WO2022191311A1 - 光学フィルムおよび表示装置 - Google Patents
光学フィルムおよび表示装置 Download PDFInfo
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- WO2022191311A1 WO2022191311A1 PCT/JP2022/010832 JP2022010832W WO2022191311A1 WO 2022191311 A1 WO2022191311 A1 WO 2022191311A1 JP 2022010832 W JP2022010832 W JP 2022010832W WO 2022191311 A1 WO2022191311 A1 WO 2022191311A1
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- layer
- optical film
- light
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- wavelength
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Images
Classifications
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- G02B5/22—Absorbing filters
- G02B5/223—Absorbing filters containing organic substances, e.g. dyes, inks or pigments
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- G—PHYSICS
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- 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
- G02B1/11—Anti-reflection coatings
- G02B1/111—Anti-reflection coatings using layers comprising organic materials
-
- 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
- H10K59/30—Devices specially adapted for multicolour light emission
- H10K59/32—Stacked devices having two or more layers, each emitting at different wavelengths
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
- C09B57/00—Other synthetic dyes of known constitution
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- G—PHYSICS
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- 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
- G02B1/12—Optical coatings produced by application to, or surface treatment of, optical elements by surface treatment, e.g. by irradiation
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- 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
- G02B1/16—Optical coatings produced by application to, or surface treatment of, optical elements having an anti-static effect, e.g. electrically conducting coatings
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- G—PHYSICS
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- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
- G02B1/10—Optical coatings produced by application to, or surface treatment of, optical elements
- G02B1/18—Coatings for keeping optical surfaces clean, e.g. hydrophobic or photo-catalytic films
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- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B5/00—Optical elements other than lenses
- G02B5/003—Light absorbing elements
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- G—PHYSICS
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- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B5/00—Optical elements other than lenses
- G02B5/20—Filters
- G02B5/208—Filters for use with infrared or ultraviolet radiation, e.g. for separating visible light from infrared and/or ultraviolet radiation
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- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B5/00—Optical elements other than lenses
- G02B5/20—Filters
- G02B5/22—Absorbing filters
-
- 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
- H10K50/86—Arrangements for improving contrast, e.g. preventing reflection of ambient light
- H10K50/865—Arrangements for improving contrast, e.g. preventing reflection of ambient light comprising light absorbing layers, e.g. light-blocking layers
-
- 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
- H10K59/10—OLED displays
- H10K59/12—Active-matrix OLED [AMOLED] displays
- H10K59/1201—Manufacture or treatment
-
- 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
- H10K59/30—Devices specially adapted for multicolour light emission
- H10K59/38—Devices specially adapted for multicolour light emission comprising colour filters or colour changing media [CCM]
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- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B5/00—Optical elements other than lenses
- G02B5/02—Diffusing elements; Afocal elements
- G02B5/0273—Diffusing elements; Afocal elements characterized by the use
- G02B5/0294—Diffusing elements; Afocal elements characterized by the use adapted to provide an additional optical effect, e.g. anti-reflection or filter
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- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B5/00—Optical elements other than lenses
- G02B5/20—Filters
- G02B5/205—Neutral density filters
-
- 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
-
- 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
- H10K2102/302—Details of OLEDs of OLED structures
-
- 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
- H10K59/8791—Arrangements for improving contrast, e.g. preventing reflection of ambient light
Definitions
- the present invention relates to optical films and display devices.
- This application claims priority to Japanese Patent Application No. 2021-040749 filed in Japan on March 12, 2021, the content of which is incorporated herein.
- self-luminous display devices equipped with self-luminous elements are excellent in miniaturization, and have excellent features such as low power consumption, high brightness, and high reaction speed. It is expected to be the next-generation display device. Electrodes and wirings made of metal are formed within the region of the display surface of the self-luminous display device. As a result, light incident from the outside of the display screen (that is, external light) is reflected by the electrodes and wirings, which tends to cause deterioration in display quality such as deterioration in contrast.
- color purity indicates the range of colors that can be displayed by a display device, and is also called color reproduction range. Therefore, high color purity means a wide color reproduction range and good color reproducibility.
- As means for improving color reproducibility there is a method of separating colors using a color filter for a light source that emits white light, or a method of correcting a light source that emits monochromatic light of the three primary colors RGB with a color filter to narrow the half value.
- a display device that emits monochromatic light of three primary colors, RGB requires a color filter forming process, which poses a problem of increased cost.
- Patent Document 1 discloses a display substrate including an organic light-emitting element and a display substrate separated from the display substrate. and a sealing substrate, wherein a space between the display substrate and the sealing substrate is filled with a filler that selectively absorbs external light for each wavelength band and adjusts transmittance. disclosed.
- the visibility is improved by suppressing the reflection of external light
- the color purity is also improved by selectively absorbing the light in the wavelength band that particularly reduces the color purity among the light emitted from the display device.
- the disclosed technology is insufficient in suppressing reflection of external light, and there is a problem that the reflected light is colored.
- the colorant that absorbs light of a specific wavelength has insufficient reliability such as light resistance, and is difficult to put into practical use.
- a device using a polarizing plate and a phase delay plate can suppress the amount of light reflected by external light, but there is a problem that the amount of display light generated by the organic light-emitting element is also reduced.
- a dye having a maximum absorption wavelength in a wavelength range of 480 nm to 510 nm and a dye having a maximum absorption wavelength in a wavelength range of 580 nm to 610 nm are used. Contained configurations have been proposed. Therefore, there is a problem that it is difficult to remove the influence of external light in the wavelength band of less than 480 nm and the wavelength band of more than 610 nm.
- the present invention provides an optical film capable of improving display quality and extending the life of light-emitting elements, and a display device using the same.
- the optical film of the first aspect of the present invention comprises: a transparent substrate; one or more colored layers disposed over the transparent substrate and containing a dye; and one or more functional layers disposed on the opposite side of the transparent substrate with the layer interposed therebetween.
- the colored layer has a maximum absorption wavelength in the range of 470 nm or more and 530 nm or less, a first coloring material having a half width of the absorption spectrum of 15 nm or more and 45 nm or less, and a maximum absorption wavelength in the range of 560 nm or more and 620 nm or less, a second coloring material having an absorption spectrum half width of 15 nm to 55 nm; and each of the chromaticness indices a * and b * of the reflected hue defined by the following formulas (1) to (9) is in the range of -5 to +5 .
- the functional layer includes at least an ultraviolet absorption layer having an ultraviolet shielding rate of 85% or more according to JIS L 1925.
- ⁇ is a variable representing wavelength
- t is a variable representing the ratio of X, Y, and Z to X n , Y n , and Zn .
- the a * and b * calculated from the formulas (1) to (3) are calculated according to the calculation method in the CIE1976L * a * b * color space (CIELAB color space).
- X n , Y n , Z n are the tristimulus values at the white point of the D65 illuminant.
- R E ( ⁇ ) is a function representing the reflectance [%] on the perfect diffuse reflection surface (each wavelength 100%)
- R2 ( ⁇ ) is the optical film on the opposite side of the transparent substrate
- T( ⁇ ) is a function representing the transmittance [%] of the optical film.
- P D65 ( ⁇ ) is the D65 light source spectrum
- overline x( ⁇ ), overline y( ⁇ ), and overline z( ⁇ ) are color matching in CIE1931 2° field of view. is a function.
- Definite integrals in equations (6) to (9) can be obtained by appropriate numerical integration.
- the wavelength intervals for numerical integration are, for example, 1 nm intervals.
- R( ⁇ ) represents the reflectance of the optical film for incident light from the opposite side of the transparent substrate, taking into account the internal reflection of the transparent substrate in the optical film.
- X, Y, Z represented by equations (6)-(8) represent the tristimulus values at the white point of the D65 illuminant.
- a display device includes a light source and the optical film.
- an optical film and a display device that can improve the display quality due to the reflection of external light and improve the life of the light-emitting elements of the display device.
- FIG. 4 is an explanatory diagram of a method for calculating chromaticness indices a * and b * of the reflection hue of the optical film of the present invention.
- FIG. 5 is a schematic cross-sectional view showing an example of an optical film and a display device according to a second embodiment of the invention;
- FIG. 7 is a schematic cross-sectional view showing an example of an optical film and a display device according to a third embodiment of the invention;
- 5 is a schematic cross-sectional view showing an example of an optical film and a display device according to a fourth embodiment of the invention.
- 4 is a graph showing a spectrum during white display output through an organic EL light source and a color filter in an example.
- 4 is a graph of each spectrum during red display, green display, and blue display output through an organic EL light source and a color filter in an example. It is the electrode reflectance of the organic EL display device for calculating the display device reflection characteristic 2 and the display device reflection hue 2 in the example.
- FIG. 1 is a schematic cross-sectional view showing an example of the optical film and the display device according to the first embodiment of the invention.
- a display device 50A of the present embodiment whose cross section in the thickness direction is shown in FIG. 1, displays a color image based on an image signal.
- the display device 50A includes the display section 20 and the optical film 10A of the present embodiment.
- the display section 20 includes a substrate 21 , a light emitting element 22 and a color filter section 23 .
- the substrate 21 is formed of, for example, a silicon substrate.
- the light emitting element 22 emits white light.
- an organic EL element may be used as the light emitting element 22 .
- An organic EL element generates excitons by applying a DC voltage between an anode and a cathode, injecting electrons and holes into the organic light-emitting layer and recombining them, and deactivating the excitons. It emits light using the emission of light.
- Light from the light emitting element 22 is emitted in a light emitting direction from the lower side to the upper side in the figure, centering on the optical axis orthogonal to the organic light emitting layer.
- the light emitting element 22 is manufactured on the substrate 21 using, for example, a semiconductor manufacturing process.
- Electrodes in each light emitting element 22 are connected to a drive circuit (not shown) through metal wiring formed on the substrate 21 .
- the drive circuit controls lighting and extinguishing of each light emitting element 22 based on the image signal.
- the light-emitting elements 22 are composed of a first light-emitting element 22R that is lit according to a red component image signal, a second light-emitting element 22G that is lit according to a green component image signal, and a blue component image signal. are arranged in each pixel for color display.
- the color filter section 23 is arranged in the light emission direction of each light emitting element 22 .
- the color filter section 23 has a red filter that transmits red light, a green filter that transmits green light, and a blue filter that transmits blue light.
- the red filter is arranged to face the first light emitting element 22R
- the green filter is arranged to face the second light emitting element 22G
- the blue filter is arranged to face the third light emitting element 22B.
- the color filter section 23 may have a lens that condenses light passing through each red filter, each green filter, and each blue filter.
- the optical film 10A of this embodiment is arranged on the color filter section 23 of the display section 20 .
- the optical film 10A is provided to improve the color purity in the display area of the display section 20 and improve the display quality due to external light reflection.
- the optical film 10A includes a transparent substrate 11, a colored layer 12, an ultraviolet absorbing layer 13 (functional layer), and a low refractive index layer 14A (functional layer) in this order in the light emission direction of the display section 20.
- the transparent substrate 11 is a plate or sheet having a first surface 11a and a second surface 11b in the thickness direction.
- the second surface 11 b of the transparent substrate 11 is arranged on the color filter section 23 side of the display section 20 . It is preferable that the visible light transmittance of the material of the transparent substrate 11 is as close to 100% as possible.
- visible light is light in the visible light wavelength band of 380 nm or more and 780 nm or less.
