WO2023054468A1 - Corps multicouche pour dispositifs d'affichage, et dispositif d'affichage - Google Patents

Corps multicouche pour dispositifs d'affichage, et dispositif d'affichage Download PDF

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WO2023054468A1
WO2023054468A1 PCT/JP2022/036159 JP2022036159W WO2023054468A1 WO 2023054468 A1 WO2023054468 A1 WO 2023054468A1 JP 2022036159 W JP2022036159 W JP 2022036159W WO 2023054468 A1 WO2023054468 A1 WO 2023054468A1
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Prior art keywords
layer
inorganic compound
laminate
display device
fluorine
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PCT/JP2022/036159
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English (en)
Japanese (ja)
Inventor
純 佐藤
研一 小野寺
和也 本田
紗緒里 川口
佳奈 堀井
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大日本印刷株式会社
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Priority claimed from JP2022146208A external-priority patent/JP2023051786A/ja
Application filed by 大日本印刷株式会社 filed Critical 大日本印刷株式会社
Priority to CN202280064705.2A priority Critical patent/CN117980785A/zh
Priority to KR1020247010024A priority patent/KR20240070544A/ko
Publication of WO2023054468A1 publication Critical patent/WO2023054468A1/fr

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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
    • G02B1/11—Anti-reflection coatings
    • G02B1/113—Anti-reflection coatings using inorganic layer materials only
    • G02B1/115—Multilayers
    • 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
    • B32B7/022—Mechanical 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
    • 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
    • B32B9/00—Layered products comprising a layer of a particular substance not covered by groups B32B11/00 - B32B29/00
    • 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
    • G02B1/11—Anti-reflection coatings
    • G02B1/111—Anti-reflection coatings using layers comprising organic materials
    • 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
    • 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
    • G09F9/301—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 flexible foldable or roll-able electronic displays, e.g. thin LCD, OLED

Definitions

  • the present disclosure relates to a laminate for a display device and a display device.
  • display devices such as displays for display purposes have a surface with low reflectance to prevent external light such as sunlight and fluorescent lamps from reflecting on the display screen, and to improve the visibility of characters and images. transformation is required.
  • the display device is required to have abrasion resistance so that it is hard to be scratched.
  • Patent Document 1 discloses an antireflection laminate having at least a resin film, a hard coat layer, and an inorganic oxide layer, wherein the laminate has a pencil hardness of 4H or more and a rigidity of 8.0 N mm or more, and a Knoop An antireflection laminate having a hardness of 150 to 300 mN/mm 2 is disclosed, and by laminating it to the surface of a display, it is possible to effectively suppress reflections on the surface of the display while imparting sufficient scratch resistance. It states what you can do.
  • the laminate arranged on the surface of the display device is required to have high abrasion resistance.
  • the laminate becomes brittle against bending, and cracks may occur during the production or transportation of the laminate.
  • flexible display devices are required to have no display defects even when repeatedly bent. Endurance is required.
  • the wear resistance may deteriorate.
  • the laminate for a display device has a problem that it is impossible to achieve both bending resistance and abrasion resistance while maintaining low reflectivity.
  • the present disclosure has been made in view of the above problems, and a main object thereof is to provide a laminate for a display device that has low reflectivity and excellent bending resistance and abrasion resistance.
  • One embodiment of the present disclosure is a laminate for a display device having, in this order, a fluorine-containing layer containing fluorine atoms, a first inorganic compound layer, a second inorganic compound layer, and a substrate layer.
  • the first inorganic compound layer has a first inorganic compound that is a low refractive index material, the relative film density D1 is 0.70 or more and 1.20 or less
  • the second inorganic compound layer is , a second inorganic compound that is a high refractive index material, a relative film density D2 of 0.50 or more and less than 1.00, and an incident angle of 5 on the surface of the display device laminate on the fluorine-containing layer side.
  • a laminate for a display device which has a luminous reflectance of 2.0% or less for specularly reflected light when light is incident at 100°.
  • One embodiment of the present disclosure is a laminate for a display device having, in this order, a fluorine-containing layer containing fluorine atoms, a first inorganic compound layer, a second inorganic compound layer, and a substrate layer.
  • the first inorganic compound layer has a first inorganic compound that is a low refractive index material and has a fluorine atom content of 6.5 atomic % or less
  • the second inorganic compound layer is It has a second inorganic compound that is a high refractive index material, has a relative film density D2 of 0.50 or more and less than 1.00, and has an incident angle of 5° on the fluorine-containing layer side surface of the laminate for a display device.
  • a laminate for a display device which has a luminous reflectance of 2.0% or less for specularly reflected light when light is incident at .
  • One embodiment of the present disclosure is a laminate for a display device having, in this order, a fluorine-containing layer containing fluorine atoms, a first inorganic compound layer, and a substrate layer, wherein the first inorganic compound
  • the layer has a first inorganic compound that is a low refractive index material, has a relative film density D1 of 0.70 or more and 1.20 or less, and is between the first inorganic compound layer and the base layer , a high refractive index dispersion layer in which inorganic compound particles having a high refractive index are dispersed in a binder resin, and the relative film density D4 of the high refractive index dispersion layer is 0.10 or more and 0.70 or less, and the display Provided is a laminate for a display device having a luminous reflectance of 2.0% or less for specularly reflected light when light is incident on the fluorine-containing layer side surface of the laminate for a device at an incident angle of 5°. .
  • Another embodiment of the present disclosure provides a display device comprising a display panel and the above-described display device laminate disposed on the viewer side of the display panel.
  • the present disclosure can provide a laminate for a display device that has low reflectivity and excellent bending resistance and abrasion resistance.
  • FIG. 1 is a schematic cross-sectional view showing an example of a laminate for a display device according to a first embodiment and a second embodiment of the present disclosure
  • FIG. 4 is a schematic cross-sectional view showing another example of the display device laminate of the first embodiment and the second embodiment of the present disclosure
  • FIG. 4 is a schematic cross-sectional view showing another example of the display device laminate of the first embodiment and the second embodiment of the present disclosure
  • FIG. 2 is a schematic cross-sectional view of a first inorganic compound layer and a fluorine-containing layer for explaining a difference in content ratio of fluorine atoms in the first inorganic compound layer.
  • FIG. 1 is a schematic cross-sectional view showing an example of a laminate for a display device according to a first embodiment and a second embodiment of the present disclosure
  • FIG. 4 is a schematic cross-sectional view showing another example of the display device laminate of the first embodiment and the second embodiment of the present disclosure
  • FIG. 2 is a schematic cross-sectional view of
  • FIG. 10 is a schematic cross-sectional view showing an example of a laminate for a display device according to a third embodiment of the present disclosure
  • 1 is a schematic cross-sectional view showing an example of a display device of the present disclosure
  • FIG. It is a figure for demonstrating the method of a dynamic bending test.
  • 2 when expressing a mode of arranging another member on top of a certain member, when simply describing “above” or “below”, unless otherwise specified, 2 includes both cases in which another member is arranged directly above or directly below, and cases in which another member is arranged above or below a certain member via another member.
  • 2 when expressing a mode in which another member is arranged on the surface of a certain member, when simply describing “on the surface side” or “on the surface”, unless otherwise specified, It includes both the case of arranging another member directly above or directly below so as to be in contact with it, and the case of arranging another member above or below a certain member via another member.
  • the inventors of the present invention have found that, in a laminated body arranged on the surface of a display device, the bending resistance of the inorganic compound layer exhibiting low reflectivity may be low.
  • we investigated the resistance of the inorganic compound layer to stress changes and found that by using the relative film density of the inorganic compound layer as a parameter, it is possible to determine the degree of resistance to stress changes for each material. I found out that. Specifically, when the measured value of the film density of the inorganic compound layer is close to the literature value (that is, the relative film density is about 1), it was found that there is almost no difference in bending resistance due to the difference in materials. . Furthermore, even if the material has a high film density in the literature, when the film density is lower than the literature value (that is, the relative film density is low), the bending resistance of the inorganic compound layer is improved. .
  • the inventors of the present invention conducted repeated studies to improve bending resistance and wear resistance while maintaining low reflectivity for a laminate disposed on the surface of a display device. It was found that the configuration of the laminate for a display device according to the second embodiment and the third embodiment can improve bending resistance and abrasion resistance.
  • the fluorine-containing layer is disposed on one surface of the laminate for a display device, and the first inorganic compound layer (low refractive index layer) which is the inorganic compound layer on the fluorine-containing layer side is relative to It was found that abrasion resistance can be obtained by setting the film density within a predetermined range. Furthermore, by setting the relative film density of the second inorganic compound layer (high refractive index layer) to a predetermined low range, it was found that a laminate for a display device having high resistance to stress change and good bending resistance can be obtained. , completed the present invention.
  • the laminate for a display device of this embodiment will be described in detail.
  • FIG. 1 is a schematic cross-sectional view showing an example of the laminate for a display device according to this embodiment.
  • the display device laminate 1a of the present embodiment includes a fluorine-containing layer 2, a first inorganic compound layer 3, a second inorganic compound layer 4, and a substrate layer 5. have in this order.
  • the first inorganic compound layer contains the first inorganic compound, which is a low refractive index material, and has a relative film density D1 of 0.70 or more and 1.20 or less.
  • the second inorganic compound layer contains a second inorganic compound having a higher refractive index than the first inorganic compound, and has a relative film density D2 of 0.50 or more and less than 1.00.
  • the luminous reflectance of specularly reflected light when light is incident on the surface 1A on the fluorine-containing layer 2 side at an incident angle of 5° is 2.0% or less.
  • the laminate for a display device has a fluorine-containing layer on one surface, and the relative film density D1 of the first inorganic compound layer is within a predetermined range, thereby exhibiting excellent abrasion resistance. will have. Furthermore, by setting the relative film density D2 of the second inorganic compound layer to be within a predetermined low range, excellent bending resistance can be obtained.
  • the laminate for a display device in the present embodiment includes a first inorganic compound layer that is a low refractive index layer and a second inorganic compound layer that is a high refractive index layer, thereby achieving a predetermined luminous reflectance. will have. Therefore, the laminate for a display device has low reflectivity and excellent bending resistance and abrasion resistance.
  • each configuration in the laminate for display device of the present embodiment will be described in detail.
