必ずしも透明である必要はなく、半透明であってもよい。
樹脂基材11は、光透過性を有する樹脂からなる基材である。樹脂基材11の厚みは、10μm以上100μm以下となっていることが好ましい。樹脂基材の厚みが10μm未満であると、光学フィルムのカールが大きくなり、また硬度も不充分となるおそれがあり、更に、光学フィルムをRoll to Rollで製造する場合、シワが発生しやすくなるため外観の悪化を招くおそれがある。一方、樹脂基材の厚みが100μmを超えると、光学フィルムの折り畳み性能が不充分となり、連続折り畳み試験の要件を満たせないことがあり、また、光学フィルムが重くなり、軽量化の面で好ましくない。樹脂基材の厚みは、走査型電子顕微鏡(SEM)を用いて、樹脂基材の断面を撮影し、その断面の画像において樹脂基材の膜厚を20箇所測定し、その20箇所の膜厚の算術平均値とする。樹脂基材の断面写真の撮影方法は、ハードコート層の断面写真の撮影方法と同様である。樹脂基材11の下限は25μm以上であることがより好ましく、樹脂基材11の上限は80μm以下であることがより好ましい。
ハードコート層12は、ハードコート層12の断面中央におけるマルテンス硬度が375MPa以上の層を意味するものとする。本明細書において、「マルテンス硬度」とは、ナノインデンテーション法による硬度測定により、圧子を500nm押込んだときの硬度である。上記ナノインデンテーション法によるマルテンス硬度の測定は、HYSITRON(ハイジトロン)社製の「TI950 TriboIndenter」を用いて行うものとする。すなわち、以下の測定条件で、上記圧子としてBerkovich圧子(三角錐)をハードコート層の断面中央に500nm押し込み、一定時間保持して残留応力の緩和を行った後、除荷させて、緩和後の最大荷重を計測し、該最大荷重Pmax(μN)と深さ500nmのくぼみ面積A(nm2)とを用い、Pmax/Aにより、マルテンス硬度を算出する。マルテンス硬度は、10箇所測定して得られた値の算術平均値とする。
(測定条件)
・荷重速度:10nm/秒
・保持時間:5秒
・荷重除荷速度:10nm/秒
・測定温度:25℃
第1のハードコート層12Bは、主に光学フィルムに硬度を付与するための層である。第1のハードコート層12Bは、第1のハードコート層12Bの断面中央におけるマルテンス硬度が500MPa以上2000MPa以下であることが好ましい。500MPa未満であると、ハードコート層の硬度が不充分となることがあり、2000MPaを超えると、光学フィルムの折り畳み性能が不充分となることがある。第1のハードコート層12Bの断面中央におけるマルテンス硬度の下限は600MPa以上であることが好ましく、上限は1500MPa以下であることが好ましい。
樹脂は、重合性化合物(硬化性化合物)の重合体(硬化物)を含む。重合性化合物は、分子内に重合性官能基を少なくとも1つ有するものである。重合性官能基としては、例えば、(メタ)アクリロイル基、ビニル基、アリル基等のエチレン性不飽和基が挙げられる。なお、「(メタ)アクリロイル基」とは、「アクリロイル基」および「メタクリロイル基」の両方を含む意味である。
無機粒子としては、硬度を向上させることができれば、特に限定されないが、優れた硬度を得る観点から、シリカ粒子が好ましい。シリカ粒子の中でも、反応性シリカ粒子が好ましい。上記反応性シリカ粒子は、上記多官能(メタ)アクリレートとの間で架橋構造を構成することが可能なシリカ粒子であり、この反応性シリカ粒子を含有することで、第1のハードコート層12Bの硬度を充分に高めることができる。
第2のハードコート層12Cは、上述した連続折り畳み試験を充足させるための層である。第2のハードコート層12Cは、第2のハードコート層12Cの断面中央におけるマルテンス硬度が375MPa以上1500MPa以下であることが好ましい。375MPa未満であると、ハードコート層の耐擦傷性が不充分となることがあり、1500MPaを超えると、光学フィルムの耐折り畳み性能が不充分となって上述した連続折り畳み試験を充足できないことがある。第2のハードコート層12Cの断面中央におけるマルテンス硬度の下限は450MPa以上であることがより好ましく、上限は575MPa以下であることがより好ましい。
樹脂は、重合性化合物(硬化性化合物)の重合体(硬化物)を含む。重合性化合物としては、多官能(メタ)アクリレートが好ましい。上記多官能(メタ)アクリレートとしては、第1のハードコート層12Bの欄の多官能(メタ)アクリレートと同様のものが挙げられる。また、第2のハードコート層12Cは、上記多官能(メタ)アクリレートに加えて、多官能ウレタン(メタ)アクリレート及び/又は多官能エポキシ(メタ)アクリレート等が含まれてもよい。