- Materials for the transparent substrate 11 include polyolefins such as polyethylene and polypropylene, polyesters such as polybutylene terephthalate and polyethylene naphthalate, polyacrylates such as polymethyl methacrylate, polyamides such as nylon 6 and nylon 66, polyimides, polyarylates, and polycarbonates. , triacetyl cellulose, polyvinyl alcohol, polyvinyl chloride, cycloolefin copolymer, norbornene-containing resin, polyethersulfone, polysulfone, and other transparent resins and inorganic glass can be used.
- a film made of polyethylene terephthalate (PET), a film made of triacetyl cellulose (TAC), a film made of polymethyl methacrylate (PMMA), and a film made of polyester can be preferably used.
- the thickness of the transparent substrate 11 is not particularly limited, it is preferably 10 ⁇ m to 100 ⁇ m.
- the colored layer 12 is a layered portion containing a dye, and is arranged so as to overlap the first surface 11 a of the transparent base material 11 .
- the colored layer 12 contains, as pigments, a first coloring material, a second coloring material, and a third coloring material.
- the first colorant has a maximum absorption wavelength in the range of 470 nm or more and 530 nm or less, and a half width (full width at half maximum) of an absorption spectrum of 15 nm or more and 45 nm or less.
- the maximum absorption wavelength means the wavelength that gives the maximum value among the maximum values of the light absorption rate in the spectrum of the light absorption rate (absorption spectrum).
- the second colorant In the light transmittance spectrum, it means the wavelength that gives the minimum value among the minimum values.
- the second colorant has a maximum absorption wavelength in the range of 560 nm or more and 620 nm or less, and a half width of the absorption spectrum of 15 nm or more and 55 nm or less.
- the wavelength with the lowest transmittance of the third color material In the wavelength range of 400 nm to 780 nm, the wavelength with the lowest transmittance of the third color material is in the range of 650 nm or more and 780 nm or less.
- the half width of the absorption spectrum of the third colorant is, for example, 10 nm or more and 300 nm or less, but is not particularly limited.
- coloring materials when the first coloring material, the second coloring material, and the third coloring material are collectively referred to, they may simply be referred to as coloring materials.
- a porphyrin structure As the first colorant, the second colorant, and the third colorant contained in the colored layer 12, a porphyrin structure, a merocyanine structure, a phthalocyanine structure, an azo structure, a cyanine structure, a squarylium structure, a coumarin structure, a polyene structure, A compound containing one or more compounds selected from the group consisting of compounds having any of a quinone structure, a tetradiporphyrin structure, a pyrromethene structure and an indigo structure, and metal complexes thereof can be used.
- the colored layer 12 in this embodiment does not contain a dye having a main absorption wavelength band of 390 to 435 nm.
- the colored layer 12 may contain a dye having a main absorption wavelength band in the wavelength range of 390 to 435 nm. does not have the function of improving the reliability of Therefore, simply to adjust the color properties of the colored layer 12, the colored layer 12 can contain a dye having a main absorption wavelength band between 390 and 435 nm. Further, by incorporating a dye having a main absorption wavelength band in the wavelength range of 390 to 435 nm into the functional layer above the colored layer 12, the reliability of the colored layer 12 can be improved.
- the optical film 10A of the present invention is irradiated with a D65 light source from the surface 10a side, which is the outermost surface opposite to the transparent substrate 11, and is completely diffusely reflected on the second surface 11b side of the lowermost layer of the optical film.
- the chromaticness indices (values) a * and b * of the hue reflected by the optical film represented by the above formulas (1) to (9) are Each is in the range of -5 or more and +5 or less.
- the aforementioned hue is one of the uniform color spaces defined by the International Commission on Illumination (CIE) (also referred to as the CIE 1976 L * a * b * color space, or CIE LAB color space), and the above equation (1 ), and the three values of the lightness index L * represented by the following equation (10) in addition to the equation (2).
- CIE International Commission on Illumination
- Y is the tristimulus value of the reflected light at the reflectance R ( ⁇ ) of the D65 light source and is calculated from the above equations (4), (5), (7), and (9), and Y n is the D65 Tristimulus values at the white point of the light source.
- the light emitted from the optical film 10A is divided into a surface reflection component and an internal reflection component.
- the surface reflection component is defined by R2( ⁇ ) [%], which is the surface reflectance on the surface 10a.
- the internal reflection component is the reflectance R E ( ⁇ ) [%], the transmittance T ( ⁇ ) of the optical film 10A, and the surface reflectance R2 ( ⁇ ) [%] of the surface 10a, R1 ( ⁇ ) [%] calculated by the formula (4) defined by Assuming that the reflectance of the optical film 10A on the side of the surface 10a irradiated with the D65 light source is R( ⁇ ) [%], R( ⁇ ) is calculated from the above equation (5). Similar to R1( ⁇ ) and R2( ⁇ ), R( ⁇ ) is a function of the wavelength ⁇ . Therefore, the tristimulus values X, Y, Z is found.
- the definite integral may be obtained by appropriate numerical integration.
- the wavelength intervals in numerical integration may be equal intervals, such as 1 nm intervals.
- X, Y, and Z in formulas (1) and (2) are tristimulus values of reflected light at the reflectance R ( ⁇ ) of the D65 light source on the surface 10a side of the optical film 10A
- X n , Y n , Z n represent the tristimulus values at the white point of the D65 illuminant.
- the chromaticness indices a * and b * which are indexes of the external light reflection hue of the optical film 10A, can be calculated.
- each of the hue chromaticness index (value) a * and the value b * of the optical film 10A is in the range of -5 or more and +5 or less.
- the internal reflectance generated on the inner surface such as the display portion and the electrode wiring portion of a self-luminous display device such as an organic light-emitting display device generally has a different value at each wavelength from 380 nm to 780 nm, but the present invention
- R E ( ⁇ ) is defined as the reflectance on the perfect diffuse reflection surface with 100% at all wavelengths
- the chromaticness index (value) a * and the value When each of b * is in the range of ⁇ 5 or more and +5 or less, even when R E ( ⁇ ) is replaced with the internal reflectance of the display section 20 of the actual self-luminous display device, it is an index of the external light reflection hue. It has been found that certain chromaticness indices a * and b * are within
- the colored layer 12 having such a configuration, as a whole, it has maximum absorption wavelengths in the range of 470 nm to 530 nm and in the range of 560 nm to 620 nm, and the maximum absorption in the range of 400 nm to 780 nm is 650 nm or more.
- a spectral absorption spectrum having a minimum absorption wavelength in the range of 620 nm to 780 nm is obtained because the third colorant is included in the range of 780 nm or less. Therefore, most of the red light, green light, and blue light emitted from the display section 20 pass through the colored layer 12 .
- the colored layer 12 wavelength components between the maximum wavelengths of red light and green light, wavelength components between the maximum wavelengths of green light and blue light, ultraviolet light, and infrared light A part of the transmitted light amount is reduced. Therefore, for example, the colored layer 12 absorbs the wavelength component of the light reflected by the wiring of the display unit 20 , which reduces the color purity of the display light.
- the colored layer 12 may contain at least one of a radical scavenger, a singlet oxygen quencher, and a peroxide decomposer as an additive.
- a radical scavenger e.g., a fluoride
- a singlet oxygen quencher e.g., a peroxide decomposer
- a peroxide decomposer e.g., a peroxide decomposer
- Radical scavengers capture radicals when pigments are oxidatively deteriorated, and have the function of suppressing autoxidation, suppressing pigment deterioration (fading).
- a hindered amine light stabilizer having a molecular weight of 2000 or more is used as the radical scavenger, a high effect of suppressing fading can be obtained.
- the molecular weight of the radical scavenger is low, it is easy to volatilize, so few molecules remain in the colored layer, making it difficult to obtain a sufficient anti-fading effect.
- Examples of materials suitably used as radical scavengers include Chimassorb (registered trademark) 2020FDL, Chimassorb (registered trademark) 944FDL, Tinuvin (registered trademark) 622 manufactured by BASF, and LA-63P manufactured by ADEKA.
- the singlet oxygen quencher inactivates the highly reactive singlet oxygen, which tends to cause oxidative deterioration (fading) of the pigment, and works to suppress the oxidative deterioration (fading) of the pigment.
- singlet oxygen quenchers include transition metal complexes, dyes, amines, phenols, and sulfides. Materials that are particularly preferably used include transition metals such as dialkyl phosphates, dialkyldithiocarbates, and benzenedithiols.
- nickel, copper or cobalt is preferably used as the central metal. Examples thereof include NKX1199, NKX113, and NKX114 manufactured by Hayashibara Biochemical Laboratory Co., Ltd., and D1781, B1350, B4360, and T3204 manufactured by Tokyo Kasei Co., Ltd.
- peroxide decomposer As a peroxide decomposer, it works to decompose the peroxide generated when the pigment is oxidatively deteriorated, stop the auto-oxidation cycle, and suppress the pigment deterioration (fading). Phosphorus-based antioxidants and sulfur-based antioxidants can be used as peroxide decomposers.
- Phosphorus antioxidants include, for example, 2,2′-methylenebis(4,6-di-t-butyl-1-phenyloxy)(2-ethylhexyloxy)phosphorus, 3,9-bis(2,6-di -tert-butyl-4-methylphenoxy)-2,4,8,10-tetraoxa-3,9-diphosphaspiro[5.5]undecane, and 6-[3-(3-t-butyl-4-hydroxy- 5-methylphenyl)propoxy]-2,4,8,10-tetra-t-butyldibenz[d,f][1,3,2]dioxaphosphepine and the like.
- sulfur-based antioxidants examples include 2,2-bis( ⁇ [3-(dodecylthio)propionyl]oxy ⁇ methyl)-1,3-propanediyl-bis[3-(dodecylthio)propionate], 2-mercaptobenz imidazole, dilauryl-3,3'-thiodipropionate, dimyristyl-3,3'-thiodipropionate, distearyl-3,3'-thiodipropionate, pentaerythrityl-tetrakis(3-laurylthiopropionate pionate), 2-mercaptobenzothiazole, and the like.
- the ultraviolet absorbing layer 13 is a layered portion having an ultraviolet shielding rate of 85% or more.
- the UV shielding rate is measured and calculated based on JIS L 1925, and is represented by the value [%] obtained by subtracting the average transmittance (unit: [%]) in the wavelength range from 290 nm to 400 nm from 100%.
- the absorption wavelength range in the ultraviolet region of the ultraviolet absorption layer 13 is in the range of 290 nm or more and 370 nm or less.
- the absorption wavelength range is defined as a wavelength range in which the absorption rate of ultraviolet rays is 90% or more.
- the ultraviolet absorbing layer 13 is arranged on the side opposite to the transparent substrate 11 with the colored layer 12 interposed therebetween.
- the ultraviolet absorbing layer 13 is laminated on the colored layer 12, but the ultraviolet absorbing layer 13 and the colored layer 12 may be arranged with another layer sandwiched therebetween.
- each colorant contained in the colored layer 12 has an excellent color correction function, it does not have sufficient resistance to light rays, especially ultraviolet rays. become unable.
- the ultraviolet absorption layer 13 is arranged on the side on which the external light is incident earlier than the colored layer 12, when the external light contains ultraviolet rays, the colored layer 12 can suppress the amount of incident ultraviolet rays. Therefore, the light resistance of the colored layer 12 to ultraviolet rays can be improved.
- the ultraviolet absorbing layer 13 is formed by applying a composition containing an energy ray-curable resin, a photopolymerization initiator, an ultraviolet absorber, and a solvent, drying it, and curing it by irradiating it with energy rays such as ultraviolet rays.
- the energy ray-curable resin contained in the ultraviolet absorption layer 13 is a resin that is polymerized and cured by irradiation with active energy rays such as ultraviolet rays and electron beams.