  • the first inorganic compound layer is composed of a first inorganic compound that is a low refractive index material.
  • the inorganic compound layer is a layer mainly composed of an inorganic compound, and is distinguished from a layer in which inorganic compound particles are dispersed in a binder resin.
  • the first inorganic compound constituting the first inorganic compound layer is not particularly limited as long as it is an inorganic compound having a lower refractive index than the second inorganic compound constituting the second inorganic compound layer, but preferably Inorganic oxides such as silicon oxides and gallium oxides, magnesium fluoride, lithium fluoride, calcium fluoride, barium fluoride and the like can be mentioned. In this embodiment, among others, silicon oxide is preferable from the viewpoint of refractive index and versatility.
  • the average composition of the inorganic oxide is represented by, for example, MOx (wherein M represents a metal element, and the value of x varies depending on the metal element).
  • MOx metal element
  • x can be 0 ⁇ x ⁇ 2, preferably 1 ⁇ x ⁇ 2, more preferably SiO 2 .
  • the average composition of the inorganic oxide is not limited to the stoichiometric optimum as described above.
  • the first inorganic compound layer is preferably a deposited film.
  • a silicon oxide (silica) deposited film is preferred.
  • one type of inorganic compound is preferably contained in the first inorganic compound layer, but a plurality of types of inorganic compounds may be contained.
  • the film density calculated according to the content ratio of multiple types of inorganic compounds is adopted as the film density (literature value) described later.
  • the refractive index of the first inorganic compound layer is preferably 1.60 or less, more preferably 1.50 or less. On the other hand, for example, it is 1.30 or more, and may be 1.40 or more.
  • the refractive index of each layer refers to the refractive index for light with a wavelength of 550 nm.
  • a method of measuring the refractive index can include a method of measuring using an ellipsometer. Examples of the ellipsometer include "UVSEL" manufactured by Jobin-Evon and "DF1030R” manufactured by Techno Synergy.
  • the relative film density D1 of the first inorganic compound layer which is the low refractive index layer, is 0.70 or more and 1.20 or less.
  • the relative film density D1 of the first inorganic compound layer is preferably 0.75 or more, more preferably 0.80 or more. On the other hand, it is preferably 1.17 or less, more preferably 1.15 or less. If the relative film density D1 is too high, the bending resistance may be poor and cracks may occur in the first inorganic compound layer. If the relative film density D1 is too low, the wear resistance may be poor.
  • the relative film density of the inorganic compound layer is calculated by the following formula.
  • Relative film density film density (measured value) / film density (literature value)
  • the measured value of the film density can be obtained from the surface density measured by Rutherford Backscattering Spectrometry (RBS) under the following measurement equipment and the following measurement conditions, and the film thickness measured by a transmission electron microscope (TEM).
  • Rutherford backscattering analysis detects the energy value of the backscattered light element ions when the sample is irradiated with light element ions such as helium (He) at high energy. It is a method to measure the abundance of
  • the atomic number density (atoms/cm 3 ) was calculated from the area density (atoms/cm 2 ) obtained from the RBS analysis and the film thickness (cm) measured by a transmission electron microscope (TEM) or the like, and determined by RBS.
  • the density (g/cm 3 ) of the inorganic compound layer is calculated by performing conversion based on the composition information.
  • the film density (literature value) of the inorganic compound layer is a theoretical film density, and typical film density values of the inorganic compound layer are as follows. ⁇ SiO 2 (2.2 g/cm 3 ) ⁇ ZrO 2 (5.9 g/cm 3 ) - Nb2O5 ( 4.6g / cm3 ) -Al2O3 (4.0 g / cm3 ) ⁇ TiO 2 (4.3 g/cm 3 ) ⁇ ZnO (5.5 g/cm 3 ) - SnO2 (6.9g/ cm3 )
  • values described in literature such as Filler Data Utilization Book (author: Isao Soma) and resource platforms such as Chemical Book can be adopted.
  • the composition of the actual inorganic compound layer is, for example, SiOx (0 ⁇ x ⁇ 2)
  • the film density of SiO2 having a stoichiometric composition where x is 2 (literature value ).
  • a method for adjusting the relative film density of the first inorganic compound layer within the above range includes, for example, a method for adjusting the film forming speed of the first inorganic compound layer. By increasing the deposition rate, the relative film density can be lowered. A method of changing the composition of the first inorganic compound layer can also be used.
  • the first inorganic compound layer may contain fluorine atoms derived from the fluorine-containing layer.
  • the content ratio of fluorine atoms in the first inorganic compound layer is preferably low. This is because when the fluorine atom content is low, softening of the first inorganic compound layer can be suppressed for the reason described in detail in the second embodiment, and abrasion resistance is improved.
  • the content ratio of fluorine atoms in the first inorganic compound layer can be the same value as the value described in the second embodiment described later.
  • the thickness of the first inorganic compound layer is not particularly limited, but is preferably 30 nm or more and 200 nm or less, more preferably 50 nm or more and 150 nm or less.
  • the thickness of each layer is the thickness of the display device laminate observed with a transmission electron microscope (TEM), a scanning electron microscope (SEM), or a scanning transmission electron microscope (STEM). It can be an average value of thicknesses at arbitrary 10 points obtained by measuring from cross sections in the same direction.
  • the first inorganic compound layer for example, selects particles having a desired refractive index from among low refractive index particles, and performs physical vapor deposition such as vacuum deposition, sputtering, and ion plating. method (Physical Vapor Deposition method, PVD method) or the like. Among these, the vacuum deposition method is preferable from the viewpoint of productivity (deposition speed).
  • the first inorganic compound layer is preferably in direct contact with the fluorine-containing layer. Also, the first inorganic compound layer is preferably in direct contact with the second inorganic compound layer.
  • Second Inorganic Compound Layer is composed of a second inorganic compound having a higher refractive index than the first inorganic compound.
  • the second inorganic compound constituting the second inorganic compound layer aluminum oxide, zirconium oxide, hafnium oxide, tantalum oxide, cerium oxide, titanium oxide, zinc oxide, tin oxide, magnesium Examples include oxides, inorganic oxides such as yttrium oxide and niobium oxide, lanthanum fluoride, and cerium fluoride.
  • the average composition of aluminum oxide is represented by AlOx, where x can take 0 ⁇ x ⁇ 1.5 and is preferably Al 2 O 3 .
  • the average composition of zirconium oxide is represented by ZrOx, where x can take 0 ⁇ x ⁇ 2 and is preferably ZrO2 .
  • the average composition of niobium oxide is represented by NbOx, where x can take 0 ⁇ x ⁇ 2.5, preferably Nb 2 O 5 .
  • the second inorganic compound layer is preferably a deposited film.
  • any one of an aluminum oxide (alumina) vapor deposition film, a zirconium oxide vapor deposition film, a titanium oxide vapor deposition film, a zinc oxide vapor deposition film, a tin oxide vapor deposition film, and a niobium oxide vapor deposition film is preferable.
  • one type of inorganic compound is preferably contained in the second inorganic compound layer, but a plurality of types of inorganic compounds may be contained.
  • the refractive index of the second inorganic compound layer is preferably 1.60 or more, more preferably 1.80 or more. On the other hand, it is, for example, 3.00 or less, and may be 2.50 or less.
  • the relative film density D2 of the second inorganic compound layer which is a high refractive index layer, is 0.50 or more and less than 1.00.
  • the relative film density D2 in this embodiment is preferably 0.60 or more, more preferably 0.70 or more. On the other hand, it is preferably 0.95 or less, more preferably 0.90 or less. If the relative film density D2 is too high, the bending resistance may be poor and cracks may occur in the second inorganic compound layer. If the relative film density D2 is too low, the second inorganic compound layer may peel off after bending, and the visibility may deteriorate. This is because the adhesion of the second inorganic compound layer is insufficient and the stress applied during bending cannot be endured.
  • a method for adjusting the relative film density of the second inorganic compound layer within the above range includes, for example, a method for adjusting the film forming speed of the second inorganic compound layer. By increasing the deposition rate, the relative film density can be lowered. Also, a method of changing the composition of the second inorganic compound layer can be used. In this case, the relative film density can be lowered by shifting the elemental ratio of the inorganic compound in the inorganic compound layer (the elemental ratio of the inorganic oxide in the inorganic compound layer) from the stoichiometrically optimum ratio.
  • the thickness of the second inorganic compound layer is not particularly limited, but is preferably 10 nm or more and 200 nm or less, more preferably 20 nm or more and 170 nm or less.
  • the second inorganic compound layer selects particles having a desired refractive index from among high refractive index particles, and performs physical vapor deposition such as vacuum deposition, sputtering, and ion plating. method (Physical Vapor Deposition method, PVD method) or the like. Among these, the vacuum deposition method is preferable from the viewpoint of productivity (deposition speed).
  • the second inorganic compound layer is preferably in direct contact with the first inorganic compound layer. Moreover, the second inorganic compound layer is preferably in direct contact with any one of the base material layer, the hard coat layer, the intervening layer, and the third inorganic compound layer, which will be described later.
  • the fluorine-containing layer in the present embodiment is arranged on the side of the first inorganic compound layer opposite to the side of the second inorganic compound layer. is preferably arranged on the outermost surface.
  • the fluorine-containing layer may be any layer as long as it contains fluorine atoms, and by containing fluorine atoms, it is possible to impart abrasion resistance to the display device laminate. Specifically, the coefficient of dynamic friction of the surface of the display device laminate on the fluorine-containing layer side can be set within a predetermined range.
  • the dynamic friction coefficient of the fluorine-containing layer-side surface of the laminate for display device in the present embodiment is preferably 0.01 or more and 0.30 or less, more preferably 0.03 or more and 0.20 or less. If the coefficient of dynamic friction is equal to or less than the above value, the slipperiness of the surface will be improved, and the wear resistance will be more excellent.
  • the dynamic friction coefficient can be measured by a method conforming to JIS K7125:1999 (friction coefficient test method).
  • the method for measuring the coefficient of dynamic friction is, for example, using a variable load friction and wear test system (HEIDON Type HHS2000 manufactured by Shinto Kagaku Co., Ltd.), using cashmere felt of 2 cm ⁇ 2 cm, a load of 200 g, and a speed of 5 mm / sec. conditions can be measured.