無機粒子としては、第1のハードコート層12Bの欄の無機粒子と同様のものが挙げられる。第2のハードコート層12Cにおける無機粒子の含有量としては、特に限定されないが、例えば、第2のハードコート層12Cに対し0~50質量%であることが好ましい。
光学フィルムは、折り畳み可能なスマートフォンやタブレット端末のようなモバイル端末に特に好適に用いられるが、このようなモバイル端末は屋外で使用されることが多く、そのため、光学フィルムより表示素子側に配置された偏光子が紫外線に晒されて劣化しやすいという問題がある。しかしながら、樹脂層は、偏光子の表示画面側に配置されるため、樹脂層に紫外線吸収剤が含有されていると、偏光子が紫外線に晒されることによる劣化を好適に防止することができる。なお、上記紫外線吸収剤(UVA)は、樹脂基材11および/または樹脂層13に含有されていてもよい。この場合、紫外線吸収剤(UVA)は、ハードコート層12に含有されていなくてもよい。
分光透過率調整剤は、光学フィルムの分光透過率を調整するものである。ハードコート層12に、例えば、下記一般式(25)で表されるセサモール型ベンゾトリアゾール系単量体を含ませた場合には、上述した分光透過率を好適に満たすことができる。
防汚剤は、ハードコート層に均一に防汚剤が分散されていてもよいが、少ない添加量で充分な防汚性を得るとともにハードコート層の強度低下を抑制する観点から、ハードコート層の表面側に偏在して含まれていることが好ましい。ハードコート層が単層構造の場合において、防汚剤をハードコート層の表面側に偏在させる方法としては、例えば、ハードコート層を形成時において、ハードコート層用組成物を用いて形成した塗膜を乾燥させ、硬化させる前に、塗膜を加熱して、塗膜に含まれる樹脂成分の粘度を下げることにより流動性を上げて、防汚剤をハードコート層の表面側に偏在させる方法や、表面張力の低い防汚剤を選定して用い、塗膜の乾燥時に熱をかけずに塗膜の表面に防汚剤を浮かせ、その後塗膜を硬化させることで、上記防汚剤をハードコート層の最表面側に偏在させる方法等が挙げられる。また、ハードコート層12のようにハードコート層が多層構造の場合には、表面側のハードコート層に防汚剤を含有させることによってハードコート層の表面側に防汚剤を偏在させることができる。
樹脂層13は、光透過性を有する樹脂からなる層である。樹脂層13は、衝撃吸収性を有する層である。樹脂層は、2以上の樹脂層からなる多層構造となっていてもよい。
アクリル系ゲルとしては、粘着剤などに用いられている、アクリル酸エステルを含むモノマーを重合してなるポリマーであれば種々のものを使用することができる。具体的には、アクリル系ゲルとしては、例えば、エチル(メタ)アクリレート、n-プロピル(メタ)アクリレート、i-プロピル(メタ)アクリレート、n-ブチル(メタ)アクリレート、i-ブチル(メタ)アクリレート、2-エチルヘキシル(メタ)アクリレート、n-ヘキシル(メタ)アクリレート、n-アミル(メタ)アクリレート、i-アミル(メタ)アクリレート、オクチル(メタ)アクリレート、i-オクチル(メタ)アクリレート、i-ミリスチル(メタ)アクリレート、ラウリル(メタ)アクリレート、ノニル(メタ)アクリレート、i-ノニル(メタ)アクリレート、i-デシル(メタ)アクリレート、トリデシル(メタ)アクリレート、ステアリル(メタ)アクリレート、i-ステアリル(メタ)アクリレート等のアクリル系モノマーを重合または共重合したものを用いることができる。本明細書において、「(メタ)アクリレート」とは、「アクリレート」および「メタクリレート」の両方を含む意味である。なお、上記(共)重合する際に使用するアクリル酸エステルは、単独で用いる他、2種類以上併用してもよい。
ウレタン系樹脂は、ウレタン結合を有する樹脂である。ウレタン系樹脂としては、電離放射線硬化性ウレタン系樹脂組成物の硬化物や熱硬化性ウレタン系樹脂組成物の硬化物等が挙げられる。これらの中でも、高硬度が得られ、硬化速度も早く量産性に優れる観点から、電離放射線硬化性ウレタン系樹脂組成物の硬化物であることが好ましい。