- Acrylate monomers can be used.
- (meth)acrylate is a generic term for both acrylate and methacrylate
- (meth)acryloyl is a generic term for both acryloyl and methacryloyl.
- Examples of monofunctional (meth)acrylate compounds include 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, n-butyl (meth)acrylate, isobutyl ( meth)acrylate, t-butyl (meth)acrylate, glycidyl (meth)acrylate, acryloylmorpholine, N-vinylpyrrolidone, tetrahydrofurfuryl acrylate, cyclohexyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, isobornyl (meth)acrylate ) acrylate, isodecyl (meth) acrylate, lauryl (meth) acrylate, tridecyl (meth) acrylate, cetyl (meth) acrylate, stearyl (meth) acrylate, benzyl (meth) acrylate,
- bifunctional (meth)acrylate compounds include ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, butanediol di(meth)acrylate, hexanediol di(meth)acrylate, nonanediol di(meth) Acrylates, ethoxylated hexanediol di(meth)acrylate, propoxylated hexanediol di(meth)acrylate, diethylene glycol di(meth)acrylate, polyethylene glycol di(meth)acrylate, tripropylene glycol di(meth)acrylate, polypropylene glycol di(meth)acrylate Di(meth)acrylates such as meth)acrylate, neopentyl glycol di(meth)acrylate, ethoxylated neopentyl glycol di(meth)acrylate, tripropylene glycol di(meth)acrylate, neopentyl
- tri- or higher functional (meth)acrylate compounds include trimethylolpropane tri(meth)acrylate, ethoxylated trimethylolpropane tri(meth)acrylate, propoxylated trimethylolpropane tri(meth)acrylate, and tris-2-hydroxyethyl.
- Tri(meth)acrylates such as isocyanurate tri(meth)acrylate, glycerin tri(meth)acrylate, pentaerythritol tri(meth)acrylate, dipentaerythritol tri(meth)acrylate, ditrimethylolpropane tri(meth)acrylate, etc.) Functional (meth)acrylate compounds, pentaerythritol tetra(meth)acrylate, ditrimethylolpropane tetra(meth)acrylate, dipentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, ditrimethylolpropane penta(meth)acrylate ) acrylate, dipentaerythritol hexa (meth) acrylate, ditrimethylolpropane hexa (meth) acrylate trifunctional or higher polyfunctional (meth) acrylate compounds, and
- Urethane (meth)acrylate can also be used as an active energy ray-curable resin.
- urethane (meth)acrylates include those obtained by reacting a product obtained by reacting a polyester polyol with an isocyanate monomer or a prepolymer with a (meth)acrylate monomer having a hydroxyl group. .
- urethane (meth)acrylates examples include pentaerythritol triacrylate hexamethylene diisocyanate urethane prepolymer, dipentaerythritol pentaacrylate hexamethylene diisocyanate urethane prepolymer, pentaerythritol triacrylate toluene diisocyanate urethane prepolymer, dipentaerythritol pentaacrylate toluene diisocyanate.
- Examples include urethane prepolymers, pentaerythritol triacrylate isophorone diisocyanate urethane prepolymers, and dipentaerythritol pentaacrylate isophorone diisocyanate urethane prepolymers.
- the resins described above may be used alone or in combination of two or more. Further, the above resin may be a monomer in the hard coat layer forming composition, or may be a partially polymerized oligomer.
- the ultraviolet absorbent contained in the ultraviolet absorbing layer 13 can be exemplified by benzophenone-based, benzotriazole-based, triazine-based, oxalic acid anilide-based, and cyanoacrylate-based compounds.
- the absorption wavelength range is preferably in the range of 290 nm to 370 nm.
- the photopolymerization initiator contained in the ultraviolet absorption layer 13 contains one or more of those whose absorption wavelength range in the ultraviolet region is different from that of the ultraviolet absorber in the ultraviolet region. In this case, light in the ultraviolet region that is not absorbed by the ultraviolet absorber can cure the energy ray-curable compound, so that a cured film can be efficiently formed.
- an acylphosphine oxide-based photopolymerization initiator having a different absorption wavelength range from the wavelength range can be suitably used, and diphenyl (2, Examples include 4,6-trimethylbenzoyl)phosphine oxide and phenylbis(2,4,6-trimethylbenzoyl)phosphine oxide.
- photopolymerization initiators used in the composition for forming the ultraviolet absorbing layer 13 include, for example, 2,2-ethoxyacetophenone, 1-hydroxycyclohexylphenylketone, dibenzoyl, benzoin, benzoin methyl ether, benzoin ethyl ether, p -chlorobenzophenone, p-methoxybenzophenone, Michler's ketone, acetophenone, 2-chlorothioxanthone and the like can also be used. One type of these may be used alone, or two or more types may be used in combination.
- Solvents used in the composition for forming the ultraviolet absorbing layer 13 include dibutyl ether, dimethoxymethane, dimethoxyethane, diethoxyethane, propylene oxide, 1,4-dioxane, 1,3-dioxolane, and 1,3,5-trioxane.
- ketones such as acetone, methyl ethyl ketone, diethyl ketone, dipropyl ketone, diisobutyl ketone, methyl isobutyl ketone, cyclopentanone, cyclohexanone, methylcyclohexanone and methyl cyclohexanone, and ethyl formate.
- the surface hardness of the optical film 10A including the ultraviolet absorbing layer 13 is H or higher in terms of pencil hardness with a load of 500 g. Pencil hardness is measured according to JIS-K5600-5-4:1999. Therefore, the ultraviolet absorbing layer 13 in this embodiment functions as an ultraviolet protective layer that protects the colored layer 12 from ultraviolet rays from the outside of the optical film 10A, and also protects the colored layer 12 against external loads. Also functions as a hard coat layer. As in the present embodiment, the ultraviolet absorption layer 13, which serves both as an ultraviolet protective layer and a hard coat layer, uses, for example, the energy ray-curable resin described above, and balances the absorption wavelengths of the ultraviolet absorber and the photopolymerization initiator. A hard resin layer can be produced by controlling the curing inhibition.
- metal oxide fine particles may be contained for the purpose of adjusting the refractive index of the hard coat layer and imparting hardness.
- Metal oxide fine particles include zirconium oxide, titanium oxide, niobium oxide, antimony trioxide, antimony pentoxide, tin oxide, indium oxide, indium tin oxide, and zinc oxide.
- the ultraviolet absorbing layer 13 may contain other additives such as a leveling agent, an antifoaming agent, an antioxidant, a light stabilizer, a photosensitizer, and a conductive material.
- the low refractive index layer 14A is arranged on the side closest to the user (viewer) viewing the display when the optical film 10A is applied to the display device 50A.
- the low refractive index layer 14A is laminated on the surface of the ultraviolet absorption layer 13 opposite to the colored layer 12 .
- the thickness of the low refractive index layer 14A is, for example, but not limited to, about 40 nm to 1 ⁇ m.
- the low refractive index layer 14A is made of a material having a lower refractive index than the ultraviolet absorption layer 13. As shown in FIG.
- the low refractive index layer 14A is a layered portion made of an inorganic substance or an inorganic compound.
- inorganic substances and inorganic compounds include fine particles such as LiF, MgF, 3NaF.AlF, AlF, Na 3 AlF 6 and silica fine particles.
- silica fine particles it is effective to use porous silica fine particles, hollow silica fine particles, or the like having voids inside the particles to lower the refractive index.
- the photopolymerization initiator, solvent, and other additives described for the ultraviolet absorbing layer 13 may be appropriately added to the composition for forming a low refractive index.
- the material of the low refractive index layer 14A further contains any one of silicon oxide, fluorine-containing silane compound, fluoroalkylsilazane, fluoroalkylsilane, fluorine-containing silicon-based compound, and perfluoropolyether group-containing silane coupling agent. may By containing these materials, at least one of water repellency and oil repellency is imparted to the low refractive index layer 14, and antifouling properties can be enhanced.
- the ultraviolet absorbing layer 13 and the low refractive index layer 14A form one or more functional layers arranged on the opposite side of the transparent substrate with the colored layer interposed therebetween.
- the optical film 10A may be provided with an appropriate functional layer between the colored layer 12 and the ultraviolet absorbing layer 13 as long as the required front luminance, external light reflection visibility, and color purity of display light are obtained.
- the optical film 10A can be manufactured by forming the colored layer 12, the ultraviolet absorbing layer 13, and the low refractive index layer 14A on the first surface 11a of the transparent substrate 11 in this order.
- the colored layer 12, the ultraviolet absorbing layer 13, and the low refractive index layer 14A are formed, for example, by applying a coating liquid containing the constituent materials of each layer, drying it, irradiating it with an active energy ray such as ultraviolet rays, and curing it. be able to.
- the low refractive index layer 14A can also be formed by vapor deposition, sputtering, or the like.
- the composition for forming the colored layer 12 contains an active energy ray-curable resin, a photopolymerization initiator, a dye, and a solvent, and may further contain additives as necessary.
- the active energy ray-curable resin, photopolymerization initiator, and solvent those described for the ultraviolet absorbing layer 13 can be used.
- the pigment includes the above-described first colorant, second colorant, and third colorant.
- the additive may contain at least one of a radical scavenger, a peroxide decomposer, and a singlet oxygen quencher.
- the ultraviolet absorbing layer 13 is formed by applying a composition containing at least an energy ray-curable compound, a photopolymerization initiator, an ultraviolet absorber, and a solvent onto the colored layer 12, and then applying an energy ray to initiate photopolymerization. can be formed by curing the composition.
- the low refractive index layer 14A is formed by applying a material for forming the low refractive index layer 14A on the ultraviolet absorbing layer 13, and then irradiating an energy beam for initiating photopolymerization. , can be formed by curing the composition.
- the display device 50A is manufactured by preparing the display section 20 and bonding and fixing the second surface 11b of the transparent substrate 11 of the optical film 10A to the surface of the color filter section 23 via an adhesive layer or the like. can be done.
- display light generated by the light emitting element 22 is transmitted through the color filter section 23 when the light emitting element 22 is turned on according to an image signal.
- the light from the first light emitting element 22R is red light
- the light from the second light emitting element 22G is green light
- the light from the third light emitting element 22B is blue light.
- the ultraviolet absorption layer 13, and the low refractive index layer 14A and exits the optical film 10A.
- the colored layer 12 has a wavelength band in which the transmittance of the red, green, and blue wavelength lights of the display light is excellent, each display light is emitted while maintaining the color purity.
- the ultraviolet absorption layer 13 mainly absorbs light in the ultraviolet region, the display light is transmitted with almost no decrease in luminance. Since the low refractive index layer 14A has a good transmittance for visible light, the display light is emitted to the outside with almost no decrease in brightness.
- the substrate 21 includes, for example, metal portions with high reflectance such as wiring and electrodes.
- the external light is reflected by the wiring, electrodes, etc., sequentially passes through the color filter portion 23, the transparent base material 11, the colored layer 12, the ultraviolet absorbing layer 13, and the low refractive index layer 14A, and is emitted to the outside. do.
- An observer of the display device 50A sees reflected light including display light, surface reflected light from the external light of the display device 50A, and external light transmitted through the interior of the display device 50A, and reflected internally reflected light.
- the external light passes through the colored layer 12 twice and is emitted to the outside, thereby reducing the wavelength component different from the wavelength component of the display light.
- a decrease in luminance of display light can be suppressed, and good color purity of display light can be maintained even when external light is superimposed on display light.