  • the coefficient of dynamic friction is measured at five different positions on the surface of the laminate for a display device on the fluorine-containing layer side, and is taken as the average value of the measured values.
  • the thickness of the fluorine-containing layer is relatively thin, it is presumed that it does not affect thin film interference.
  • the thickness of the fluorine-containing layer is, for example, preferably 1 nm or more and 30 nm or less, more preferably 2 nm or more and 20 nm or less, and even more preferably 3 nm or more and 10 nm or less.
  • the fluorine-containing layer is not particularly limited as long as it contains fluorine atoms.
  • the fluorine-containing layer may contain, for example, a fluorine compound, may contain a fluorine compound and a resin, or may contain a fluorine resin.
  • the fluorine compound for example, those known as fluorine-based antifouling agents, fluorine-based leveling agents, fluorine-based surfactants, and the like can be used.
  • fluorine compounds include organic fluorine compounds, and specific examples include perfluoro compounds.
  • Perfluoro compounds include, for example, perfluoro compounds having perfluoropolyether groups, perfluoroalkylene groups, perfluoroalkyl groups, and the like. Perfluoroalkylene groups and perfluoroalkyl groups may be linear or branched.
  • a fluorine compound may be used individually by 1 type, and may be used in mixture of 2 or more types.
  • the fluorine compound is preferably bound to the resin component.
  • binding the fluorine compound to the resin component bleeding out of the fluorine compound can be suppressed, and wear resistance and antifouling properties can be maintained over a long period of time.
  • the fluorine compound a fluorine compound having a reactive functional group is preferably used because it is preferably bonded to the resin component. That is, the fluorine-containing layer preferably contains a cured product of a resin composition containing a fluorine compound having a reactive functional group and a polymerizable compound to be described later.
  • reactive functional groups include ethylenically unsaturated bond groups such as (meth)acryloyl groups, vinyl groups, and allyl groups, epoxy groups, and oxetanyl groups.
  • the number of reactive functional groups possessed by the fluorine compound should be 1 or more, preferably 2 or more. Abrasion resistance can be enhanced by using a fluorine compound having two or more reactive functional groups.
  • the fluorine compound may contain silicon. That is, the fluorine-containing layer may contain fluorine and silicon.
  • silicon-containing fluorine compounds include fluorine compounds having a siloxane bond in the molecule. By using a fluorine compound having a siloxane bond, it is possible to improve lubricity and wear resistance.
  • the fluorine compound is preferably, for example, a fluorine compound having a reactive functional group or a fluorine compound containing a reactive functional group and silicon.
  • fluorine compounds having a reactive functional group examples include fluorine-containing monomers having an ethylenically unsaturated bond, fluorine-containing polymers or oligomers having a fluoroalkylene group in the main chain, fluoroalkylene groups or fluoroalkyl groups in the main chain and side chains. Fluorine-containing polymers or oligomers having groups are included.
  • fluorine compounds having reactive functional groups for example, JP-A-2017-19247 can be referred to.
  • fluorine compound containing a reactive functional group and silicon for example, a silicone-containing vinylidene fluoride copolymer obtained by reacting an organic silicone having a reactive functional group in the molecule with the above fluorine compound having a reactive functional group. etc.
  • fluorine compound containing a reactive functional group and silicon for example, a fluorine compound having a reactive functional group and a perfluoropolyether group, especially a silane unit having a reactive functional group and a silane having a perfluoropolyether group Fluorine compounds containing units are also preferably used. International publication 2012/157682 can be referred to for such a fluorine compound, for example.
  • the fluorine-containing layer may be a layer containing a fluorine compound and a resin.
  • the resin include cured products of polymerizable compounds.
  • the cured product of the polymerizable compound can be obtained by polymerizing the polymerizable compound by a known method using a polymerization initiator as necessary.
  • the polymerizable compound has at least one polymerizable functional group in its molecule.
  • the polymerizable compound for example, at least one of a radically polymerizable compound and a cationic polymerizable compound can be used.
  • examples of the fluorine resin include a cured product of a polymerizable compound containing fluorine.
  • a cured product of a fluorine-containing polymerizable compound can be obtained by polymerizing a fluorine-containing polymerizable compound by a known method using a polymerization initiator as necessary.
  • a polymerizable compound containing fluorine has at least one polymerizable functional group in its molecule.
  • the fluorine-containing polymerizable compound for example, at least one of a radically polymerizable compound and a cationic polymerizable compound can be used.
  • the fluorine-containing polymerizable compound for example, fluorine-containing monomers, oligomers, and polymers can be used.
  • the fluorine-containing layer contains inorganic particles, organic particles, ultraviolet absorbers, antioxidants, light stabilizers, antiglare agents, leveling agents, surfactants, lubricants, various sensitizers, flame retardants, if necessary. , tackifiers, polymerization inhibitors, surface modifiers, and other additives.
  • the fluorine-containing layer may be a single layer or multiple layers. Further, the method for forming the fluorine-containing layer is appropriately selected according to the material. is mentioned.
  • the fluorine-containing layer is preferably in direct contact with the first inorganic compound layer.
  • the base material layer in the present embodiment is a member that supports the second inorganic compound layer, the first inorganic compound layer and the fluorine-containing layer.
  • the substrate layer is not particularly limited as long as it has transparency, and examples thereof include resin substrates and glass substrates.
  • Resin substrate The resin constituting the resin substrate is not particularly limited as long as it can obtain a transparent resin substrate.
  • Examples include polyimide resins, polyamide resins, Examples include polyester-based resins.
  • Examples of polyimide-based resins include polyimide, polyamideimide, polyetherimide, and polyesterimide.
  • polyester resins include polyethylene terephthalate, polypropylene terephthalate, polybutylene terephthalate, and polyethylene naphthalate.
  • the glass constituting the glass substrate is not particularly limited as long as it has transparency, and examples thereof include silicate glass and silica glass. Among them, borosilicate glass, aluminosilicate glass, and aluminoborosilicate glass are preferable, and alkali-free glass is more preferable.
  • Commercially available glass substrates include, for example, ultra-thin sheet glass G-Leaf manufactured by Nippon Electric Glass Co., Ltd., ultra-thin glass manufactured by Matsunami Glass Industry Co., Ltd., and the like.
  • the glass constituting the glass substrate is chemically strengthened glass.
  • Chemically strengthened glass is excellent in mechanical strength and is preferable in that it can be made thinner accordingly.
  • Chemically strengthened glass is glass whose mechanical properties are strengthened by a chemical method, typically by partially exchanging ion species, such as replacing sodium with potassium, in the vicinity of the surface of the glass. It has a compressive stress layer.
  • glass constituting the chemically strengthened glass substrate examples include aluminosilicate glass, soda lime glass, borosilicate glass, lead glass, alkali barium glass, and aluminoborosilicate glass.
  • Examples of commercial products of chemically strengthened glass substrates include Corning's Gorilla Glass (Gorilla Glass), AGC's Dragontrail, and Schott's chemically strengthened glass.
  • the thickness of the base layer is not particularly limited as long as it is a thickness that allows flexibility, and is appropriately selected according to the type of base layer. be.
  • the thickness of the resin base material is, for example, preferably 10 ⁇ m or more and 100 ⁇ m or less, and more preferably 25 ⁇ m or more and 80 ⁇ m or less.
  • the thickness of the resin base material is within the above range, good flexibility and sufficient hardness can be obtained.
  • curling of the laminate for a display device can also be suppressed.
  • the thickness of the glass substrate is, for example, preferably 200 ⁇ m or less, more preferably 15 ⁇ m or more and 100 ⁇ m or less, further preferably 20 ⁇ m or more and 90 ⁇ m or less, and 25 ⁇ m or more and 80 ⁇ m or less. is particularly preferred.
  • the thickness of the glass substrate is within the above range, good flexibility and sufficient hardness can be obtained.
  • curling of the laminate for a display device can also be suppressed.
  • Laminate for display device (1) Luminous reflectance When light is incident at an incident angle of 5°, the specular reflectance of the incident light has a luminous reflectance of 2.0% or less. It is preferably 1.7% or less, more preferably 1.5% or less. If the luminous reflectance is too high, it is impossible to prevent the viewer from being reflected in the display area.
  • the luminous reflectance can be obtained in accordance with JIS Z8722:2009.
  • the luminous reflectance is obtained from the reflection spectrum obtained by making light in the wavelength range of 380 nm or more and 780 nm or less incident on the fluorine-containing layer side surface of the laminate for a display device.
  • the tristimulus values X, Y, and Z in the XYZ color system are obtained, and the value of Y is the luminous reflectance. That is, the luminous reflectance refers to the Y value of the CIE1931 standard color system. In the measurement of luminous reflectance, the following conditions can be used.
  • a black vinyl tape having a width larger than the measurement spot area (for example, product name "Yamato vinyl tape NO200-19-21 , Yamato Co., Ltd., 19 mm width) is attached to the surface of the laminate for display device on the side of the substrate layer, and then the measurement is performed.
  • a spectrophotometer can be used as a device for measuring luminous reflectance.
  • a spectrophotometer “UV-2600” manufactured by Shimadzu Corporation can be used.
  • the laminate for a display device in this embodiment has bending resistance. Specifically, when the display device laminate is subjected to a dynamic bending test described below, it is preferable that the display device laminate does not crack or break.
  • the dynamic bending test is performed as follows. First, a laminate for a display device having a size of 20 mm ⁇ 100 mm is prepared. Then, in the dynamic bending test, as shown in FIG. 7A, the short side portion 1C of the display device laminate 1 and the short side portion 1D facing the short side portion 1C are arranged in parallel. are fixed by the fixing portion 51. As shown in FIG. Further, as shown in FIG. 7(a), the fixed portion 51 is horizontally slidable. Next, as shown in FIG. 7(b), the fixing portions 51 are moved closer to each other, thereby deforming the laminate for display device 1 so as to be folded, and furthermore, as shown in FIG.
  • a dynamic bending test was performed so that the bent portion 1E of the laminated body 1 for a display device did not protrude from the lower end of the fixed portion 51, and by controlling the distance when the fixed portion 51 was closest, the display device
  • the distance d between the two opposing short sides 1C and 1D of the laminate 1 can be set to a predetermined value. For example, when the interval d between the short sides 1C and 1D is 10 mm, the outer diameter of the bent portion 1E is considered to be 10 mm.