図1に示される光学フィルム10においては、樹脂層13が樹脂基材11の第2の面11Bに直接設けられているが、光学フィルムとしては、樹脂層が粘着層を介して樹脂基材に貼り付けられた光学フィルムであってもよい。具体的には、図5に示される光学フィルム40は、樹脂基材11と、樹脂基材11の第1の面11A側に設けられたハードコート層12と、樹脂基材11の第1の面11Aとは反対側の面である第2の面11B側に設けられた樹脂層13と、樹脂基材11と樹脂層13の間に介在した粘着層41とを備えるものである。樹脂層13は、粘着層41を介して樹脂基材11に貼り付けられている。なお、図5において、図1と同じ符号が付されている部材は、図1で示した部材と同じものであるので、説明を省略するものとする。
粘着層41は、粘着フィルムであってもよい。粘着層41としては、特に限定されないが、例えば、OCA(Optical Clear Adhesive)を用いることができる。粘着層41の膜厚は、5μm以上であることが好ましい。粘着層41の膜厚が、5μm以上であれば、樹脂基材11に樹脂層13を確実に貼り付けることができる。粘着層41の膜厚の下限は、薄型化を図る観点から50μm以下であることが好ましい。
光学フィルム10は、樹脂層13を構成する樹脂の種類によって様々な方法によって作製することができる。例えば、樹脂層13がアクリル系ゲルからなる層である場合には、例えば、以下のようにして作製することができる。まず、樹脂基材11の第1の面11A上に、バーコーター等の塗布装置によって、第1のハードコート層用組成物を塗布して、第1のハードコート層用組成物の塗膜を形成する。
第1のハードコート層用組成物は、第1のハードコート層12Bを形成するための重合性化合物を含んでいる。第1のハードコート層用組成物は、その他、必要に応じて、紫外線吸収剤、分光透過率調整剤、防汚剤、無機粒子、レベリング剤、溶剤、重合開始剤を含んでいてもよい。
上記溶媒としては、アルコール(例、メタノール、エタノール、プロパノール、イソプロパノール、n-ブタノール、s-ブタノール、t-ブタノール、ベンジルアルコール、PGME、エチレングリコール、ジアセトンアルコール)、ケトン(例、アセトン、メチルエチルケトン、メチルイソブチルケトン、シクロペンタノン、シクロヘキサノン、ヘプタノン、ジイソブチルケトン、ジエチルケトン、ジアセトンアルコール)、エステル(酢酸メチル、酢酸エチル、酢酸ブチル、酢酸n-プロピル、酢酸イソプロピル、蟻酸メチル、PGMEA)、脂肪族炭化水素(例、ヘキサン、シクロヘキサン)、ハロゲン化炭化水素(例、メチレンクロライド、クロロホルム、四塩化炭素)、芳香族炭化水素(例、ベンゼン、トルエン、キシレン)、アミド(例、ジメチルホルムアミド、ジメチルアセトアミド、N-メチルピロリドン)、エーテル(例、ジエチルエーテル、ジオキサン、テトラヒドロフラン)、エーテルアルコール(例、1-メトキシ-2-プロパノール)、カーボネート(炭酸ジメチル、炭酸ジエチル、炭酸エチルメチル)、等が挙げられる。これらの溶媒、単独で用いられてもよく、2種類以上が併用されてもよい。なかでも、上記溶媒としては、ウレタン(メタ)アクリレート等の成分、並びに、他の添加剤を溶解或いは分散させ、第1のハードコート層用組成物を好適に塗工できる点で、メチルイソブチルケトン、メチルエチルケトンが好ましい。
重合開始剤は、電離放射線照射より分解されて、ラジカルを発生して重合性化合物の重合(架橋)を開始または進行させる成分である。
第2のハードコート層用組成物は、第2のハードコート層12Cを形成するための重合性化合物を含んでいる。第2のハードコート層用組成物は、その他、必要に応じて、紫外線吸収剤、溶剤、重合開始剤を含んでいてもよい。第2のハードコート層用組成物は、第1のハードコート層用組成物と同様に、総固形分が25~55%であることが好ましい。溶剤および重合開始剤は、第1のハードコート層用組成物で説明した溶剤および重合開始剤と同様であるので、ここでは説明を省略するものとする。
樹脂層用組成物は、例えば、ウレタン(メタ)アクリレート等を含んでいる。樹脂層組成物は、その他、必要に応じて、紫外線吸収剤、分光透過率調整剤、レベリング剤、溶剤、重合開始剤を含んでいてもよい。溶剤、重合開始剤は、第1のハードコート層用組成物の欄で説明した溶剤、重合開始剤と同様のものを用いることができる。
光学フィルム10、40は、折り畳み可能な画像表示装置に組み込んで使用することが可能である。図6は、本実施形態に係る画像表示装置の概略構成図である。図6に示されるように、画像表示装置50は、観察者側に向けて、主に、電池等が収納された筐体51、保護フィルム52、表示パネル53、タッチセンサ54、円偏光板55、および光学フィルム10がこの順で積層されている。表示パネル53とタッチセンサ54との間、タッチセンサ54と円偏光板55との間、円偏光板55と光学フィルム10との間には、光透過性を有する粘着層56が配置されており、これら部材は粘着層56によって互いに固定されている。また、光学フィルム10の裏面10Bの一部には、黒色層57が設けられている。なお、粘着層56は、表示パネル53とタッチセンサ54との間、タッチセンサ54と円偏光板55との間、円偏光板55と光学フィルム10との間に配置されているが、粘着層の配置箇所は、光学フィルムと表示パネルとの間であれば、特に限定されない。