- the chromaticness indices a * and b * which are indicators of the reflection hue of the externally reflected light of the optical film 10A, are set to ⁇ 5 or more and +5 or less. The influence of the color tone of the film is reduced, and the blackness of the display screen is maintained.
- the ultraviolet light component of the external light is absorbed by the ultraviolet absorption layer 13, so that the colorant is prevented from deteriorating due to the ultraviolet light received by the colored layer 12.
- FIG. Therefore, the spectral characteristics of the colorant in the colored layer 12 are likely to be maintained over time.
- FIG. 3 is a schematic cross-sectional view showing an example of the optical film and the display device according to the second embodiment of the invention.
- a display device 50B of the present embodiment whose cross section in the thickness direction is shown in FIG. 3 includes the optical film 10B of the present embodiment instead of the optical film 10A of the display device 50A of the first embodiment.
- the optical film 10B is configured in the same manner as the optical film 10A except that an oxygen barrier layer 15 (functional layer) is provided between the colored layer 12 and the ultraviolet absorbing layer 13 .
- an oxygen barrier layer 15 functional layer
- the oxygen barrier layer 15 is a transparent layer having optical transparency.
- the oxygen permeability of the oxygen barrier layer 15 is 10 cc/m 2 ⁇ day ⁇ atm or less.
- the main constituent material of the oxygen barrier layer 15 preferably contains polyvinyl alcohol (PVA), ethylene-vinyl alcohol copolymer (EVOH), vinylidene chloride, siloxane resin, and the like. (registered trademark), EVAL and POVAL manufactured by Kuraray Co., Ltd., Saran Latex and Saran Resin manufactured by Asahi Kasei Corporation can be used.
- Inorganic particles such as silica particles, alumina particles, silver particles, copper particles, titanium particles, zirconia particles, and tin particles may be dispersed in the oxygen barrier layer 15 to reduce oxygen permeability.
- an oxygen barrier layer may be provided on the second surface 11b side of the transparent substrate 11 as well.
- the oxygen barrier layer protects each colorant of the colored layer 12 from oxygen present in the display device 50B.
- the colored layer 12, the ultraviolet absorbing layer 13, and the low refractive index layer 14A which are the same as those of the first embodiment, are provided. have action.
- the optical film 10B of the present embodiment further includes the oxygen barrier layer 15, it is possible to suppress the oxidative deterioration of the dye in the colored layer 12 due to the influence of oxygen.
- FIG. 4 is a schematic cross-sectional view showing an example of the optical film and the display device according to the third embodiment of the invention.
- a display device 50C of the present embodiment whose cross section in the thickness direction is shown in FIG. 4 includes the optical film 10C of the present embodiment instead of the optical film 10A of the display device 50A of the first embodiment.
- the optical film 10C is configured in the same manner as the optical film 10A except that the low refractive index layer 14A and the ultraviolet absorption layer 13 are replaced with an ultraviolet absorption antiglare layer 16 (ultraviolet absorption layer, functional layer, antiglare layer). be.
- the following description will focus on the differences from the first embodiment.
- the UV-absorbing antiglare layer 16 is a layered portion having UV absorption and antiglare functions. Similar to the UV absorbing layer 13, the UV absorbing antiglare layer 16 has a UV blocking rate of 85% or more. More preferably, the absorption wavelength range of the ultraviolet absorbing antiglare layer 16 is in the range of 290 nm or more and 370 nm or less.
- the anti-glare function is a function of reducing reflection of external light by having minute unevenness on the surface and scattering external light with the unevenness.
- the pencil hardness of the UV-absorbing antiglare layer 16 is H or higher, like the UV-absorbing layer 13 .
- the UV-absorbing antiglare layer 16 can be formed by curing a coating liquid containing at least one of organic fine particles and inorganic fine particles imparting an antiglare function to a composition similar to that of the UV absorbing layer 13. can.
- the organic fine particles form fine unevenness on the surface of the UV-absorbing antiglare layer 16 and impart a function of diffusing external light.
- two or more kinds of resin particles having different materials may be mixed and used.
- the inorganic fine particles adjust sedimentation and aggregation of the organic fine particles in the ultraviolet absorbing antiglare layer 16, and silica fine particles, metal oxide fine particles, various mineral fine particles, and the like can be used.
- silica fine particles that can be used include colloidal silica and silica fine particles surface-modified with reactive functional groups such as (meth)acryloyl groups.
- metal oxide fine particles that can be used include alumina, zinc oxide, tin oxide, antimony oxide, indium oxide, titania, and zirconia.
- Mineral fine particles include, for example, mica, synthetic mica, vermiculite, montmorillonite, iron montmorillonite, bentonite, beidellite, saponite, hectorite, stevensite, nontronite, magadiite, islarite, kanemite, layered titanate, smectite, synthetic Smectite and the like can be used.
- Mineral fine particles may be either natural products or synthetic products (including substituted products and derivatives), and a mixture of both may be used.
- layered organoclays are more preferred.
- a layered organic clay is a swelling clay in which an organic onium ion is introduced between layers.
- the organic onium ion is not limited as long as it can be organized by utilizing the cation exchange property of the swelling clay.
- the synthetic smectites described above can be suitably used.
- Synthetic smectite has the function of increasing the viscosity of the coating liquid for forming the antiglare layer, suppressing the sedimentation of resin particles and inorganic fine particles, and adjusting the irregular shape of the surface of the optical function layer.
- the composition for forming the ultraviolet absorbing antiglare layer 16 is any one of silicon oxides, fluorine-containing silane compounds, fluoroalkylsilazanes, fluoroalkylsilanes, fluorine-containing silicon compounds, and perfluoropolyether group-containing silane coupling agents. may contain These materials impart at least one of water repellency and oil repellency to the ultraviolet absorbing antiglare layer 16, and can enhance the antifouling property of the optical film 10C.
- the ultraviolet absorbing antiglare layer 16 may be formed as a layer in which a layer with a relatively high refractive index and a layer with a relatively low refractive index are laminated in order from the colored layer 12 side.
- the refractive index of the layer with a relatively high refractive index on the colored layer 12 side is set to 1.50 to 2.40, and the optical film 10C surface side It is preferable that the refractive index of the layer having a relatively low refractive index is 1.20 to 1.55.
- the optical film 10C of this embodiment is an example in which the ultraviolet absorbing antiglare layer 16, which is an ultraviolet absorbing layer, also serves as an antiglare layer.
- the colored layer 12 similar to that of the first embodiment and the UV-absorbing antiglare layer 16 having UV-absorbing properties similar to the UV-absorbing layer 13 are provided. Therefore, it has the same function as the first embodiment.
- the optical film 10 ⁇ /b>C of this embodiment includes the ultraviolet absorbing antiglare layer 16 that also serves as an antiglare layer, external light is scattered in the ultraviolet absorbing antiglare layer 16 . Therefore, surface reflection and glare of external light are suppressed, so that visibility of the display screen and display light is improved, and degradation of display quality due to external light reflection can be suppressed.
- a display device 50D of this modification includes an optical film 10D of this modification instead of the optical film 10C of the display device 50C of the third embodiment.
- the optical film 10D is the same as the optical film 10C, except that instead of the ultraviolet absorbing antiglare layer 16, the ultraviolet absorbing layer 13 similar to that of the first embodiment and the antiglare layer 17 (functional layer) are provided. configured to In the following, the points different from the third embodiment will be mainly described.
- the antiglare layer 17 is a layered portion having an antiglare function.
- the arrangement of the antiglare layer 17 is not particularly limited as long as it is arranged on the opposite side of the transparent substrate 11 from the colored layer 12 of the ultraviolet absorption layer 13 .
- the antiglare layer 17 is arranged to cover the outside of the ultraviolet absorption layer 13 and is positioned on the outer surface of the optical film 10D.
- the optical film 10D of this modified example is an example in which the ultraviolet absorbing layer 13, which is an ultraviolet absorbing layer, and the antiglare layer 17 are separate layers.
- the optical film 10D and the display device 50D of this modified example since the colored layer 12 and the ultraviolet absorption layer 13 similar to those of the first embodiment are provided, they have the same effects as those of the first embodiment.
- the optical film 10 ⁇ /b>D of this modified example includes the antiglare layer 17 , external light is scattered by the antiglare layer 17 . Therefore, surface reflection and glare of external light are suppressed, so that visibility of the display screen and display light is improved, and degradation of display quality due to external light reflection can be suppressed.
- FIG. 5 is a schematic cross-sectional view showing an example of an optical film and a display device according to a fourth embodiment of the invention.
- a display device 50E of the present embodiment whose cross section in the thickness direction is shown in FIG. 5 includes the optical film 10E of the present embodiment instead of the optical film 10C of the display device 50C of the third embodiment.
- the optical film 10E is configured in the same manner as the optical film 10C, except that the low refractive index layer 14E (functional layer) is laminated on the ultraviolet absorbing antiglare layer 16.
- the points different from the third embodiment will be mainly described.
- the low refractive index layer 14E is the same as the low refractive index layer 14A in the first embodiment, except that it has a lower refractive index than the ultraviolet absorbing antiglare layer 16.
- FIG. 1 the reflected light from the interface with the ultraviolet absorbing antiglare layer 16 and the reflected light from the surface of the low refractive index layer 14E of the external light entering from the outside interfere with each other, so that the surface reflectance of the external light is reduced. be done. Since the surface reflection of external light can be suppressed by providing the low refractive index layer 14E, the visibility of the display device 50E is improved.
- the material of the low refractive index layer 14E is not particularly limited as long as it is a transparent material having a refractive index lower than that of the ultraviolet absorbing antiglare layer 16.
- the material of the low refractive index layer 14E the same material as the low refractive index layer 14A in the first embodiment can be used.
- the optical film 10E and the display device 50E of the present embodiment since the colored layer 12 and the ultraviolet absorbing antiglare layer 16 similar to those of the third embodiment are provided, the effects similar to those of the third embodiment can be achieved. Prepare. In particular, since the optical film 10E of the present embodiment has the low refractive index layer 14E on the outer side, surface reflection and glare of external light are suppressed. A decrease in display quality due to light reflection can be suppressed.
- the light-emitting element is an organic EL element.
- the type of light emitting element is not limited to organic EL elements.
- examples of light-emitting elements include LED elements, inorganic phosphor light-emitting elements, and quantum dot light-emitting elements. configuration is also possible.
- the configurations of the functional layers are not limited to these.
- the ultraviolet absorbing layer 13 has been described as serving both as an ultraviolet absorbing layer and a hard coat layer, even if it includes an ultraviolet absorbing layer with a pencil hardness of less than H and a hard coat layer with a pencil hardness of H or higher, good.
- the hard coat layer is more preferably provided outside the ultraviolet absorbing layer.
- the low refractive index layer or the antiglare layer may have a structure that also serves as a hard coat layer.
- the functional layer may further include at least one of an antistatic layer containing an antistatic agent and an antifouling layer having water repellency.
- the antistatic layer and the antifouling layer may be composed of the various functional layers described above.
- optical film according to the present invention will be further described using Examples 1-10 and Comparative Examples 1-6.
- the present invention is not limited at all by the specific contents of each of the following examples.
- optical films 1 to 16 having layer structures shown in [Table 1] and [Table 2] were produced.
- the optical film properties of the produced optical films 1 to 13 were evaluated.
- the display device characteristics of the organic EL panel were confirmed by simulation.