  • a dynamic bending test was repeated 200,000 times in which the display device laminate 1 was folded 180° so that the distance d between the opposing short sides 1C and 1D was 10 mm. It is preferable that no cracking or breakage occurs when it is repeatedly repeated 500,000 times. Above all, it is preferable that no cracks or breaks occur when a dynamic bending test is repeated 200,000 times in which the display device laminate is folded 180° so that the distance d between the opposing short sides 1C and 1D is 6 mm. .
  • the display laminate may be folded so that the fluorine-containing layer is on the outside, or the display laminate may be folded so that the fluorine-containing layer is on the inside. Even so, it is preferable that the display device laminate does not crack or break.
  • the laminate for a display device in the present embodiment preferably has a total light transmittance of, for example, 85% or more, more preferably 88% or more, and 90% or more. It is even more preferable to have Due to such a high total light transmittance, a laminate for a display device with good transparency can be obtained.
  • the total light transmittance of the laminate for display devices can be measured according to JIS K7361-1:1999, and can be measured, for example, with a haze meter HM150 manufactured by Murakami Color Research Laboratory.
  • the haze of the laminate for a display device in the present embodiment is, for example, preferably 5% or less, more preferably 2% or less, and even more preferably 1% or less. Such a low haze makes it possible to obtain a laminate for a display device with good transparency.
  • the haze of the laminate for a display device can be measured according to JIS K-7136:2000, and can be measured, for example, with a haze meter HM150 manufactured by Murakami Color Research Laboratory.
  • FIG. 2 is a schematic cross-sectional view showing another example of the display device laminate according to the present embodiment.
  • the display device laminate 1a of the present embodiment includes a fluorine-containing layer 2, a first inorganic compound layer 3, a second inorganic compound layer 4, a substrate layer 5, and Furthermore, it is preferable to have another inorganic compound layer 6 (for example, a third inorganic compound layer) and a hard coat layer 7 .
  • FIG. 3 is a schematic cross-sectional view showing an example of a preferred aspect of the laminate for display device in this embodiment.
  • the display device laminate 1a of the present embodiment includes a fluorine-containing layer 2, a first inorganic compound layer 3, a second inorganic compound layer 4, a substrate layer 5, It is preferable to have an intervening layer 9 having a relative film density D3 of 0.10 or more and 0.70 or less between the second inorganic compound layer 4 and the substrate layer 5 .
  • the laminate for a display device in the present embodiment can have one or more other inorganic compound layers between the second inorganic compound layer and the substrate layer.
  • a lower reflectance can be obtained by arranging another inorganic compound layer.
  • the other inorganic compound layer is arranged between the second inorganic compound layer and the hard coat layer when the laminate for a display device in the present embodiment has a hard coat layer.
  • other inorganic compound layers are referred to as a third inorganic compound layer, a fourth inorganic compound layer, etc. from the second inorganic compound layer side.
  • the laminate for a display device in the present embodiment has a multilayer film having a different refractive index.
  • a high refractive index layer (fourth inorganic compound layer) / medium refractive index layer (third inorganic compound layer) / high refractive index layer (second inorganic compound layer) / low refractive index layer (second 1 inorganic compound layer) can be adopted.
  • the refractive index of the third inorganic compound layer is, for example, 1.40 or more and 2.50 or less
  • the refractive index of the fourth inorganic compound layer is, for example, 1.60 or more and 3.00 or less.
  • the medium refractive index layer (third inorganic compound layer)/high refractive index layer (second inorganic compound layer) A structure such as /low refractive index layer (first inorganic compound layer) can be employed.
  • the refractive index of the third inorganic compound layer is, for example, 1.40 or more and 2.50 or less.
  • Inorganic compounds contained in other inorganic compound layers include silicon oxide, gallium oxide, aluminum oxide, zirconium oxide, hafnium oxide, tantalum oxide, cerium oxide, titanium oxide, zinc oxide, tin oxides, magnesium oxide, yttrium oxide, niobium oxide, magnesium fluoride, lithium fluoride, calcium fluoride, barium fluoride, lanthanum fluoride and cerium fluoride.
  • the thickness of the other inorganic compound layer is not particularly limited, it is preferably 10 nm or more and 200 nm or less, more preferably 20 nm or more and 170 nm or less.
  • the total thickness of all the inorganic compound layers included in the laminate for display device in the present embodiment is preferably 500 nm or less, more preferably 400 nm or less. On the other hand, for example, it may be 50 nm or more, or may be 80 nm or more. If the total thickness is too thick, the bending resistance of the laminate for display device may deteriorate.
  • the laminate for display device in the present embodiment may have a hard coat layer between the second inorganic compound layer and the substrate layer.
  • the adhesion of the inorganic compound layer can be improved.
  • the abrasion resistance can be improved by arranging the hard coat layer.
  • the base material layer is a resin base material, the abrasion resistance can be effectively improved by disposing the hard coat layer.
  • the material of the hard coat layer is preferably an organic material.
  • the hard coat layer preferably contains a cured product of a resin composition containing a polymerizable compound.
  • a cured product of a resin composition containing a polymerizable compound can be obtained by subjecting the polymerizable compound to a polymerization reaction by a known method using a polymerization initiator as necessary.
  • the polymerizable compound has at least one polymerizable functional group in its molecule.
  • the polymerizable compound for example, at least one of a radically polymerizable compound and a cationic polymerizable compound can be used.
  • a radically polymerizable compound is a compound having a radically polymerizable group.
  • the radically polymerizable group possessed by the radically polymerizable compound is not particularly limited as long as it is a functional group capable of causing a radical polymerization reaction. Examples thereof include a group containing a carbon-carbon unsaturated double bond. Specific examples include a vinyl group and a (meth)acryloyl group. When the radically polymerizable compound has two or more radically polymerizable groups, these radically polymerizable groups may be the same or different.
  • the number of radically polymerizable groups in one molecule of the radically polymerizable compound is preferably 2 or more, more preferably 3 or more, from the viewpoint of increasing the surface hardness of the hard coat layer and improving the scratch resistance. Preferably.
  • compounds having a (meth)acryloyl group are preferable from the viewpoint of high reactivity.
  • urethane (meth)acrylate, polyester (meth)acrylate, epoxy (meth)acrylate, melamine Polyfunctional (meth)acrylate monomers having several (meth)acryloyl groups in the molecule and having a molecular weight of several hundred to several thousand, called meth)acrylates, polyfluoroalkyl (meth)acrylates, silicone (meth)acrylates, etc. and oligomers can be preferably used, and polyfunctional (meth)acrylate polymers having two or more (meth)acryloyl groups in side chains of the acrylate polymer can also be preferably used.
  • polyfunctional (meth)acrylate monomers having two or more (meth)acryloyl groups in one molecule can be preferably used.
  • a cured product of a polyfunctional (meth)acrylate monomer in the hard coat layer the surface hardness of the hard coat layer can be increased and the scratch resistance can be improved.
  • adhesion can be improved.
  • Polyfunctional (meth)acrylate oligomers or polymers having two or more (meth)acryloyl groups in one molecule can also be preferably used.
  • a cured polyfunctional (meth)acrylate oligomer or polymer in the hard coat layer the surface hardness of the hard coat layer can be increased and the scratch resistance can be improved. Furthermore, bending resistance and adhesion can be improved.
  • (meth)acryloyl represents acryloyl and methacryloyl
  • (meth)acrylate represents acrylate and methacrylate
  • polyfunctional (meth)acrylate monomers include those described in JP-A-2019-132930. Among them, those having 3 or more and 6 or less (meth)acryloyl groups in one molecule are preferable from the viewpoint of high reactivity, high surface hardness of the hard coat layer, and improvement of scratch resistance.
  • polyfunctional (meth)acrylate monomers examples include pentaerythritol triacrylate (PETA), dipentaerythritol hexaacrylate (DPHA), pentaerythritol tetraacrylate (PETTA), dipentaerythritol pentaacrylate (DPPA), tri Methylolpropane tri(meth)acrylate, tripentaerythritol octa(meth)acrylate, tetrapentaerythritol deca(meth)acrylate and the like can be preferably used.
  • PETA pentaerythritol triacrylate
  • DPHA dipentaerythritol hexaacrylate
  • PETTA pentaerythritol tetraacrylate
  • DPPA dipentaerythritol pentaacrylate
  • tri Methylolpropane tri(meth)acrylate tripentaerythrito
  • the scratch resistance may decrease due to the flexible group in the molecular structure. Therefore, in order to suppress deterioration of scratch resistance due to a flexible component (soft segment), it is preferable to use a radically polymerizable compound that does not have a flexible group introduced into its molecular structure. Specifically, it is preferable to use a radically polymerizable compound that is not EO- or PO-modified. By using such a radically polymerizable compound, it is possible to increase cross-linking points and improve scratch resistance.
  • the hard coat layer may contain a monofunctional (meth)acrylate monomer as a radically polymerizable compound in order to adjust hardness and viscosity, improve adhesion, and the like.
  • monofunctional (meth)acrylate monomers include those described in JP-A-2019-132930.
  • a cationically polymerizable compound is a compound having a cationically polymerizable group.
  • the cationically polymerizable group possessed by the cationically polymerizable compound is not particularly limited as long as it is a functional group capable of causing a cationic polymerization reaction. Examples thereof include an epoxy group, an oxetanyl group, and a vinyl ether group.
  • these cationically polymerizable groups may be the same or different.
  • the number of cationically polymerizable groups in one molecule of the cationically polymerizable compound is preferably two or more, more preferably three or more, in order to increase the surface hardness of the hard coat layer and improve the scratch resistance. Preferably.
  • a compound having at least one of an epoxy group and an oxetanyl group as a cationically polymerizable group is preferable, and a compound having two or more of at least one of an epoxy group and an oxetanyl group in one molecule. is more preferred.
  • a cyclic ether group such as an epoxy group or an oxetanyl group is preferable from the viewpoint that shrinkage accompanying a polymerization reaction is small.
  • compounds having epoxy groups are readily available in various structures, do not adversely affect the durability of the resulting hard coat layer, and are easy to control compatibility with radically polymerizable compounds. There is an advantage.