まず、下記に示す組成となるように各成分を配合して、ハードコート層用組成物を得た。
・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(製品名「M403」、東亜合成社製):25質量部
・ジペンタエリスリトールEO変性ヘキサアクリレート(製品名「A-DPH-6E」、新中村化学社製):25質量部
・異形シリカ粒子(平均粒子径25nm、日揮触媒化成社製):50質量部(固形分100%換算値)
・光重合開始剤(1-ヒドロキシシクロヘキシルフェニルケトン、製品名「Irgacure(登録商標)184」、BASFジャパン社製):4質量部
・フッ素系レベリング剤(製品名「F568」、DIC社製):0.2質量部(固形分100%換算値)
・メチルイソブチルケトン(MIBK):150質量部
・ウレタンアクリレート(製品名「UX5000」、日本化薬社製):25質量部
・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(製品名「M403」、東亜合成社製):50質量部
・多官能アクリレートポリマー(製品名「アクリット8KX-012C」、大成ファインケミカル社製):25質量部(固形分100%換算値)
・防汚剤(製品名「BYKUV3500」、ビックケミー社製):1.5質量部(固形分100%換算値)
・光重合開始剤(1-ヒドロキシシクロヘキシルフェニルケトン、製品名「Irgacure(登録商標)184」、BASFジャパン社製):4質量部
・メチルイソブチルケトン(MIBK):150質量部
まず、下記に示す組成となるように各成分を配合して、樹脂層用組成物を得た。
(樹脂層用組成物1)
・ウレタンアクリレート(製品名「UV3310B」、日本合成化学社製、2官能):85質量部
・フェノキシエチルアクリレート(製品名「ビスコート#192」、大阪有機化学工業社製):5質量部
・トリペンタエリスリトールアクリレート、モノおよびジペンタエリスリトールアクリレート、ならびにポリメンタエリスリトールアクリレートの混合物(製品名「ビスコート#802」、大阪有機化学工業社製):10質量部
・重合開始剤(1-ヒドロキシシクロヘキシルフェニルケトン、製品名「Irgacure(登録商標)184」、BASFジャパン社製):5質量部
・メチルイソブチルケトン:10質量部
・ウレタンアクリレート(製品名「UV3310B」、日本合成化学社製、2官能):85質量部
・フェノキシエチルアクリレート(製品名「ビスコート#192」、大阪有機化学工業社製):15質量部
・重合開始剤(1-ヒドロキシシクロヘキシルフェニルケトン、製品名「Irgacure(登録商標)184」、BASFジャパン社製):5質量部
・メチルイソブチルケトン:10質量部
・ウレタンアクリレート(製品名「UV3310B」、日本合成化学社製、2官能):80質量部
・フェノキシエチルアクリレート(製品名「ビスコート#192」、大阪有機化学工業社製):5質量部
・トリペンタエリスリトールアクリレート、モノおよびジペンタエリスリトールアクリレート、ならびにポリメンタエリスリトールアクリレートの混合物(製品名「ビスコート#802」、大阪有機化学工業社製):10質量部
・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(製品名「KAYARAD DPHA」、日本化薬株式会社製):5質量部
・重合開始剤(1-ヒドロキシシクロヘキシルフェニルケトン、製品名「Irgacure(登録商標)184」、BASFジャパン社製):5質量部
・メチルイソブチルケトン:10質量部
・ウレタンアクリレート(製品名「UV3310B」、日本合成化学社製、2官能):95質量部
・フェノキシエチルアクリレート(製品名「ビスコート#192」、大阪有機化学工業社製):5質量部
・重合開始剤(1-ヒドロキシシクロヘキシルフェニルケトン、製品名「Irgacure(登録商標)184」、BASFジャパン社製):5質量部
・メチルイソブチルケトン:10質量部
・ウレタンアクリレート(製品名「UV3310B」、日本合成化学社製、2官能):85質量部