- ⁇ Second color material Dye-2 tetraazaporphyrin copper complex dye (FDG-007 manufactured by Yamada Chemical Co., Ltd., maximum absorption wavelength 595 nm, half width 22 nm)
- Dye-3 Tetraazaporphyrin copper complex dye (PD-311S manufactured by Yamamoto Kasei Co., Ltd., maximum absorption wavelength 586 nm, half width 22 nm)
- Dye-4 phthalocyanine copper complex dye Yamada Chemical Co., Ltd. FDN-002, maximum absorption wavelength 800 nm
- Dye-5 phthalocyanine cobalt complex dye Yamada Chemical Co., Ltd.
- Example 9 (Oxygen barrier layer formation) On the structure of Example 9 shown in [Table 1], the composition for forming an oxygen barrier layer was applied and dried to form an oxygen barrier layer 1 having an oxygen permeability of 1 cc/m 2 ⁇ day ⁇ atm. did.
- Hard coat layer formation The composition for forming a hard coat layer shown in [Table 4] below was applied onto the colored layer or transparent substrate shown in [Table 1] and [Table 2], dried in an oven at 80°C for 60 seconds, After that, the coating film is cured by performing ultraviolet irradiation (light source H bulb manufactured by Fusion UV Systems Japan Co., Ltd.) at an irradiation dose of 150 mJ / cm 2 using an ultraviolet irradiation device, and the film thickness after curing is 5.0 ⁇ m. Hard coat layers 1 to 3 described in [Table 1] and [Table 2] were formed.
- ultraviolet irradiation light source H bulb manufactured by Fusion UV Systems Japan Co., Ltd.
- ⁇ Ultraviolet absorber Tinuvin (registered trademark) 479 (manufactured by BASF Japan, maximum absorption wavelength 322 nm) LA-36 (manufactured by ADEKA, maximum absorption wavelength 310 nm, 350 nm)
- Active energy ray curable resin Light acrylate PE-3A (manufactured by Kyoeisha Chemical Co., Ltd., refractive index 1.52)
- Photopolymerization initiator Omnirad (registered trademark) TPO (manufactured by IGM Resins B.V., absorption wavelength peaks 275 nm, 379 nm)
- ⁇ Resin particles Styrene-methyl methacrylate copolymer particles (refractive index 1.515, average particle size 2.0 ⁇ m)
- Inorganic fine particles 1 Synthetic smectite/inorganic fine particles 2: Alumina nanoparticles, average particle size 40
- the composition for forming an antiglare layer shown in the following [Table 5] is applied, dried in an oven at 80 ° C. for 60 seconds, and then an ultraviolet irradiation device.
- the coating film is cured by performing ultraviolet irradiation (light source H bulb manufactured by Fusion UV Systems Japan Co., Ltd.) at an irradiation dose of 150 mJ / cm 2 using [Table 1].
- the antiglare layers 1 and 2 described were formed.
- composition for forming low refractive index layer 1 As the low refractive index layer-forming composition used for forming the low refractive index layer 1, the following was used.
- ⁇ Refractive index adjuster Porous silica fine particle dispersion (average particle diameter 75 nm, solid content 20%, solvent methyl isobutyl ketone) 8.5 parts by mass
- Antifouling agent Optool (registered trademark) AR-110 (manufactured by Daikin Industries, Ltd., solid content 15%, solvent methyl isobutyl ketone) 5.6 parts by mass
- Active energy ray curable resin Pentaerythritol triacrylate 0.4 parts by mass Initiator: Omnirad (registered trademark) 184 (manufactured by IGM Resins B.V.) 0.07 parts by mass
- Leveling agent RS-77 (manufactured by DIC) 1.7 parts by mass
- Solvent Methyl isobutyl ketone 83.73 parts by mass
- the composition for forming a low refractive index layer having the above composition is applied, dried in an oven at 80 ° C. for 60 seconds, and then The coating film is cured by irradiating with ultraviolet rays at an irradiation dose of 200 mJ/cm 2 using an ultraviolet irradiation device (light source H bulb manufactured by Fusion UV Systems Japan), and the film thickness after curing is 100 nm [Table 1 ] and [Table 2] were formed.
- an ultraviolet irradiation device light source H bulb manufactured by Fusion UV Systems Japan
- optical films 1 to 13 were evaluated as follows.
- UV shielding rate The ultraviolet absorbing layer formed on the colored layer of the obtained optical film was peeled off from the colored layer using cellophane tape conforming to JIS-K5600 adhesion test, and an automatic spectrophotometer (manufactured by Hitachi, Ltd., U -4100), measure the transmittance of the single layer of the ultraviolet absorbing layer with the adhesive tape as a reference, calculate the average transmittance [%] in the ultraviolet region (290 nm to 400 nm), and set the ultraviolet shielding rate [%] to 100%. It was calculated as a value obtained by subtracting the average transmittance [%] in the ultraviolet region (290 nm to 400 nm) from the value.
- a xenon weather meter tester manufactured by Suga Test Instruments Co., Ltd., X75
- a xenon lamp illuminance 60 W/cm 2 (300 nm to 400 nm) and a tester temperature of 45.
- transmittance was measured using an automatic spectrophotometer (manufactured by Hitachi, Ltd., U-4100), and tested in a wavelength range of 470 nm to 530 nm.
- the transmittance difference ⁇ T ⁇ 1 at the wavelength ⁇ 1 indicating the minimum transmittance before the test at the wavelength ⁇ 2 indicating the minimum transmittance before the test in the wavelength range 560 nm to 620 nm.
- the transmittance difference ⁇ T ⁇ 3 before and after the test at the wavelength showing the minimum transmittance before the test was calculated.
- the transmittance difference is preferably close to zero, preferably
- ⁇ 20 (N 1 to 3), more preferably
- ⁇ 10 (N 1 to 3).
- the light resistance of the colored layers containing the first to third colorants is greatly improved by providing an upper layer with an ultraviolet absorption layer having an ultraviolet shielding rate of 85% or more. Improved. If the colored layer is provided with the ultraviolet absorbing ability, the effect is small, and it is preferable to dispose it as a separate layer on the upper layer.
- an oxygen blocking layer and containing a high molecular weight hindered amine light stabilizer as a radical scavenger and a dialkyldithiocarbanate nickel complex as a singlet oxygen quencher in the colored layer the light resistance of the colored layer is improved. performance was further improved. Further, by shifting the absorption wavelength regions of the photopolymerization initiator and the ultraviolet absorbent contained in the ultraviolet absorbing layer, it was possible to achieve both the ultraviolet absorbing ability and the hardness.
- the transmittance of the obtained optical film was measured using an automatic spectrophotometer (U-4100, manufactured by Hitachi, Ltd.), and the efficiency of light transmitted through the optical film during white display was calculated using this transmittance. It was calculated and evaluated as a white display transmission characteristic.
- the optical film was calculated as a ratio of the light intensity value at each wavelength of the transmitted light. The higher the light intensity ratio, the higher the luminance efficiency of the light source.
- FIG. 6 shows the spectrum of light emitted from the EL light source. In FIG. 6, the horizontal axis represents wavelength (nm) and the vertical axis represents transmitted light intensity (au).
- the transmittance T( ⁇ ) and surface reflectance R2( ⁇ ) of the obtained optical film were measured using an automatic spectrophotometer (U-4100, manufactured by Hitachi, Ltd.).
- U-4100 automatic spectrophotometer
- the surface of the triacetyl cellulose film of the transparent substrate on which the colored layer and the functional layer are not formed is coated with a matte black paint to prevent reflection. °, and the surface reflectance R2( ⁇ ) was obtained.
- the relative reflection value at the interface at each layer is It was calculated based on the above-described formulas (4), (5), (7), and (9) without considering reflection and surface reflection, and was evaluated as the reflection characteristic 1 of the display device. The lower the relative reflection value, the lower the intensity of the reflected light and the higher the display quality.
- the transmittance T( ⁇ ) and the surface reflectance R2( ⁇ ) of the obtained optical film were measured using an automatic spectrophotometer (model number: U-4100, manufactured by Hitachi, Ltd.).
- the surface reflectance R2( ⁇ ) the surface of the triacetyl cellulose film of the transparent substrate on which the colored layer and the functional layer are not formed is coated with a matte black paint to prevent reflection. °, and the surface reflectance R2( ⁇ ) was obtained.
- the chromaticness indices (values) a * and b * of the reflected hue for the D65 light source are calculated without considering the interface reflection and surface reflection at each layer. It was calculated based on the above formulas (1) to (9) and evaluated as display device reflection hue 1. The closer a * and b * are to zero, the better there is no tint, and preferably -5 or more and +5 or less.
- the electrode reflectance R E ( ⁇ ) was the electrode reflectance obtained from the reflectance measurement of the organic light-emitting display device (OLED 55C8PJA manufactured by LG Electronics) shown in FIG. The result calculated in the same manner was evaluated as the reflection characteristic 2 of the display device. Similar to the display device reflection characteristic 1, the lower the relative reflection value, the lower the intensity of the reflected light and the higher the display quality. In FIG. 8, the horizontal axis represents wavelength (nm) and the vertical axis represents reflectance (%).
- the electrode reflectance R E ( ⁇ ) was the electrode reflectance obtained by measuring the reflectance of the organic light-emitting display device (OLED 55C8PJA, manufactured by LG Electronics) shown in FIG. The result calculated in the same manner was evaluated as the reflection hue 2 of the display device. Similar to Display Device Reflection Hue 1, the closer a * and b * are to zero, the better there is no tint, and preferably -5 or more and +5 or less.
- the transmittance of the resulting optical film was measured using an automatic spectrophotometer (U-4100, manufactured by Hitachi, Ltd.).
- the NTSC ratio was calculated from the CIE1931 chromaticity values calculated using the red display, green display, and blue display spectra shown in FIG. The higher the NTSC ratio, the wider the color reproducibility, which is preferable.
- the horizontal axis represents wavelength (nm) and the vertical axis represents transmitted light intensity (au).
- the reflective properties of the display device with the colored layer were significantly reduced.
- the circularly polarizing plate reduces the transmittance by half
- the display device with the colored layer has excellent luminance efficiency and improved color reproducibility as shown in the evaluation value of white display transmittance.
- the colored layer provided with the first, second, and third color materials shown in this embodiment has the chromaticity of the reflected hue when the electrode reflection R E ( ⁇ ) is 100% at all wavelengths from 380 nm to 780 nm. It was possible to adjust the absorption intensity of the coloring material so that each of the indices a * and b * was within the range of -5 or more and +5 or less.
- the reflection hue of the optical film provided with the colored layer is adjusted by adjusting the compounding ratio of the first, second, and third color materials with respect to the electrode reflectance of the organic light-emitting display device having various wavelength dispersion properties. It is also an aspect of the present invention to set to neutral.
- an optical film and a display device that can improve the display quality due to the reflection of external light and improve the life of the light-emitting elements of the display device.