  • the oxetanyl group has a higher degree of polymerization and is less toxic than the epoxy group, and when the resulting hard coat layer is combined with a compound having an epoxy group,
  • advantages such as increasing the network formation rate obtained from the cationically polymerizable compound and forming an independent network without leaving unreacted monomers in the film even in a region mixed with the radically polymerizable compound.
  • Examples of cationic polymerizable compounds having an epoxy group include polyglycidyl ethers of polyhydric alcohols having an alicyclic ring, or compounds containing cyclohexene rings or cyclopentene rings, which are treated with a suitable oxidizing agent such as hydrogen peroxide or peracid.
  • Examples include alicyclic epoxy resins obtained by epoxidation.
  • Aliphatic epoxy resins such as polyglycidyl ethers of aliphatic polyhydric alcohols or their alkylene oxide adducts, polyglycidyl esters of aliphatic long-chain polybasic acids, and homopolymers and copolymers of glycidyl (meth)acrylates are also included.
  • Bisphenols such as bisphenol A, bisphenol F and hydrogenated bisphenol A, or derivatives such as alkylene oxide adducts and caprolactone adducts thereof, are reacted with epichlorohydrin, glycidyl ethers, and novolac epoxy resins. and glycidyl ether type epoxy resins derived from bisphenols.
  • alicyclic epoxy resins examples include those described in JP-A-2018-104682.
  • the hard coat layer may contain a polymerization initiator as necessary.
  • the hard coat layer may contain an antistatic agent. Antistatic properties can be imparted to the laminate for display device.
  • the hard coat layer can further contain additives as needed.
  • the additive is appropriately selected according to the function to be imparted to the hard coat layer, and is not particularly limited. Examples include inorganic particles, organic particles, ultraviolet absorbers, infrared absorbers, antifouling agents, antiglare agents, and leveling agents. , surfactants, lubricants, various sensitizers, flame retardants, adhesion promoters, polymerization inhibitors, antioxidants, light stabilizers, surface modifiers and the like.
  • the material for the hard coat layer is a radically polymerizable compound having at least one of urethane (meth)acrylate and polyfunctional (meth)acrylate monomers in order to obtain better bending resistance.
  • an organic inorganic material in which a radically polymerizable compound and reactive inorganic particles having a reactive functional group capable of forming a covalent bond are used in combination is preferred, and an adhesion promoter is more preferably used in combination as an additive.
  • reactive inorganic particles include silica having a reactive functional group.
  • reactive functional groups include vinyl groups, (meth)acryloyl groups, allyl groups, epoxy groups, and silanol groups.
  • the thickness of the hard coat layer may be appropriately selected depending on the function of the hard coat layer and the application of the laminate for display devices.
  • the thickness of the hard coat layer is, for example, preferably 0.5 ⁇ m or more and 50 ⁇ m or less, more preferably 1.0 ⁇ m or more and 40 ⁇ m or less, further preferably 1.5 ⁇ m or more and 30 ⁇ m or less. It is particularly preferable to be 0 ⁇ m or more and 20 ⁇ m or less. If the thickness of the hard coat layer is within the above range, it is possible to obtain sufficient hardness as the hard coat layer.
  • Examples of the method of forming the hard coat layer include a method of applying a hard coat layer resin composition containing the polymerizable compound and the like onto the base material layer and curing the resin composition.
  • the laminate for a display device in the present embodiment can have an adhesive layer for sticking on the surface of the substrate layer opposite to the second inorganic compound layer.
  • the laminate for a display device can be attached to, for example, a display panel or the like via the adhesive layer for attachment.
  • the adhesive used for the sticking adhesive layer is not particularly limited as long as it has transparency and is capable of adhering the laminate for a display device to a display panel or the like.
  • Curable adhesives ultraviolet curable adhesives, two-liquid curable adhesives, hot-melt adhesives, pressure-sensitive adhesives (so-called adhesives), and the like can be mentioned.
  • the thickness of the sticking adhesive layer is, for example, preferably 10 ⁇ m or more and 100 ⁇ m or less, more preferably 25 ⁇ m or more and 80 ⁇ m or less, and even more preferably 40 ⁇ m or more and 60 ⁇ m or less. If the thickness of the sticking adhesive layer is too thin, there is a possibility that the display device laminate and the display panel or the like cannot be sufficiently adhered. On the other hand, if the adhesive layer for sticking is too thick, the flexibility may be impaired.
  • an adhesive film may be used as the sticking adhesive layer.
  • an adhesive composition may be applied onto a support or a substrate layer to form an adhesive layer for attachment.
  • the adhesive layer for attachment may be a layer having adhesion to the extent that it can be peeled off after being attached to the display panel of the display device, or may be a layer having high adhesion without the purpose of peeling. good.
  • an interlayer adhesive layer may be arranged between each layer.
  • the adhesive used for the interlayer adhesive layer the same adhesive as used for the adhesive layer for attachment can be used.
  • an intervening layer 9 having a relative film density D3 of 0.10 or more and 0.70 or less is provided between the second inorganic compound layer 4 and the base layer 5. It is preferred to have By arranging such an intervening layer, bending resistance is further improved.
  • the display device laminate having the intervening layer is subjected to a dynamic bending test in which the display device laminate 1 is folded 180° so that the distance d between the opposing short sides 1C and 1D is 5 mm. It is preferable that no cracks or breaks occur when repeated 200,000 times, and more preferably no cracks or breaks occur when repeated 500,000 times.
  • the display laminate may be folded so that the fluorine-containing layer is on the outside, or the display laminate may be folded so that the fluorine-containing layer is on the inside. Even so, it is preferable that the display device laminate does not crack or break.
  • the intervening layer in the present embodiment has a relative film density D3 of 0.10 or more and 0.70 or less, preferably 0.20 or more and 0.60 or less.
  • the intervening layer is preferably a dispersed layer in which inorganic compound particles are dispersed in a binder resin. This is because it is easy to set the relative film density within the above range. Also, the intervening layer may be an inorganic compound layer other than the first inorganic compound layer and the second inorganic compound layer.
  • the relative film density of dispersion layer film density of dispersion layer (measured value) / film density (literature value)
  • the film density (literature value) for calculating the relative film density of the intervening layer the film density (literature value) of the inorganic compound layer mainly composed of the inorganic compound contained in the inorganic compound particles is used.
  • the relative film density D1 of the first inorganic compound layer, the relative film density D2 of the second inorganic compound layer, and the relative film density D3 of the intervening layer preferably satisfy the relationship D3 ⁇ D2 ⁇ D1. .
  • the difference in relative film density between adjacent layers can be reduced, and stress concentration can be suppressed. Therefore, bending resistance is further improved, and cracks and peeling can be suppressed.
  • the relative film density D2 of the second inorganic compound layer and the relative film density D3 of the intermediate layer satisfy 1.0 ⁇ D2/D3 ⁇ 7.0.
  • D2/D3 is 1.0 or more, peeling at the interface between the first inorganic compound layer and the second inorganic compound layer can be effectively suppressed in the bending test.
  • D2/D3 is 7.0 or less, peeling at the interface between the intervening layer and the second inorganic compound layer can be effectively suppressed in the bending test.
  • the relative film density D1 of the first inorganic compound layer and the relative film density D3 of the intermediate layer satisfy 1.0 ⁇ D1/D3 ⁇ 12.0.
  • D1/D3 is 1.0 or more, wear resistance tends to be further improved.
  • D1/D3 is 12.0 or less, the bending resistance is further improved, and the occurrence of cracks in the dispersion layer can be suppressed.
  • the intermediate layer is preferably a dispersion layer in which inorganic compound particles are dispersed in a binder resin.
  • the dispersion layer contains inorganic compound particles and a binder resin.
  • inorganic compound particles are not particularly limited, silicon oxide, gallium oxide, aluminum oxide, zirconium oxide, hafnium oxide, tantalum oxide, cerium oxide, titanium oxide, zinc oxides, tin oxides, magnesium oxides, yttrium oxides, niobium oxides, magnesium fluoride, lithium fluoride, calcium fluoride, barium fluoride, lanthanum fluoride and cerium fluoride.
  • inorganic compound particles having a refractive index higher than that of the first inorganic compound are preferable.
  • Specific examples of such inorganic compound particles include aluminum oxide, zirconium oxide, niobium oxide, zinc oxide, tin oxide, and titanium oxide.
  • the content of the inorganic compound particles in the dispersed layer is not particularly limited as long as the content is such that the relative film density D3 of the intervening layer is the above value.
  • Binder resin is preferably a cured product of a polymerizable compound.
  • the polymerizable compound can be the same as that described in the section of the hard coat layer of the laminate for a display device of the first embodiment, so the description is omitted here.
  • the refractive index of the dispersion layer is preferably 1.60 or more, more preferably 1.65 or more. On the other hand, it is, for example, 2.00 or less, and may be 1.80 or less.
  • the thickness of the dispersion layer is not particularly limited, but is preferably 10 nm or more and 500 nm or less, more preferably 30 nm or more and 300 nm or less.
  • a method for forming the dispersion layer for example, a method of applying a resin composition for a dispersion layer containing inorganic compound particles and a polymerizable compound onto a substrate layer or a hard coat layer to be described later and curing the composition can be used. mentioned.
  • the intervening layer may be another inorganic compound layer.
  • Inorganic compounds contained in the inorganic compound layer as the intermediate layer include silicon oxide, gallium oxide, aluminum oxide, zirconium oxide, hafnium oxide, tantalum oxide, cerium oxide, and titanium oxide. oxide, zinc oxide, tin oxide, magnesium oxide, yttrium oxide, niobium oxide, magnesium fluoride, lithium fluoride, calcium fluoride, barium fluoride, lanthanum fluoride and cerium fluoride.
  • a material having a higher refractive index than the first inorganic compound is preferable.
  • inorganic compounds examples include aluminum oxide, zirconium oxide, hafnium oxide, tantalum oxide, cerium oxide, titanium oxide, zinc oxide, tin oxide, magnesium oxide, yttrium oxide, and niobium oxide. inorganic oxides, lanthanum fluoride, cerium fluoride, and the like.
  • the refractive index of the inorganic compound layer as an intervening layer is preferably 1.60 or higher, more preferably 1.65 or higher. On the other hand, it is, for example, 2.00 or less, and may be 1.80 or less.