・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(製品名「KAYARAD DPHA」、日本化薬株式会社製):15質量部
・重合開始剤(1-ヒドロキシシクロヘキシルフェニルケトン、製品名「Irgacure(登録商標)184」、BASFジャパン社製):5質量部
・メチルイソブチルケトン:10質量部
樹脂基材として、厚さ50μmのポリイミド基材(製品名「ネオプリム」、三菱ガス化学社製)を準備し、ポリイミド基材の一方の面である第1の面に、バーコーターでハードコート層用組成物1を塗布し、塗膜を形成した。その後、形成した塗膜に対して、70℃、1分間加熱させることにより塗膜中の溶剤を蒸発させ、紫外線照射装置(フュージョンUVシステムジャパン社製、光源Hバルブ)を用いて、紫外線を空気中にて積算光量が100mJ/cm2になるように照射して塗膜を半硬化(ハーフキュア)させた。次いで、半硬化させたハードコート層用組成物1の塗膜の表面に、バーコーターでハードコート層用組成物2を塗布し、塗膜を形成した。形成した塗膜に対して、70℃、1分間加熱させることにより塗膜中の溶剤を蒸発させ、紫外線照射装置(フュージョンUVシステムジャパン社製、光源Hバルブ)を用いて、紫外線を酸素濃度が200ppm以下の条件下にて積算光量が200mJ/cm2になるように照射して塗膜を完全硬化(フルキュア)させた。これにより、ポリイミド基材上に、膜厚が10μmの第1のハードコート層と、第1のハードコート層上に積層された膜厚が5μmの第2のハードコート層とからなるハードコート層を形成した。ポリイミド基材上にハードコート層を形成した後、ポリイミド基材の第1の面とは反対側の第2の面にバーコーターで樹脂層用組成物1を塗布して、塗膜を形成した。そして、形成した塗膜に対して、70℃、1分間加熱させることにより塗膜中の溶剤を蒸発させ、紫外線照射装置(フュージョンUVシステムジャパン社製、光源Hバルブ)を用いて、紫外線を空気中にて積算光量が1200mJ/cm2になるように照射して塗膜を硬化させて、膜厚が200μmのウレタン系樹脂からなる樹脂層を形成して、光学フィルムを得た。
実施例2においては、樹脂層の膜厚を50μmとしたこと以外は、実施例1と同様にして、光学フィルムを得た。
実施例3においては、樹脂層の膜厚を300μmとしたこと以外は、実施例1と同様にして、光学フィルムを得た。
実施例4においては、樹脂層用組成物1の代わりに樹脂層用組成物2を用いたこと以外は、実施例1と同様にして、光学フィルムを得た。
実施例5においては、樹脂層用組成物1の代わりに樹脂層用組成物3を用いたこと以外は、実施例1と同様にして、光学フィルムを得た。
樹脂基材として、厚さ50μmのポリイミド基材(製品名「ネオプリム」、三菱ガス化学社製)を準備し、ポリイミド基材の第1の面に、バーコーターでハードコート層用組成物1を塗布し、塗膜を形成した。その後、形成した塗膜に対して、70℃、1分間加熱させることにより塗膜中の溶剤を蒸発させ、紫外線照射装置(フュージョンUVシステムジャパン社製、光源Hバルブ)を用いて、紫外線を空気中にて積算光量が100mJ/cm2になるように照射して塗膜を半硬化(ハーフキュア)させた。次いで、半硬化させたハードコート層用組成物1の塗膜の表面に、バーコーターでハードコート層用組成物2を塗布し、塗膜を形成した。形成した塗膜に対して、70℃、1分間加熱させることにより塗膜中の溶剤を蒸発させ、紫外線照射装置(フュージョンUVシステムジャパン社製、光源Hバルブ)を用いて、紫外線を酸素濃度が200ppm以下の条件下にて積算光量が200mJ/cm2になるように照射して塗膜を完全硬化(フルキュア)させた。これにより、ポリイミド基材上に、膜厚が10μmの第1のハードコート層と、第1のハードコート層上に積層された膜厚が5μmの第2のハードコート層とからなるハードコート層を形成した。
比較例1においては、樹脂層の膜厚を350μmとしたこと以外は、実施例1と同様にして、光学フィルムを得た。
比較例2においては、樹脂層の膜厚を30μmとしたこと以外は、実施例1と同様にして、光学フィルムを得た。
比較例3においては、樹脂層用組成物1の代わりに樹脂層用組成物4を用いたこと以外は、実施例1と同様にして、光学フィルムを得た。
比較例4においては、樹脂層用組成物1の代わりに樹脂層用組成物5を用いたこと以外は、実施例1と同様にして、光学フィルムを得た。