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Abstract
Description
本願は、2021年3月12日に日本に出願された特願2021-040749号について優先権を主張し、その内容をここに援用する。
偏光板および位相遅延板を用いた装置では、外部光による反射光の光量を抑制できるが、有機発光素子で発生する表示光の光量も低下するという問題がある。
さらに、特許文献1に開示されている波長選択吸収性を有する充填剤では、480nm~510nmの波長領域に吸収極大波長を有する色素と、580nm~610nmの波長領域に吸収極大波長を有する色素、を含有した構成が提案されている。このため、480nm未満の波長帯域、および610nmを超える波長帯域における外部光の影響を除去しにくいという問題がある。このような波長帯域の外部光が抑制できないと、反射率の低減効果が十分でなく、また反射色相の悪化が生じるという問題がある。さらに、前述の波長選択吸収性が付与される色素は耐光性などの信頼性が不十分で、信頼性の改善しなければ実用化は困難である。
式(1)~(3)から算出されるa*、b*はCIE1976L*a*b*色空間(CIELAB色空間)での算出方法に準じて算出される。式(1)、(2)において、Xn、Yn、Znは、D65光源の白色点における3刺激値である。
式(4)において、RE(λ)は完全拡散反射面での反射率[%]を表す関数(各波長100%)、R2(λ)は前記透明基材と反対側の前記光学フィルムにおける最表面での表面反射率[%]を表す関数、T(λ)は前記光学フィルムの透過率[%]を表す関数である。
式(6)~(9)においてPD65(λ)は、D65光源スペクトル、オーバーラインx(λ)、オーバーラインy(λ)、オーバーラインz(λ)は、CIE1931 2°視野での等色関数である。
式(6)から式(9)における定積分は、適宜の数値積分で求めることができる。数値積分を行う場合の波長間隔は、例えば1nm間隔である。
式(6)~(8)で表されるX、Y、Zは、D65光源の白色点における3刺激値を表す。
本発明の第1の実施形態に係る光学フィルムおよび表示装置について説明する。
図1は、本発明の第1の実施形態に係る光学フィルムおよび表示装置の一例を示す模式的な断面図である。
図1に厚さ方向の断面を示す本実施形態の表示装置50Aは、画像信号に基づいてカラー画像を表示する。表示装置50Aは、表示部20と、本実施形態の光学フィルム10Aと、を備える。
基板21は、例えば、シリコン基板で形成される。
発光素子22は、白色光を発光する。例えば、発光素子22としては、有機EL素子が用いられてもよい。有機EL素子は、陽極と陰極との間に直流電圧を印加し、有機発光層に電子および正孔を注入して再結合させることにより励起子を生成し、この励起子が失活する際の光の放出を利用して発光する。発光素子22からの光は、有機発光層と直交する光軸を中心として、図示下側から上側に向かう光出射方向に出射する。
発光素子22は、例えば、半導体製造プロセスを用いて基板21上に製造される。
例えば、発光素子22は、赤色成分の画像信号に応じて点灯される第1発光素子22Rと、緑色成分の画像信号に応じて点灯される第2発光素子22Gと、青色成分の画像信号に応じて点灯される第3発光素子22Bと、が、カラー表示を行う各画素内に配置されている。
カラーフィルタ部23は、赤色光を透過させる赤色フィルタ、緑色光を透過させる緑色フィルタ、および青色光を透過させる青色フィルタを有する。赤色フィルタは第1発光素子22Rに対向する位置に配置され、緑色フィルタは第2発光素子22Gに対向する位置に配置され、青色フィルタは第3発光素子22Bに対向する位置に配置されている。
カラーフィルタ部23は、各赤色フィルタ、各緑色フィルタ、および各青色フィルタを透過する光を集光するレンズを有していてもよい。
光学フィルム10Aは、表示部20の光出射方向において、透明基材11、着色層12、紫外線吸収層13(機能層)、および低屈折率層14A(機能層)をこの順に備える。
ここで可視光とは、380nm以上780nm以下の可視光波長帯域の光である。
着色層12は、色素として、第1の色材と、第2の色材と、第3の色材と、を含有する。
第1の色材は、極大吸収波長が470nm以上530nm以下の範囲にあり、吸光スペクトルの半値幅(半値全幅)が15nm以上45nm以下である。ここで、極大吸収波長とは、光吸収率のスペクトル(吸収スペクトル)において、光吸収率の極大値のうちの最大値を与える波長を意味する。光透過率のスペクトルでは、極小値のうち最小値を与える波長を意味する。以下も同様である。
第2の色材は、極大吸収波長が560nm以上620nm以下の範囲にあり、吸光スペクトルの半値幅が15nm以上55nm以下である。
第3の色材は、400nm~780nmの波長範囲において最も透過率の低い波長が650nm以上780nm以下の範囲内にある。第3の色材の吸光スペクトルの半値幅は、例えば10nm以上300nm以下であるが、特に限定されない。
以下、第1の色材、第2の色材、および第3の色材を総称する場合には、単に色材と称する場合がある。
例えば、特に分子内にポルフィリン構造、ピロメテン構造、フタロシアニン構造、スクアリリウム構造を持つ化合物を用いるのが好ましい。
本実施形態における着色層12は、波長390~435nmに主吸収波長帯域を有する染料を含んでいない。
着色層12は、波長390~435nmに主吸収波長帯域を有する染料を含んでいてもよいが、波長390~435nmに主吸収波長帯域を有する染料は、本発明の目的とする耐光性や耐熱性の信頼性向上の機能を有していない。したがって、単純に着色層12の色特性を調整するために、着色層12に波長390~435nmに主吸収波長帯域を有する染料を含ませることができる。また、着色層12の上層の機能層に波長390~435nmに主吸収波長帯域を有する染料を含有させることで、着色層12の信頼性向上を図ることが可能となる。
D65光源照射側の表面10a側での光学フィルム10Aの反射率をR(λ) [%]とするとR(λ)は、上述の式(5)から算出される。
R(λ)は、R1(λ)およびR2(λ)同様、波長λの関数であるので、式(6)から式(9)のλに関する定積分を求めることで3刺激値X、Y、Zが求まる。ここで、定積分は、適宜の数値積分で求められてもよい。例えば、数値積分を行う場合の波長間隔は、例えば1nm間隔のような等間隔であってもよい。
これに対して、着色層12において、赤色光および緑色光の各極大波長の間の波長成分、緑色光および青色光の各極大波長の間の波長成分、紫外光、および赤外光のそれぞれの一部の透過光量は低下する。このため、例えば、外部光が表示部20の配線などで反射した光のうち、表示光の色純度を低下させる波長成分が着色層12で吸収される。
紫外線吸収層13の紫外線領域における吸収波長域は、290nm以上370nm以下の範囲であることがより好ましい。ここで、吸収波長域は、紫外線の吸収率が90%以上となる波長領域であると定義する。
着色層12に含まれる各色材は、優れた色補正機能を有するものの、光線、特に紫外線に対する耐性が十分でないため、紫外線が照射されると経時的に劣化し、極大吸収波長付近の光を吸収できなくなる。
本実施形態では、光学フィルム10Aにおいて、着色層12よりも外部光が先に入射する側に、紫外線吸収層13が配置されているので、外部光に紫外線が含まれる場合に、着色層12への紫外線の入射量を抑制できる。このため、着色層12の紫外線に対する耐光性を向上できる。
このため、本実施形態における紫外線吸収層13は、光学フィルム10Aの外部からの紫外線から着色層12を保護する紫外線の防護層として機能するとともに、外部からの荷重に対して着色層12を保護するハードコート層としても機能する。
本実施形態のように、紫外線の防護層とハードコート層とを兼ねる紫外線吸収層13は、例えば、上述したエネルギー線硬化性樹脂を用い、紫外線吸収剤と光重合開始剤の吸収波長のバランスを調整し、硬化阻害を抑制することで硬質な樹脂層を製造することができる。
低屈折率層14Aは、紫外線吸収層13よりも屈折率が低い材料から構成されている。これにより、外部から入射する外部光の紫外線吸収層13との界面における反射光と、低屈折率層14Aの表面での反射光とが干渉を起こすので、外部光の表面反射率が低減される。
低屈折率層14Aを設けることによって外部光の表面反射を抑制することができるので、表示装置50Aの視認性が向上する。
低屈折率層14Aは、無機物や無機化合物からなる層状部である。無機物や無機化合物としては、LiF、MgF、3NaF・AlF、AlF、Na3AlF6等の微粒子やシリカ微粒子などを例示できる。また、シリカ微粒子として、多孔質シリカ微粒子や中空シリカ微粒子などの粒子内部に空隙を有するものを用いることが、低屈折率化に有効である。また、低屈折率形成用組成物には、紫外線吸収層13で説明した光重合開始剤や溶剤、その他添加剤を適宜配合してもよい。
光学フィルム10Aは、必要な正面輝度、外部光反射視認性、および表示光の色純度が得られれば、着色層12と紫外線吸収層13との間に適宜の機能層が設けられてもよい。
着色層12、紫外線吸収層13、及び低屈折率層14Aは、例えば各層の構成材料を含む塗工液を塗工、乾燥し、紫外線などの活性エネルギー線を照射し、硬化させることで形成することができる。低屈折率層14Aについては、蒸着やスパッタリング等によっても形成することができる。
色素は、上述した、第1の色材と、第2の色材と、第3の色材と、を含んでいる。添加剤としては、ラジカル捕捉剤、過酸化物分解剤、および一重項酸素クエンチャーの少なくとも1種類を含有してもよい。
低屈折率層14Aも、紫外線吸収層13と同様に、紫外線吸収層13上に、低屈折率層14Aを形成する材料を、塗工した後、光重合を開始させるエネルギー線を照射することによって、組成物を硬化させることによって形成することができる。
このとき、着色層12は、表示光の赤色、緑色、および青色の波長光の透過率が良好な波長帯域を有するので、各表示光は色純度を保って出射する。
紫外線吸収層13では、主に紫外線領域の光を吸収するので、表示光はほとんど輝度が低下することなく透過する。
低屈折率層14Aは、可視光に対する透過率が良好なので、表示光はほとんど輝度が低下することなく外部に出射する。
低屈折率層14Aによって、外部光の表面反射率が抑制されるので、外部光の表面反射が強すぎることによる視認性の低下が抑制される。
紫外線吸収層13に入射する外部光は、紫外線領域の波長成分が紫外線吸収剤によって吸収された状態で、着色層12に入射する。
着色層12では、外部光における着色層12に含まれる各色材の吸収波長付近の波長成分がさらに吸収される。この後、外部光は、透明基材11およびカラーフィルタ部23を透過し、基板21に到達する。基板21には、例えば、配線や電極などの反射率が高い金属部分が含まれる。
このため、外部光は、配線や電極などで反射して、カラーフィルタ部23、透明基材11、着色層12、紫外線吸収層13、および低屈折率層14Aを順次透過して、外部に出射する。
表示装置50Aの観察者は、表示光に加えて、表示装置50Aの外部光による表面反射光及び外部光が表示装置50A内部を透過し、反射する内部反射光をあわせたに反射光を見る。
また、表示装置50Aが非表示状態の場合においても、光学フィルム10Aの外部反射光の反射色相の指標であるクロマティクネス指数a*、b*の値を-5以上かつ+5以下にすることで光学フィルムの色味影響が小さくなり表示画面の黒味が保たれる。