  • the thickness of the inorganic compound layer as the intermediate layer is not particularly limited, but is preferably 10 nm or more and 500 nm or less, more preferably 30 nm or more and 300 nm or less.
  • the laminate for a display device according to the present embodiment can be used as a front plate in a display device, which is arranged closer to the viewer than the display panel. Since the laminate for a display device according to the present embodiment has excellent bending resistance and wear resistance, it can be suitably used as a front plate of a flexible display device such as a foldable display, a rollable display, and a bendable display. In particular, the laminate for a display device according to the present embodiment can improve bending resistance, and thus can be suitably used for a front panel of a foldable display.
  • the thickness of the display device laminate in the present embodiment is, for example, preferably 10 ⁇ m or more and 500 ⁇ m or less, more preferably 20 ⁇ m or more and 400 ⁇ m or less, and even more preferably 30 ⁇ m or more and 300 ⁇ m or less.
  • the thickness of the laminate for a display device is within the above range, the flexibility can be enhanced.
  • the display device laminate in the present embodiment is used as a front plate in a display device such as a smartphone, a tablet terminal, a wearable terminal, a personal computer, a television, a digital signage, a public information display (PID), or an in-vehicle display. be able to.
  • a display device such as a smartphone, a tablet terminal, a wearable terminal, a personal computer, a television, a digital signage, a public information display (PID), or an in-vehicle display.
  • Second Embodiment The inventors of the present invention conducted repeated studies to improve bending resistance and wear resistance while maintaining low reflectivity of a laminate disposed on the surface of a display device.
  • a fluorine-containing layer containing fluorine atoms is arranged on one surface of the laminate, and an inorganic compound layer having a predetermined fluorine content ratio is used as the low refractive index layer for realizing a low reflectance of the laminate. It has been found that bending resistance and wear resistance can be improved by using an inorganic compound layer having a predetermined relative film density for the high refractive index layer that realizes a low reflectance.
  • the fluorine-containing layer is arranged on one surface of the laminate for a display device, and fluorine in the first inorganic compound layer (low refractive index layer) which is the inorganic compound layer on the fluorine-containing layer side It has been found that wear resistance can be obtained by setting the content ratio within a predetermined range. Furthermore, by setting the relative film density of the second inorganic compound layer (high refractive index layer) to a predetermined low range, it was found that a laminate for a display device having high resistance to stress change and good bending resistance can be obtained. , completed the present invention.
  • the present embodiment is a laminate for a display device having a fluorine-containing layer containing fluorine atoms, a first inorganic compound layer, a second inorganic compound layer, and a substrate layer in this order, , the first inorganic compound layer has a first inorganic compound that is a low refractive index material, the content ratio of fluorine atoms is 6.5 atomic % or less, and the second inorganic compound layer has a high It has a second inorganic compound that is a refractive index material, has a relative film density D2 of 0.50 or more and less than 1.00, and is applied to the fluorine-containing layer side surface of the display device laminate at an incident angle of 5°.
  • a laminate for a display device which has a luminous reflectance of 2.0% or less for specularly reflected light when light is incident thereon.
  • the laminate for a display device of this embodiment will be described in detail.
  • FIG. 1 is a schematic cross-sectional view showing an example of the laminate for a display device according to this embodiment.
  • the display device laminate 1b of the present embodiment includes a fluorine-containing layer 2 containing fluorine atoms, a first inorganic compound layer 3, a second inorganic compound layer 4, a substrate 5 and , in that order.
  • the first inorganic compound layer contains the first inorganic compound, which is a low refractive index material, and has a fluorine atom content of 6.5 atomic % or less.
  • the second inorganic compound layer contains a second inorganic compound having a higher refractive index than the first inorganic compound, and has a relative film density D2 of 0.50 or more and less than 1.00. Furthermore, in the display device laminate 1b of the present embodiment, the luminous reflectance of specularly reflected light when light is incident on the surface 1A on the fluorine-containing layer 2 side at an incident angle of 5° is 2.0% or less. be.
  • the laminate for a display device in the present embodiment has a fluorine-containing layer on one surface, and furthermore, the content ratio of fluorine atoms in the first inorganic compound layer is within a predetermined range, so that excellent wear resistance will have This is presumed to be due to the following reasons.
  • FIG. 4A shows the case where the first inorganic compound layer 3 has a low fluorine atom content
  • FIG. 4B shows the first case where the first inorganic compound layer 3 has a high fluorine atom content
  • 2 shows a schematic cross-sectional view of the inorganic compound layer 3 and the fluorine-containing layer 2 of FIG. As shown in FIG.
  • the laminate for a display device has excellent bending resistance because the relative film density D2 of the second inorganic compound layer is within a predetermined low range.
  • the laminate for a display device in the present embodiment includes a first inorganic compound layer that is a low refractive index layer and a second inorganic compound layer that is a high refractive index layer, thereby achieving a predetermined luminous reflectance. will have. Therefore, the laminate for a display device has low reflectivity and excellent bending resistance and abrasion resistance.
  • each configuration in the laminate for display device of the present embodiment will be described in detail.
  • First Inorganic Compound Layer is composed of a first inorganic compound that is a low refractive index material.
  • the first inorganic compound that constitutes the first inorganic compound layer in the present embodiment include those similar to the first inorganic compound in the first embodiment.
  • silicon oxide is preferable from the viewpoint of refractive index and versatility.
  • one type of inorganic compound is preferably contained in the first inorganic compound layer, but a plurality of types of inorganic compounds may be contained.
  • the first inorganic compound layer is preferably a deposited film.
  • a silicon oxide (silica) deposited film is preferred.
  • the content ratio of fluorine atoms in the first inorganic compound layer in the present embodiment is 6.5 atomic % or less.
  • the fluorine atom content is preferably 6.3 atomic % or less, more preferably 5.0 atomic % or less. If the content ratio of fluorine atoms is within the above range, it will have excellent abrasion resistance.
  • the first inorganic compound layer in the present embodiment preferably has a low fluorine atomic ratio. That is, the first inorganic compound layer may not contain fluorine atoms, and the lower limit of the content ratio of fluorine atoms is 0%.
  • the content ratio of fluorine atoms in the first inorganic compound layer is obtained by measuring the first inorganic compound layer by Rutherford Backscattering Spectrometry (RBS) using the measurement apparatus and measurement conditions described above. It is the ratio of fluorine atoms when the total amount of (for example, inorganic elements such as silicon, oxygen, fluorine, etc.) is 100 atomic %.
  • RBS Rutherford Backscattering Spectrometry
  • the refractive index of the first inorganic compound layer in the present embodiment can be the same as the refractive index of the first inorganic compound layer in the first embodiment, so the description here is omitted. .
  • the relative film density D1 of the first inorganic compound layer which is the low refractive index layer, is preferably 0.70 or more and 1.20 or less.
  • the relative film density D1 of the first inorganic compound layer is more preferably 0.75 or more, particularly preferably 0.80 or more. If the relative film density D1 is too low, the fluorine content ratio becomes high, which may result in poor wear resistance. On the other hand, it is more preferably 1.17 or less, particularly preferably 1.15 or less. If the relative film density D1 is too high, the bending resistance may be poor and cracks may occur in the first inorganic compound layer.
  • the method for calculating the relative film density of the inorganic compound layer is the same as the method described in the first embodiment, description thereof is omitted here. Even when the first inorganic compound layer in the present embodiment contains fluorine atoms, the theoretical film density of the inorganic compound layer composed of the first inorganic compound is adopted as the film density (literature value) described later. do.
  • the method for adjusting the relative film density of the first inorganic compound layer within the above range can be the same as the method described in the first embodiment, so the description is omitted here.
  • the thickness of the first inorganic compound layer in the present embodiment is the same as the thickness of the first inorganic compound layer in the first embodiment, and thus the description thereof is omitted here.
  • the method for forming the first inorganic compound layer in this embodiment is the same as the method for forming the first inorganic compound layer in the first embodiment, and thus the description is omitted here.
  • Second Inorganic Compound Layer The content of the second inorganic compound layer in this embodiment is the same as that of the second inorganic compound layer in the first embodiment, and thus the description thereof is omitted here.
  • Fluorine-Containing Layer The content of the fluorine-containing layer in the present embodiment is the same as that of the fluorine-containing layer in the first embodiment, so the description is omitted here.
  • Base Material Layer The content of the base material layer in the present embodiment is the same as that of the base material layer in the first embodiment, so the description thereof is omitted here.
  • Laminate for display device The luminous reflectance, dynamic bending resistance, total light transmittance, and haze of the laminate for a display device in the present embodiment are the same as those in the first embodiment, and are therefore described here. are omitted.
  • the laminate for a display device in the present embodiment includes the above-described fluorine-containing layer 2, the first inorganic compound layer 3, the second inorganic compound layer 4, and the substrate layer 5, in addition to other layers. may have Other layers include other inorganic compound layers, intervening layers, hard coat layers, adhesive layers for attachment, and interlayer adhesive layers.
  • FIG. 2 is a schematic cross-sectional view showing another example of the laminate for a display device according to this embodiment.
  • the display device laminate 1b of the present embodiment includes a fluorine-containing layer 2, a first inorganic compound layer 3, a second inorganic compound layer 4, a substrate layer 5, Furthermore, it is preferable to have another inorganic compound layer 6 (for example, a third inorganic compound layer) and a hard coat layer 7 .
  • FIG. 3 is a schematic cross-sectional view showing an example of a preferred aspect of the laminate for display device in this embodiment.
  • the display device laminate 1b of the present embodiment includes a fluorine-containing layer 2, a first inorganic compound layer 3, a second inorganic compound layer 4, a substrate layer 5, and It is preferable to have an intervening layer 9 having a relative film density D3 of 0.10 or more and 0.70 or less between the second inorganic compound layer 4 and the substrate layer 5 .
  • inorganic compound layers intervening layers, hard coat layers, bonding adhesive layers, and interlayer adhesive layers can be the same as those described in the first embodiment, so descriptions thereof are omitted here.
  • the inventors of the present invention conducted repeated studies to improve bending resistance and wear resistance while maintaining low reflectivity of a laminate disposed on the surface of a display device.
  • a fluorine-containing layer containing fluorine atoms is arranged on one surface of the laminate, and an inorganic compound layer having a predetermined relative film density is used as the low refractive index layer for realizing a low reflectance of the laminate.