実施例および比較例に係る光学フィルムの剪断貯蔵弾性率G´、剪断損失弾性率G´´、および剪断損失正接tanδを測定した。具体的には、まず、光学フィルムを10mm×5mmの長方形状に打ち抜いて、サンプルとした。そして、このサンプルを2枚準備し、動的粘弾性測定装置(製品名「Rheogel-E4000」、ユービーエム社製)のオプションである固体剪断用治具に取り付ける。具体的には、固体剪断用治具は、厚みが1mmの1枚の金属製の固体剪断板と、この固体剪断板の両側に配置された2つのL型金具を備えており、固体剪断板と一方のL型金具との間で一方のサンプルを挟み、かつ固体剪断板と他方のL型金具で他方のサンプルを挟んだ。この場合、樹脂層が固体剪断板側となり、ハードコート層がL型金具側となるようにサンプルを挟んだ。そして、ビスでL型金具間を締めて、サンプルを固定した。次いで、動的粘弾性測定装置(製品名「Rheogel-E4000」、株式会社ユービーエム社製)に上部チャックおよび下部チャックからなる引張り試験用チャックを取り付けた後、上部チャックと下部チャックの間に固体剪断用治具をチャック間距離20mmで設置した。そして、設定温度を25℃とし2℃/minで昇温させた。この状態で、固体剪断板を固定しながら2つのL型金具に歪み量1%かつ周波数500Hz以上1000Hz以下の範囲の縦振動を与えながら、25℃で固体の動的粘弾性測定を行い、光学フィルムの剪断貯蔵弾性率G´、剪断損失弾性率G´´および剪断損失正接tanδを測定した。ここで、光学フィルムにおける500Hz以上1000Hz以下の周波数域での剪断貯蔵弾性率G´、剪断損失弾性率G´´および剪断損失正接tanδは、L型金具に周波数500Hz、750Hz、950Hzの縦振動をそれぞれ与えて、それぞれの周波数において光学フィルムの剪断貯蔵弾性率G´、剪断損失弾性率G´´および剪断損失正接tanδを測定し、これらの剪断貯蔵弾性率G´、剪断損失弾性率G´´および剪断損失正接tanδの算術平均値を求め、さらに、この測定を3回繰り返し、それぞれ得られた3つの算術平均値をさらに算術平均した値とした。
厚さ0.7mmのソーダガラスの表面に、ソーダガラス側が樹脂層側となるように実施例および比較例に係る光学フィルムを直接置き、高さ30cmの位置から重さ100g、直径30mmの鉄球を光学フィルムのハードコート層の表面に落下させる耐衝撃性試験Aを各3回行った。また、厚さ0.7mmのソーダガラス上に、ソーダガラス側が樹脂層側となるように実施例及び比較例に係る光学フィルムを、厚み200μmの粘着シート(製品名「高透明性両面テープ 8146-2」、スリーエム社製)を介して置き、高さ30cmの位置から重さ100g、直径30mmの鉄球を光学フィルムのハードコート層の表面に落下させる耐衝撃性試験Bを各3回行った。なお、耐衝撃性試験A、Bにおいて、鉄球を落下させる位置はその都度変えるものとした。そして、耐衝撃性試験A後の光学フィルムにおいて、目視によってハードコート層の表面に凹みが生じているかを評価するとともに、ソーダガラスに割れが生じているか評価した。また、耐衝撃性試験B後の光学フィルムにおいて、目視によってハードコート層の表面に凹みが生じているかを評価した。評価結果は、以下の通りとした。
(ハードコート層の表面の凹み評価)
○:ハードコート層を正面および斜めから観察した場合の両方において、ハードコート層の表面に凹みが確認されなかった。
△:ハードコート層を正面から観察した場合にはハードコート層の表面に凹みが観察されなかったが、斜め観察した場合にはハードコート層の表面に凹みが確認された。
×:ハードコート層を正面および斜めから観察した場合の両方において、ハードコート層の表面に明らかな凹みが観察された。
(ソーダガラスの割れ評価)
◎:ソーダガラスが割れなかった。
○:ソーダガラスに傷が入ったが割れなかった。
△:1~2回ソーダガラスに割れが生じた。
×:3回ともソーダガラスに割れが生じた。
実施例および比較例に係る光学フィルムを、30mm×100mmの長方形にカットして作製したサンプルを、耐久試験機(製品名「DLDMLH-FS」、ユアサシステム機器社製)に、サンプルの短辺(30mm)側を固定部でそれぞれ固定し、図3(C)に示したように対向する2つの辺部の最小の間隔が30mmとなるようにして取り付け、サンプルのハードコート層側の面を180°折り畳む連続折り畳み試験(ハードコート層が内側となり、樹脂層が外側となるように折り畳む試験)を10万回行い、屈曲部に割れ又は破断が生じていないか調べた。また、実施例および比較例に係る光学フィルムで上記同様に作製した新しいサンプルを、上記の耐久試験機に、上記と同様に取り付け、サンプルの樹脂側の面を180°折り畳む連続折り畳み試験(ハードコート層が外側となり、樹脂層が内側となるように折り畳む試験)を10万回行い、屈曲部に割れ又は破断が生じていないか調べた。連続折り畳み試験の結果を、以下の基準で評価した。