本実施形態では、紫外線吸収層13によって、外部光の紫外光成分が吸収されるので、着色層12が紫外線を受けることによって、色材が劣化することが防止される。このため、着色層12における色材の分光特性は、経時的に維持されやすい。
本発明の第2の実施形態に係る光学フィルムおよび表示装置について説明する。
図3は、本発明の第2の実施形態に係る光学フィルムおよび表示装置の一例を示す模式的な断面図である。
図3に厚さ方向の断面を示す本実施形態の表示装置50Bは、第1の実施形態の表示装置50Aの光学フィルム10Aに代えて、本実施形態の光学フィルム10Bを備える。
光学フィルム10Bは、着色層12と紫外線吸収層13との間に、酸素バリア層15(機能層)を備える以外は、光学フィルム10Aと同様に構成される。
以下、第1の実施形態と異なる点を中心に説明する。
特に本実施形態の光学フィルム10Bは、酸素バリア層15をさらに備えるので、着色層12の色素の酸素影響による酸化劣化を抑制できる。
本発明の第3の実施形態に係る光学フィルムおよび表示装置について説明する。
図4は、本発明の第3の実施形態に係る光学フィルムおよび表示装置の一例を示す模式的な断面図である。
図4に厚さ方向の断面を示す本実施形態の表示装置50Cは、第1の実施形態の表示装置50Aの光学フィルム10Aに代えて、本実施形態の光学フィルム10Cを備える。
光学フィルム10Cは、低屈折率層14Aおよび紫外線吸収層13に代えて、紫外線吸収防眩層16(紫外線吸収層、機能層、防眩層)を備える以外は、光学フィルム10Aと同様に構成される。
以下、第1の実施形態と異なる点を中心に説明する。
紫外線吸収防眩層16の紫外線遮蔽率は、紫外線吸収層13と同様、紫外線遮蔽率が85%以上である。紫外線吸収防眩層16における吸収波長域は、290nm以上370nm以下の範囲であることがより好ましい。
防眩機能とは、表面に微細な凹凸を有し、この凹凸で外光を散乱させることにより外光の映り込みを低減する機能である。
紫外線吸収防眩層16の鉛筆硬度は、紫外線吸収層13と同様にH以上である。
本実施形態の光学フィルム10Cおよび表示装置50Cによれば、第1の実施形態と同様の着色層12と、紫外線吸収層13と同様に紫外線吸収性を有する紫外線吸収防眩層16と、を備えるので、第1の実施形態と同様の作用を備える。
特に本実施形態の光学フィルム10Cは、防眩層を兼ねる紫外線吸収防眩層16を備えるので、外部光が、紫外線吸収防眩層16において散乱される。このため、外部光の表面反射および映り込みが抑制されるので、表示画面および表示光の視認性が向上し、外部光反射による表示品位の低下が抑制できる。
本発明の第3の実施形態の変形例(第1変形例)に係る光学フィルムおよび表示装置について説明する。
図1に厚さ方向の断面を示すように、本変形例の表示装置50Dは、第3の実施形態の表示装置50Cの光学フィルム10Cに代えて、本変形例の光学フィルム10Dを備える。
光学フィルム10Dは、紫外線吸収防眩層16に代えて、第1の実施形態と同様の紫外線吸収層13と、防眩層17(機能層)とを、を備える以外は、光学フィルム10Cと同様に構成される。
以下、第3の実施形態と異なる点を中心に説明する。
本変形例の光学フィルム10Dおよび表示装置50Dによれば、第1の実施形態と同様の着色層12と、紫外線吸収層13と、を備えるので、第1の実施形態と同様の作用を備える。
特に本変形例の光学フィルム10Dは、防眩層17を備えるので、外部光が防眩層17において散乱される。このため、外部光の表面反射および映り込みが抑制されるので、表示画面および表示光の視認性が向上し、外部光反射による表示品位の低下が抑制できる。
本発明の第4の実施形態に係る光学フィルムおよび表示装置について説明する。
図5は、本発明の第4の実施形態に係る光学フィルムおよび表示装置の一例を示す模式的な断面図である。
図5に厚さ方向の断面を示す本実施形態の表示装置50Eは、第3の実施形態の表示装置50Cの光学フィルム10Cに代えて、本実施形態の光学フィルム10Eを備える。
光学フィルム10Eは、紫外線吸収防眩層16に低屈折率層14E(機能層)を積層した以外は、光学フィルム10Cと同様に構成される。
以下、第3の実施形態と異なる点を中心に説明する。
これにより、外部から入射する外部光の紫外線吸収防眩層16との界面における反射光と、低屈折率層14Eの表面での反射光とが干渉を起こすので、外部光の表面反射率が低減される。
低屈折率層14Eを設けることによって外部光の表面反射を抑制することができるので、表示装置50Eの視認性が向上する。
低屈折率層14Eの材料は、紫外線吸収防眩層16の屈折率よりも低い透明材料であれば、特に限定されない。低屈折率層14Eの材料としては、第1の実施形態における低屈折率層14Aと同様の材料を用いることができる。
特に本実施形態の光学フィルム10Eは、外部側に低屈折率層14Eを有する点でも、外部光の表面反射および映り込みが抑制されるので、表示画面および表示光の視認性が向上し、外部光反射による表示品位の低下が抑制できる。
しかし、発光素子の種類は、有機EL素子には限定されない。例えば、発光素子の例としては、LED素子、無機蛍光体発光素子、量子ドット発光素子などが挙げられ、光源が三原色RGBの単色光を発光する場合は、カラーフィルタ部23を除いた表示部20の構成も可能である。
例えば、紫外線吸収層13は、紫外線吸収層とハードコート層とを兼ねるとして説明したが、鉛筆硬度がH未満の紫外線吸収層と、鉛筆硬度がH以上のハードコート層と、を備えていてもよい。この場合、ハードコート層は、紫外線吸収層よりも外側に設けられることがより好ましい。
例えば、低屈折率層または防眩層は、ハードコート層を兼ねる構成であってもよい。
例えば、機能層として、帯電防止剤を含有する帯電防止層および撥水性を有する防汚層の少なくとも一方をさらに備えてもよい。ただし、帯電防止層、防汚層は、上述した種々の機能層が兼ねる構成であってもよい。
以下、各層の形成方法を説明する。
(着色層形成用組成物の使用材料)
着色層形成に用いる着色層形成用組成物の使用材料として下記のものを用いた。
なお、色材の最大吸収波長及び半値幅は硬化塗膜での特性値を分光透過率より算出した。
・第1色材:
Dye-1 下記化学式1で示されるピロメテンコバルト錯体染料(最大吸収波長 493nm、半値幅 26nm)
Dye-2 テトラアザポルフィリン銅錯体染料(山田化学社製 FDG-007、最大吸収波長595nm、半値幅 22nm)
Dye-3 テトラアザポルフィリン銅錯体染料(山本化成社製 PD-311S、最大吸収波長 586nm、半値幅 22nm)
・第3色材:
Dye-4 フタロシアニン銅錯体染料(山田化学社製 FDN-002、最大吸収波長 800nm)
Dye-5 フタロシアニンコバルト錯体染料(山田化学社製 FDR-002、最大吸収波長 683nm)
・添加剤:
ヒンダードアミン系光安定剤 Chimassorb(登録商標)944FDL(BASFジャパン社製、分子量 2000~3100)
ヒンダードアミン系光安定剤 Tinuvin(登録商標)249(BASFジャパン社製、分子量 482)
一重項酸素クエンチャー D1781(東京化成工業社製)・紫外線吸収剤:
Tinuvin(登録商標)479(BASFジャパン社製、極大吸収波長 322nm)
LA-36(ADEKA社製、極大吸収波長 310nm、350nm)・活性エネルギー線硬化樹脂:
UA-306H(共栄社化学社製、ペンタエリスリトールトリアクリレート ヘキサメチレンジイソシアネート ウレタンプレポリマー)
DPHA(ジペンタエリスリトールヘキサアクリレート)
PETA(ペンタエリスリトールトリアクリレート)
・開始剤:Omnirad(登録商標) TPO(IGM Resing B.V.社製、吸収波長ピーク 275nm,379nm)
・溶剤:
MEK(メチルエチルケトン)
酢酸メチル
本実施例で使用する着色層は、波長390~435nmに主吸収波長帯域を有する染料を含んでいない。
透明基材として、厚み60μmのトリアセチルセルロースフィルムを使用し、透明基材の一方面に、[表3]に示す着色層形成用組成物を塗布し、80℃のオーブンで60秒間乾燥させた。その後、紫外線照射装置を用いて照射線量150mJ/cm2(フュージョンUVシステムズジャパン社製、光源Hバルブ)で紫外線照射を行うことにより塗膜を硬化させ、硬化後の膜厚が5.0μmとなるように、下記[表3]に示す着色層1~8を形成した。なお、添加量は質量比である。
・酸素バリア層1形成組成物:
PVA117(クラレ社製)80%水溶液
[表1]に示した実施例9の構成上に、上記の酸素バリア層形成用組成物を塗布、乾燥させ、酸素透過度が1cc/m2・day・atmである酸素バリア層1を形成した。
ハードコート層形成に用いるハードコート層形成用組成物の使用材料として下記のものを用いた。
・紫外線吸収剤:
Tinuvin(登録商標)479(BASFジャパン社製、極大吸収波長 322nm)
LA-36(ADEKA社製、極大吸収波長 310nm、350nm)・活性エネルギー線硬化樹脂:
UA-306H(共栄社化学社製、ペンタエリスリトールトリアクリレートヘキサメチレンジイソシアネート ウレタンプレポリマー)
DPHA(ジペンタエリスリトールヘキサアクリレート)
PETA(ペンタエリスリトールトリアクリレート)
・開始剤:
Omnirad(登録商標) TPO(IGM Resins B.V.社製、吸収波長ピーク 275nm,379nm)
Omnirad(登録商標) 184(IGM Resins B.V.社製、吸収波長ピーク 243nm,331nm)
・溶剤:
MEK(メチルエチルケトン)
酢酸メチル
[表1]及び[表2]に示した着色層上または透明基材上に、下記[表4]に示すハードコート層形成用組成物を塗布し、80℃のオーブンで60秒間乾燥させ、その後、紫外線照射装置を用いて照射線量150mJ/cm2で紫外線照射(フュージョンUVシステムズジャパン社製、光源Hバルブ)を行うことにより塗膜を硬化させ、硬化後の膜厚が5.0μmである[表1]及び[表2]に記載のハードコート層1~3を形成した。
・紫外線吸収剤:
Tinuvin(登録商標)479(BASFジャパン社製、極大吸収波長 322nm)
LA-36(ADEKA社製、極大吸収波長 310nm、350nm)・活性エネルギー線硬化樹脂:
ライトアクリレートPE-3A(共栄社化学株式会社製、屈折率1.52)・光重合開始剤:
Omnirad(登録商標) TPO(IGM Resins B.V.社製、吸収波長ピーク 275nm、379nm)
・樹脂粒子:
スチレン-メタクリル酸メチル共重合体粒子(屈折率1.515、平均粒径2.0μm)
・無機微粒子1:
合成スメクタイト
・無機微粒子2:
アルミナナノ粒子、平均粒径40nm
・溶剤
トルエン
イソプロピルアルコール
[表1]に示した着色層上、ハードコート層上に、下記[表5]に示す防眩層形成用組成物を塗布し、80℃のオーブンで60秒間乾燥させ、その後、紫外線照射装置を用いて照射線量150mJ/cm2で紫外線照射(フュージョンUVシステムズジャパン社製、光源Hバルブ)を行うことにより塗膜を硬化させ、硬化後の膜厚が5.0μmである[表1]に記載の防眩層1及び2を形成した。
低屈折率層1の形成に用いる低屈折率層の形成用組成物として下記のものを用いた。
・屈折率調整剤:
多孔質シリカ微粒子分散液(平均粒子径75nm、固形分20%、溶剤メチルイソブチルケトン) 8.5質量部
・防汚性付与剤:
オプツール(登録商標)AR-110(ダイキン工業社製、固形分15%、溶剤メチルイソブチルケトン) 5.6質量部
・活性エネルギー線硬化樹脂:
ペンタエリスリトールトリアクリレート 0.4質量部・開始剤:
Omnirad(登録商標) 184(IGM Resins B.V.社製) 0.07質量部
・レベリング剤:
RS-77(DIC社製) 1.7質量部
・溶剤:
メチルイソブチルケトン 83.73質量部
[表1]及び[表2]に記載のハードコート層上、防眩層上に、上記組成の低屈折率層形成用組成物を塗布し、80℃のオーブンで60秒間乾燥させ、その後、紫外線照射装置(フュージョンUVシステムズジャパン社製、光源Hバルブ)を用いて照射線量200mJ/cm2で紫外線照射を行うことにより塗膜を硬化させて、硬化後の膜厚が100nmである[表1]及び[表2]に記載の低屈折率層1を形成した。
得られた光学フィルム1~13について以下の評価を行った。
得られた光学フィルムの着色層上に形成された紫外線吸収層について、JIS-K5600付着性試験準拠のセロハンテープを用いて着色層と剥離し、自動分光光度計((株)日立製作所製、U-4100)を用い、粘着テープをリファレンスとして紫外線吸収層単層の透過率を測定し、紫外域(290nm~400nm)の平均透過率[%]を算出し、紫外線遮蔽率[%]を100%から紫外域(290nm~400nm)の平均透過率[%]を引いた値として算出した。
光学フィルムの表面に、クレメンス型引掻き硬度試験機(テスター産業株式会社製、HA-301)を用いて、JIS-K5600-5-4:1999に準拠して、500gf(4.9N)の荷重(以下、500g荷重)をかけた鉛筆(三菱鉛筆社製 UNI、鉛筆硬度H)を用いて試験を行い、キズによる外観の変化を目視で評価し、キズが観察されない場合を良い(下記[表6]、[表7]では「〇」と記載)、キズが観察される場合を不良(下記[表7]では「×」と記載)とした。
得られた着色層を含む光学フィルムの信頼性試験として、キセノンウェザーメーター試験機(スガ試験機株式会社製、X75)を用い、キセノンランプ照度60W/cm2(300nm~400nm)、試験機内温度45℃・湿度50%RH条件にて120時間試験し、試験前後に自動分光光度計((株)日立製作所製、U-4100)を用いて透過率測定を行い、波長範囲470nm~530nmにて試験前の最小透過率を示す波長λ1での試験前後透過率差ΔTλ1、波長範囲560nm~620nmにて試験前の最小透過率を示す波長λ2での試験前後透過率差ΔTλ2、波長範囲650nm~780nmにて試験前の最小透過率を示す波長での試験前後での透過率差ΔTλ3を算出した。透過率差はゼロに近い方が良好であり、|ΔTλN|≦20(N=1~3)となるものが好ましく、|ΔTλN|≦10(N=1~3)となるものが更に好ましい。
得られた光学フィルム8、10、14~16について以下の評価を行った。
得られた光学フィルムの透過率を自動分光光度計((株)日立製作所製、U-4100)を用いて測定し、この透過率を用いて、白表示時に光学フィルムを透過した光の効率を算出し、白表示透過特性として評価した。前述の効率については、白色有機EL光源(以下、有機EL光源という場合がある)から出射され、且つカラーフィルタを通して出力される白表示時の各波長における光強度を100としたときに、光学フィルムを透過した光の各波長における光強度値との比として算出した。光強度比が高いほど光源の輝度効率が高い。EL光源が出射する光のスペクトルを図6に示した。図6において、横軸は波長(nm)、縦軸は透過光強度(a.u.)を表す。
得られた光学フィルムの透過率T(λ)及び表面反射率R2(λ)を、自動分光光度計((株)日立製作所製、U-4100)を用いて測定した。表面反射率R2(λ)の測定については、透明基材のトリアセチルセルロースフィルムの着色層および機能層が形成されていない面につや消し黒色塗料を塗布して反射防止の処置を行い、入射角5°の分光反射率測定を行い、表面反射率R2(λ)とした。電極反射率RE(λ)を波長380nmから780nmまで全て100%として、光学フィルムを配置せずD65光源が反射する反射光の光強度を100とした場合の相対反射値を、各層での界面反射、表面反射を考慮せず上述の式(4)、(5)、(7)、(9)に基づいて算出し、表示装置反射特性1として評価した。相対反射値が低いほど反射光の強度が小さく、表示品位が高い。
得られた光学フィルムの透過率T(λ)及び表面反射率R2(λ)を自動分光光度計(型番;U-4100、株式会社日立製作所製)を用いて測定した。表面反射率R2(λ)の測定については、透明基材のトリアセチルセルロースフィルムの着色層および機能層が形成されていない面につや消し黒色塗料を塗布して反射防止の処置を行い、入射角5°の分光反射率測定を行い、表面反射率R2(λ)とした。電極反射率RE(λ)を波長380nmから780nmまで全て100%として、D65光源に対する反射色相のクロマティクネス指数(値)a*及びb*を、各層での界面反射及び表面反射を考慮せず上述の(1)~(9)式に基づいて算出し、表示装置反射色相1として評価した。
a*およびb*は、ゼロに近いほど色味づきがなく良好であり、-5以上+5以内となることが好ましい。
電極反射率RE(λ)を図8に示す有機発光表示装置(LGエレクトロニクス社製有機ELテレビ、OLED55C8PJA)の反射率測定より得られた電極反射率とした以外は、表示装置反射特性1と同様に算出した結果を表示装置反射特性2として評価した。表示装置反射特性1と同様に相対反射値が低いほど反射光の強度が小さく、表示品位が高い。図8において、横軸は波長(nm)、縦軸は反射率(%)を表す。
電極反射率RE(λ)を図8に示す有機発光表示装置(LGエレクトロニクス社製有機ELテレビ、OLED55C8PJA)の反射率測定より得られた電極反射率とした以外は、表示装置反射色相1と同様に算出した結果を表示装置反射色相2として評価した。表示装置反射色相1と同様に、a*およb*は、ゼロに近いほど色味づきがなく良好であり、-5以上+5以内となることが好ましい。
得られた光学フィルムの透過率を自動分光光度計((株)日立製作所製、U-4100)を用いて測定し、この透過率と、図6に示したスペクトルの有機EL光源とカラーフィルタとを通して出力される図7に示す赤色表示、緑色表示、青色表示スペクトルとを用いて算出されるCIE1931色度値からNTSC比を算出し、色再現性として評価した。
NTSC比が高いほど色再現性が広く、好ましい。図7において、横軸は波長(nm)、縦軸は透過光強度(a.u.)を表す。
また、本発明は前述した説明によって限定されることはなく、添付の特許請求の範囲によってのみ限定される。
11 透明基材
11a 第1面
11b 第2面
12 着色層
13 紫外線吸収層(機能層)
14A、14E 低屈折率層(機能層)
15 酸素バリア層(機能層)
16 紫外線吸収防眩層(紫外線吸収層、機能層、防眩層)
17 防眩層(機能層)
20 表示部
21 基板
22 発光素子
22R 第1発光素子
22G 第2発光素子
22B 第3発光素子
23 カラーフィルタ部
50A、50B、50C、50D、50E 表示装置
Claims (14)
- 透明基材と、
前記透明基材に重ねて配置されており色素を含有する1層以上から構成される着色層と、
前記着色層を挟んで前記透明基材と反対側に配置される1層以上の機能層と、を備え、
前記着色層は、
極大吸収波長が470nm以上530nm以下の範囲にあり、吸光スペクトルの半値幅が15nm以上45nm以下である第1の色材と、
極大吸収波長が560nm以上620nm以下の範囲にあり、吸光スペクトルの半値幅が15nm以上55nm以下である第2の色材と、
400nm~780nmの波長の範囲において最も透過率の低い波長が650nm以上780nm以下の範囲内にある第3の色材と、
を含んでおり、
かつ、下記式(1)~(9)で定義される色相の値a*およびb*が、それぞれ-5以上+5以下の範囲にあり、
前記機能層には、紫外線遮蔽率が85%以上の紫外線吸収層を有し、表面の500g荷重での鉛筆硬度がH以上であることを特徴とする光学フィルム。
式(1)~(3)から算出されるa*、b*はCIE1976L*a*b*色空間(CIELAB色空間)での算出方法に準じて算出される。式(1)、(2)において、Xn、Yn、Znは、D65光源の白色点における3刺激値である。
式(4)において、RE(λ)は完全拡散反射面での反射率[%]を表す関数(各波長100%)、R2(λ)は前記透明基材と反対側の前記光学フィルムにおける最表面での表面反射率[%]を表す関数、T(λ)は前記光学フィルムの透過率[%]を表す関数である。
式(6)~(9)においてPD65(λ)は、D65光源スペクトル、オーバーラインx(λ)、オーバーラインy(λ)、オーバーラインz(λ)は、CIE1931 2°視野での等色関数である。
式(6)から式(9)における定積分は、適宜の数値積分で求めることができる。数値積分を行う場合の波長間隔は、例えば1nm間隔である。 - 前記着色層は、波長390~435nmに主吸収波長帯域を有する染料を含まない、
請求項1に記載の光学フィルム。 - 前記紫外線吸収層は、エネルギー線硬化型化合物と光重合開始剤と紫外線吸収剤とを含有する組成物の硬化膜から構成され、
前記光重合開始剤の紫外線領域における吸収波長域は、前記紫外線吸収剤の紫外線領域における吸収波長域と異なり、前記紫外線吸収層の紫外線領域における吸収波長域が、290nm以上370nm以下の範囲である、
請求項1または2に記載の光学フィルム。 - 前記機能層は、前記紫外線吸収層よりも屈折率が低い低屈折率層を備え、
前記低屈折率層は、前記紫外線吸収層における前記着色層と対向する表面と反対側の表面に積層されている、
請求項1から3のいずれか一項に記載の光学フィルム。 - 前記機能層は、防眩層をさらに備え、
前記紫外線吸収層と、前記防眩層とは、前記透明基材から前記着色層に向かう方向において、この順に配置されている、
請求項1~4のいずれか1項に記載の光学フィルム。 - 前記紫外線吸収層が紫外線吸収剤を含有する防眩層である、請求項1~4のいずれか1項に記載の光学フィルム。
- 前記機能層は、帯電防止剤を含有する帯電防止層および撥水性を有する防汚層の少なくとも一方をさらに含む、
請求項1~6のいずれか1項に記載の光学フィルム。 - 前記着色層は、ラジカル捕捉剤、過酸化物分解剤、および一重項酸素クエンチャーの少なくとも1種類を含有する、
請求項1~7のいずれか1項に記載の光学フィルム。 - 前記着色層は、前記ラジカル捕捉剤として、分子量2000以上のヒンダードアミン系光安定剤を含有する、
請求項8に記載の光学フィルム。 - 前記着色層は、前記一重項酸素クエンチャーとして、ジアルキルホスフェイト、ジアルキルジチオカルバネート、ベンゼンジチオール、およびこれらの遷移金属錯体のいずれかを含有する、
請求項8または9に記載の光学フィルム。 - 前記色素は、ポルフィリン構造、メロシアニン構造、フタロシアニン構造、アゾ構造、シアニン構造、スクアリリウム構造、クマリン構造、ポリエン構造、キノン構造、テトラジポルフィリン構造、ピロメテン構造及びインジゴ構造の何れかを有する化合物及びその金属錯体からなる群から選択される少なくとも1種以上の化合物を含む請求項1~10のいずれか1項に記載の光学フィルム。
- 前記機能層は、酸素透過度が10cc/m2・day・atm以下である層を含む、請求項1~11のいずれか1項に記載の光学フィルム。
- 光源と、
請求項1~12のいずれか1項に記載の光学フィルムと、を備える、表示装置。 - 前記光源は、画像信号に基づいて発光する複数の発光素子を含む、請求項13に記載の表示装置。
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