  • the high refractive index layer that achieves low reflectance of the body has a predetermined relative film density and uses a dispersion layer of inorganic compound particles having a high refractive index (high refractive index dispersion layer) to improve bending resistance. and wear resistance can be improved.
  • the fluorine-containing layer on one surface of the display device laminate and setting the relative film density of the first inorganic compound layer (low refractive index layer) to a predetermined range. It was found that abrasion resistance can be obtained. Furthermore, between the substrate layer and the first inorganic compound layer, a dispersion layer (high refractive index dispersion layer) of inorganic compound particles having a high refractive index and having a relative film density in a predetermined low range is arranged. Thus, the inventors have found that a laminate for a display device having high resistance to stress change and good bending resistance can be obtained, and have completed the present invention.
  • the present embodiment is a laminate for a display device having a fluorine-containing layer containing fluorine atoms, a first inorganic compound layer, and a substrate layer in this order, wherein the first inorganic compound layer has a first inorganic compound that is a low refractive index material, has a relative film density D1 of 0.70 or more and 1.20 or less, and between the first inorganic compound layer and the base layer,
  • the display device has a high refractive index dispersion layer in which inorganic compound particles having a high refractive index are dispersed in a binder resin, and the relative film density D4 of the high refractive index dispersion layer is 0.10 or more and 0.70 or less.
  • a laminate for a display device which has a luminous reflectance of 2.0% or less for specularly reflected light when light is incident on the fluorine-containing layer side surface of the laminate for a display device at an incident angle of 5°.
  • the laminate for a display device of this embodiment will be described in detail.
  • FIG. 5 is a schematic cross-sectional view showing an example of the laminate for a display device according to this embodiment.
  • the display device laminate 1c of the present embodiment includes a fluorine-containing layer 2 containing fluorine atoms, a first inorganic compound layer 3, a high refractive index dispersion layer 10, and a substrate layer. 5 and , in that order.
  • the first inorganic compound layer contains the first inorganic compound, which is a low refractive index material, and has a relative film density D1 of 0.70 or more and 1.20 or less.
  • a high refractive index dispersion layer in which inorganic compound particles having a high refractive index are dispersed in a binder resin is arranged between the base material layer and the first inorganic compound layer.
  • the relative film density D4 of this high refractive index dispersion layer is 0.10 or more and 0.70 or less.
  • the luminous reflectance of specularly reflected light when light is incident on the surface 1A on the fluorine-containing layer 2 side at an incident angle of 5° is 2.0% or less. be.
  • the laminate for a display device has a fluorine-containing layer on one surface, and the relative film density D1 of the first inorganic compound layer is within a predetermined range, thereby exhibiting excellent abrasion resistance.
  • a high refractive index dispersion layer in which inorganic compound particles having a high refractive index are dispersed in a binder resin is arranged between the base material layer and the first inorganic compound layer.
  • the relative film density D4 is within the predetermined low range, the film has excellent bending resistance.
  • the high refractive index dispersion layer contains a binder resin and thus has high flexibility.
  • the laminate for a display device in the present embodiment includes a first inorganic compound layer that is a low refractive index layer and a high refractive index dispersed layer in which inorganic compound particles that are high refractive index particles are dispersed. luminous reflectance. Therefore, the laminate for a display device has low reflectivity and excellent bending resistance and abrasion resistance.
  • First Inorganic Compound Layer The content of the first inorganic compound layer in this embodiment is the same as that of the first inorganic compound layer in the first embodiment, and thus the description thereof is omitted here.
  • the high refractive index dispersion layer is disposed between the first inorganic compound layer and the substrate layer and contains inorganic compound particles having a high refractive index and a binder resin.
  • inorganic Compound Particles and Binder Resin The inorganic compound particles and the binder resin are described in "(a) inorganic compound particles” and "(b) binder resin” in the section "intervening layer" in the first embodiment. Since it is the same as that of 1, description here is abbreviate
  • the relative film density D4 of the high refractive index dispersion layer is 0.10 or more and 0.70 or less, preferably 0.20 or more and 0.60 or less.
  • the calculation method of the relative film density of the high refractive index dispersion layer can be the same as that of the dispersion layer in the above-described first embodiment, so the explanation is omitted here.
  • the relative film density D1 of the first inorganic compound layer and the relative film density D4 of the high refractive index dispersion layer preferably satisfy 1.0 ⁇ D1/D4 ⁇ 12.0.
  • D1/D4 is 1.0 or more, wear resistance tends to improve.
  • D1/D4 is 12.0 or less, the bending resistance is further improved, and the occurrence of cracks in the high refractive index dispersion layer can be suppressed.
  • the refractive index of the high refractive index dispersion layer in the present embodiment is preferably 1.60 or more, more preferably 1.65 or more. On the other hand, it is, for example, 2.00 or less, and may be 1.80 or less.
  • the thickness of the high refractive index dispersion layer is not particularly limited, but is preferably 10 nm or more and 500 nm or less, more preferably 30 nm or more and 300 nm or less.
  • a high refractive index dispersion layer containing inorganic compound particles having a high refractive index and a polymerizable compound is formed on a substrate layer or a hard coat layer described later.
  • a method of applying and curing the resin composition for the dispersion layer may be used.
  • Fluorine-Containing Layer The content of the fluorine-containing layer in the present embodiment is the same as that of the fluorine-containing layer in the first embodiment, so the description is omitted here.
  • Base Material Layer The content of the base material layer in the present embodiment is the same as that of the base material layer in the first embodiment, so the description thereof is omitted here.
  • Laminate for display device (1) Luminous reflectance When light is incident at an incident angle of 5°, the specular reflectance of the incident light has a luminous reflectance of 2.0% or less. It is preferably 1.7% or less, more preferably 1.5% or less. If the luminous reflectance is too high, it is impossible to prevent the viewer from being reflected in the display area.
  • the above luminous reflectance is a value measured by the measuring method described in the first embodiment.
  • the laminate for a display device in this embodiment has bending resistance. Specifically, when the dynamic bending test described in the first embodiment is performed on the display device laminate, it is preferable that the display device laminate does not crack or break.
  • a dynamic bending test was repeated 200,000 times in which the display device laminate 1 was folded 180° so that the distance d between the opposing short sides 1C and 1D was 5 mm. It is preferable that no cracking or breakage occurs when it is repeatedly repeated 500,000 times. Above all, it is preferable that no cracks or breaks occur when a dynamic bending test is repeated 200,000 times in which the display device laminate is folded 180° so that the distance d between the opposing short sides 1C and 1D is 4 mm. .
  • the display laminate may be folded so that the fluorine-containing layer is on the outside, or the display laminate may be folded so that the fluorine-containing layer is on the inside. Even so, it is preferable that the display device laminate does not crack or break.
  • the laminate for a display device in the present embodiment preferably has a total light transmittance of, for example, 85% or more, more preferably 88% or more, and 90% or more. It is even more preferable to have Due to such a high total light transmittance, a laminate for a display device with good transparency can be obtained.
  • the haze of the laminate for a display device in the present embodiment is, for example, preferably 5% or less, more preferably 2% or less, and even more preferably 1% or less. Such a low haze makes it possible to obtain a laminate for a display device with good transparency.
  • the total light transmittance and haze of the display device laminate are values measured by the measurement method described in the first embodiment.
  • the laminate for a display device in the present embodiment includes, in addition to the fluorine-containing layer 2, the first inorganic compound layer 3, the high refractive index dispersion layer 10, and the substrate layer 5, other layers. may have.
  • Other layers include hard coat layers, lamination adhesive layers and interlayer adhesive layers.
  • the laminate for a display device in the present embodiment preferably has a hard coat layer between the high refractive index dispersion layer and the substrate layer.
  • the hard coat layer, the bonding adhesive layer, and the interlayer adhesive layer can be the same as those described in the first embodiment, so descriptions thereof will be omitted here.
  • a display device includes a display panel and a display device according to any one of the above-described first, second, and third embodiments, which is arranged on the observer side of the display panel. and a laminate.
  • FIG. 6 is a schematic cross-sectional view showing an example of a display device according to the present disclosure.
  • the display devices 20a to 20c include a display panel 21 and the display device laminate 1a of the first embodiment arranged on the observer side of the display panel 21. , the display device laminate 1b of the second embodiment, or the display device laminate 1c of the third embodiment.
  • the display device laminates 1a, 1b, 1c and the display panel 21 can be bonded together via the bonding adhesive layer 8 of the display device laminate 1, for example.
  • the flexible display device includes a laminate for a display device having low reflectivity, and therefore has improved visibility. Furthermore, since the laminate for a display device has excellent bending resistance and wear resistance, it is less likely to be scratched and display defects are suppressed even when repeatedly bent.
  • the laminate for a display device according to the present disclosure is arranged on the surface of the display device, it is arranged so that the fluorine-containing layer is on the outside and the substrate layer is on the inside.
  • the method of disposing the laminate for a display device according to the present disclosure on the surface of the display device is not particularly limited, but includes, for example, a method of interposing an adhesive layer.
  • Examples of the display panel in the present disclosure include display panels used in display devices such as organic EL display devices and liquid crystal display devices.
  • the display device according to the present disclosure can have a touch panel member between the display panel and the laminate for display device.
  • the display device in the present disclosure is preferably a flexible display device such as a foldable display, a rollable display, or a bendable display.
  • the display device in the present disclosure is preferably foldable. That is, the display device in the present disclosure is preferably a foldable display.
  • composition of resin composition for hard coat layer ⁇ Pentaerythritol acrylate (product name “A-9550”, manufactured by Shin-Nakamura Chemical Co., Ltd.): 87 parts by mass ⁇ Pentaerythritol acrylate (product name “A-TMM-3L”, manufactured by Shin-Nakamura Chemical Co., Ltd.): 13 parts by mass ⁇ Polymerization Initiator (1-hydroxycyclohexylphenyl ketone, product name "Omnirad 184", manufactured by IGM Resins B.V.): 4 parts by mass Silica particles (average primary particle diameter 12 nm, manufactured by Nissan Chemical Industries, Ltd.): 40 parts by mass ( 100% solid content conversion value) ⁇ Methyl isobutyl ketone: 210 parts by mass
  • a second inorganic compound layer and a first inorganic compound layer were formed in this order on the hard coat layer.