○:いずれの連続折り畳み試験においても、屈曲部に割れ又は破断が生じていなかった。
×:いずれかの連続折り畳み試験において、屈曲部に割れ又は破断が生じていた。
実施例および比較例に係る光学フィルムの表面(ハードコート層の表面)における鉛筆硬度を、JIS K5600-5-4:1999に基づいてそれぞれ測定した。なお、鉛筆硬度の測定の際には、鉛筆に1kgの荷重をかけながら、鉛筆を速度1mm/秒で移動させた。鉛筆硬度は、鉛筆硬度試験において光学フィルムの表面に傷が付かなかった最も高い硬度とする。なお、鉛筆硬度の測定の際には、硬度が異なる鉛筆を複数本用いて行うが、鉛筆1本につき5回鉛筆硬度試験を行い、5回のうち4回以上蛍光灯下で光学フィルムの表面を透過観察した際に光学フィルムの表面に傷が視認されなかった場合には、この硬度の鉛筆においては光学フィルムの表面に傷が付かなかったと判断する。
(測定条件)
・荷重速度:10nm/秒
・保持時間:5秒
・荷重除荷速度:10nm/秒
・測定温度:25℃
10A、12A、40A…表面
11…樹脂基材
11A…第1の面
11B…第2の面
12…ハードコート層
12A…第1のハードコート層
12B…第2のハードコート層
13…樹脂層
50…画像表示装置
53…表示パネル
56…粘着層
Claims (6)
- 画像表示装置に用いられる折り畳み可能な光透過性の光学フィルムであって、
樹脂基材と、
前記樹脂基材の第1の面側に設けられたハードコート層と、
前記樹脂基材の前記第1の面とは反対側の第2の面側に設けられた膜厚が50μm以上300μm以下の樹脂層と、を備え、
前記光学フィルムにおける25℃、500Hz以上1000Hz以下の周波数域での剪断貯蔵弾性率G´が、200MPaを超え1200MPa以下であり、
前記光学フィルムにおける25℃、500Hz以上1000Hz以下の周波数域での剪断損失弾性率G´´が、3MPa以上150MPa以下である、光学フィルム。 - 前記光学フィルムの対向する辺部の間隔が30mmとなるように前記光学フィルムを180°折り畳む試験を10万回繰り返し行った場合に割れまたは破断が生じない、請求項1に記載の光学フィルム。
- 前記樹脂基材が、ポリイミド樹脂、ポリアミド樹脂、またはこれらの混合物からなる基材である、請求項1に記載の光学フィルム。
- 折り畳み可能な画像表示装置であって、
表示パネルと、
前記表示パネルよりも観察者側に配置された請求項1に記載の光学フィルムと、を備え、
前記光学フィルムの前記ハードコート層が、前記樹脂基材よりも観察者側に位置している、画像表示装置。 - 前記光学フィルムと前記表示パネルとの間に配置された粘着層をさらに備える、請求項4に記載の画像表示装置。
- 前記表示パネルが、有機発光ダイオードパネルである、請求項4に記載の画像表示装置。
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- 2017-12-28 TW TW106146267A patent/TWI757400B/zh active
- 2017-12-28 US US16/476,207 patent/US10935700B2/en active Active
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| JP7331829B2 (ja) | 2018-02-28 | 2023-08-23 | 大日本印刷株式会社 | 光学フィルムおよび画像表示装置 |
| KR20200126386A (ko) * | 2018-02-28 | 2020-11-06 | 다이니폰 인사츠 가부시키가이샤 | 광학 필름 및 화상 표시 장치 |
| JPWO2019168005A1 (ja) * | 2018-02-28 | 2021-03-11 | 大日本印刷株式会社 | 光学フィルムおよび画像表示装置 |
| WO2019168005A1 (ja) * | 2018-02-28 | 2019-09-06 | 大日本印刷株式会社 | 光学フィルムおよび画像表示装置 |
| US12295202B2 (en) | 2018-02-28 | 2025-05-06 | Dai Nippon Printing Co., Ltd. | Optical film and image display device |
| KR102756034B1 (ko) * | 2018-02-28 | 2025-01-20 | 다이니폰 인사츠 가부시키가이샤 | 광학 필름 및 화상 표시 장치 |
| JP2020030395A (ja) * | 2018-08-20 | 2020-02-27 | 住友化学株式会社 | 複合前面板及びその製造方法 |
| CN113167929A (zh) * | 2018-11-27 | 2021-07-23 | 富士胶片株式会社 | 硬涂膜、具备硬涂膜的物品及图像显示装置 |
| JP2020167085A (ja) * | 2019-03-29 | 2020-10-08 | 大日本印刷株式会社 | 光学フィルムおよび画像表示装置 |
| JP7572143B2 (ja) | 2019-03-29 | 2024-10-23 | 大日本印刷株式会社 | 光学フィルムおよび画像表示装置 |
| JPWO2021060560A1 (ja) * | 2019-09-27 | 2021-04-01 | ||
| JP7626069B2 (ja) | 2019-09-27 | 2025-02-04 | 大日本印刷株式会社 | 樹脂層、光学フィルムおよび画像表示装置 |
| KR102389656B1 (ko) * | 2019-10-09 | 2022-04-22 | 닛토덴코 가부시키가이샤 | 플렉서블 화상 표시 장치 및 이에 이용하는 광학 적층체 |
| KR20210047958A (ko) * | 2019-10-09 | 2021-04-30 | 닛토덴코 가부시키가이샤 | 플렉서블 화상 표시 장치 및 이에 이용하는 광학 적층체 |
| JP7198946B2 (ja) | 2019-12-05 | 2023-01-04 | 富士フイルム株式会社 | 光学積層体、偏光板、画像表示装置、抵抗膜式タッチパネル及び静電容量式タッチパネル |
| JPWO2021112253A1 (ja) * | 2019-12-05 | 2021-06-10 | ||
| WO2021112253A1 (ja) * | 2019-12-05 | 2021-06-10 | 富士フイルム株式会社 | 光学積層体、偏光板、画像表示装置、抵抗膜式タッチパネル及び静電容量式タッチパネル |
| KR102401803B1 (ko) * | 2019-12-27 | 2022-05-26 | 닛토덴코 가부시키가이샤 | 플렉서블 화상 표시 장치 및 그에 이용하는 광학 적층체 |
| KR20210106573A (ko) * | 2019-12-27 | 2021-08-30 | 닛토덴코 가부시키가이샤 | 플렉서블 화상 표시 장치 및 그에 이용하는 광학 적층체 |
| JP2023526642A (ja) * | 2020-05-21 | 2023-06-22 | 華為技術有限公司 | ディスプレイパネル及びディスプレイ装置 |
| JP7523588B2 (ja) | 2020-05-21 | 2024-07-26 | 華為技術有限公司 | ディスプレイパネル及びディスプレイ装置 |
| WO2025206337A1 (ja) * | 2024-03-29 | 2025-10-02 | 東洋紡株式会社 | 光学フィルムおよび画像表示装置 |
Also Published As
| Publication number | Publication date |
|---|---|
| US20200386917A1 (en) | 2020-12-10 |
| JP2024050562A (ja) | 2024-04-10 |
| JPWO2018128171A1 (ja) | 2019-11-21 |
| TW201831327A (zh) | 2018-09-01 |
| JP2022095687A (ja) | 2022-06-28 |
| KR20190104565A (ko) | 2019-09-10 |
| US10935700B2 (en) | 2021-03-02 |
| KR102379907B1 (ko) | 2022-03-31 |
| CN110249376A (zh) | 2019-09-17 |
| CN110249376B (zh) | 2021-08-24 |
| TWI757400B (zh) | 2022-03-11 |
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