  • the first inorganic compound layer and the second inorganic compound layer were formed by vacuum deposition using the constituent materials shown in Table 1 and at the film forming speed shown in Table 1.
  • Tables 1 and 2 show the constituent materials, thicknesses, deposition rates and refractive indices of the first inorganic compound layer and the second inorganic compound layer.
  • Examples 1-12 to 1-16, Comparative Examples 1-11 to 1-14 A hard coat layer, a third inorganic compound layer, a second inorganic compound layer, a first inorganic compound layer, and a fluorine-containing layer (thickness: 7 nm) were formed in this order on the substrate layer.
  • Tables 1 and 2 show the constituent materials, thicknesses, deposition rates and refractive indices of the first to third inorganic compound layers.
  • the methods of forming the substrate layer, hard coat layer and fluorine-containing layer used are the same as in Example 1-1 above.
  • Examples 1-17 to 1-19, Comparative Examples 1-15 to 1-16 A hard coat layer, a fourth inorganic compound layer, a third inorganic compound layer, a second inorganic compound layer, a first inorganic compound layer, and a fluorine-containing layer (thickness: 7 nm) are formed in this order on the substrate layer. bottom.
  • Tables 1 and 2 show the constituent materials, thicknesses, deposition rates and refractive indices of the first to fourth inorganic compound layers. The methods of forming the substrate layer, hard coat layer and fluorine-containing layer used were the same as in Example 1-1.
  • Example 1-1 A hard coat layer, a first inorganic compound layer, and a fluorine-containing layer (thickness: 7 nm) were formed in this order on the substrate layer.
  • Table 2 shows the constituent material, thickness, deposition rate and refractive index of the first inorganic compound layer. The methods of forming the substrate layer, hard coat layer and fluorine-containing layer used were the same as in Example 1-1.
  • Example 1-2 A hard coat layer, a second inorganic compound layer, and a fluorine-containing layer (thickness: 7 nm) were formed in this order on the substrate layer.
  • Table 2 shows the constituent material, thickness, deposition rate and refractive index of the second inorganic compound layer. The methods of forming the substrate layer, hard coat layer and fluorine-containing layer used were the same as in Example 1-1.
  • the abrasion resistance of the display device laminates obtained in Examples 1-1 to 1-19 and Comparative Examples 1-1 to 1-16 was evaluated by the following evaluation method and evaluation criteria. ⁇ Evaluation method Using Gakushin type rubbing fastness tester AB-301 manufactured by Tester Sangyo Co., Ltd., a laminate with a size of 5 cm ⁇ 10 cm is placed on a glass plate with cellophane tape (registered trademark) so that there are no folds or wrinkles. Fixed.
  • the fixing portions 51 are moved closer to each other, thereby deforming the laminate for display device 1 so as to be folded, and furthermore, as shown in FIG. 7(c), Then, after moving the fixing portion 51 to a position where the distance d between the two opposing short side portions 1C and 1D fixed by the fixing portion 51 of the display device laminate 1 becomes a predetermined value, the fixing portion 51 is removed. Deformation of the display device laminate 1 was eliminated by moving in the opposite direction. By moving the fixing portion 51 as shown in FIGS. 7A to 7C, the stack 1 for a display device was repeatedly folded by 180°.
  • the distance d between the two opposing short sides 1C and 1D of the display device laminate 1 was 6 mm ( ⁇ 6 mm dynamic bending test) or 10 mm ( ⁇ 10 mm dynamic bending test). Also, the laminate was bent so that the fluorine-containing layer was on the outside. The results of the dynamic bending test were evaluated according to the following criteria.
  • Example 2-1 to 2-24 Comparative Examples 2-1 to 2-8
  • a hard coat layer was formed on the substrate layer in the same manner as in Example 1-1.
  • a dispersion layer resin composition containing inorganic compound particles and a polymerizable compound (aliphatic urethane acrylate) was obtained with the following composition.
  • the types of inorganic compound particles shown in Tables 5 and 6 were used, and the blending amount of the inorganic compound particles was varied.
  • composition of resin composition for dispersion layer ⁇ Aliphatic urethane acrylate (product name “EBECRYL225”, manufactured by Daicel Ohnex): 74 parts by mass ⁇ Pentaerythritol (tri/tetra) acrylate (product name “PETIA”, manufactured by Daicel Ohnex): 26 parts by mass ⁇ Polymerization Initiator (1-hydroxycyclohexylphenyl ketone, product name “Omnirad 184", manufactured by IGM Resins B.V.): 4 parts by mass Inorganic compound particles (average primary particle size 10 nm, manufactured by Resinocolor): Type of inorganic compound particles and the blending amount (parts by mass (converted to 100% solid content)) are shown in Tables 5 and 6 Methyl isobutyl ketone: 300 parts by mass
  • a coating film was formed by applying the resin composition for the dispersion layer onto the hard coat layer. Then, this coating film was dried and cured to form a dispersion layer having the thickness and refractive index shown in Tables 5 and 6.
  • a second inorganic compound layer and a first inorganic compound layer were formed in this order on the dispersion layer.
  • the second inorganic compound layer was formed by vacuum deposition using the constituent materials shown in Tables 5 and 6 at the film formation rates shown in Tables 5 and 6.
  • Tables 5 and 6 show the thickness and refractive index of the second inorganic compound layer.
  • the first inorganic compound layer was formed by a vacuum deposition method using the constituent materials shown in Tables 5 and 6 at the film formation rates shown in Tables 5 and 6.
  • Tables 5 and 6 show the thickness and refractive index of the first inorganic compound layer.
  • a fluorine-containing layer having a thickness of 7 nm was formed on the first inorganic compound layer in the same manner as in Example 1-1.
  • the relative film densities D3 of the first inorganic compound layer D1, the second inorganic compound layer D2, and the dispersion layer of the obtained laminate for display device were measured according to "A. Laminate for display device, I. First embodiment, 1. First inorganic compound layer (3) Relative film density D1” and “A. Laminate for display device I. First embodiment 6. Other configurations (5) Intervening layer (i) Relative film density” It was measured.
  • the distance d between the two opposing short sides 1C and 1D of the display device laminate 1 is set to 3 mm ( ⁇ 3 mm dynamic bending test) or 4 mm ( ⁇ 4 mm dynamic bending test), and the lamination
  • the test was conducted with the fluorine-containing layer side of the body as the inside, and the dynamic flexibility was evaluated according to the following evaluation criteria.
  • the distance d between the two opposing short sides 1C and 1D of the display device laminate 1 is set to 4 mm ( ⁇ 4 mm dynamic bending test) or 5 mm ( ⁇ 5 mm dynamic bending test), and the fluorine-containing layer of the laminate
  • the test was conducted with the side facing out, and the dynamic flexibility was evaluated according to the following evaluation criteria.
  • the laminate for a display device after the dynamic bending test was performed with the fluorine-containing layer side facing out, and the display device laminate was attached to a tablet display on which the screen was displayed, and the visibility of the bent portion was confirmed under a fluorescent light. It was evaluated according to the evaluation criteria.
  • Examples 3-1 to 3-6, Comparative Example 3-1 A hard coat layer was formed on the substrate layer in the same manner as in Example 1-1. Next, a third inorganic compound layer, a second inorganic compound layer, and a first inorganic compound layer were formed in this order on the hard coat layer.
  • the third inorganic compound layer was formed by vacuum deposition using ZrO 2 as a constituent material at a deposition rate of 0.26 nm/sec.
  • the third inorganic compound layer had a thickness of 45 nm and a refractive index of 2.00.
  • the second inorganic compound layer was formed by vacuum deposition using Nb 2 O 5 as a constituent material at a film forming rate of 0.26 nm/sec.
  • the second inorganic compound layer had a thickness of 75 nm and a refractive index of 2.30.
  • the first inorganic compound layer was formed by a vacuum deposition method using SiO 2 as a constituent material at a film formation rate shown in Table 9.
  • the first inorganic compound layer had a thickness of 80 nm and a refractive index of 1.47.
  • a fluorine-containing layer having a thickness of 7 nm was formed on the first inorganic compound layer.
  • a laminate having a substrate layer, a hard coat layer, a third inorganic compound layer, a second inorganic compound layer, a first inorganic compound layer and a fluorine-containing layer in this order was obtained.
  • Example 3-7 Comparative Example 3-2
  • a laminate was obtained in the same manner as in Example 3-1, except that the following antistatic agent-containing resin composition for hard coat layer was used to form the hard coat layer.
  • composition of resin composition for antistatic agent-containing hard coat layer ⁇ Pentaerythritol acrylate (product name “A-9550”, manufactured by Shin-Nakamura Chemical Co., Ltd.): 87 parts by mass ⁇ Pentaerythritol acrylate (product name “A-TMM-3L”, manufactured by Shin-Nakamura Chemical Co., Ltd.): 13 parts by mass ⁇ Polymerization Initiator (1-hydroxycyclohexylphenyl ketone, product name “Omnirad 184", manufactured by IGM Resins B.V.): 4 parts by mass Silica particles (average primary particle diameter 12 nm, manufactured by Nissan Chemical Industries, Ltd.): 40 parts by mass ( 100% solid content conversion value) ⁇ Methyl isobutyl ketone: 190 parts by mass ⁇ Antistatic agent (product name “MT-2”, manufactured by Arakawa Chemical Industries, Ltd.): 3 parts by mass (converted to 100% solid content)
  • the relative film densities of the first inorganic compound layer and the second inorganic compound layer of the obtained laminate for display device were calculated as follows: "A. Laminate for display device I. First embodiment 1. First inorganic compound layer (3) Relative film density D1”. Further, the content ratio of fluorine atoms in the first inorganic compound layer is the content ratio of fluorine atoms described in "A. Laminate for display device II. Second embodiment 1. First inorganic compound layer (2) Content ratio of fluorine atoms" method. Table 9 shows the measurement results of the relative film density D1 and the fluorine atom content ratio of the first inorganic compound layer. The relative film density D2 of the second inorganic compound layer was 0.58.
  • the laminate was cut into a size of 100 mm ⁇ 100 mm to prepare a test piece.
  • the applied voltage was set to 1000 V according to JIS K6911: 1995, and the laminate was placed on the register table.
  • the surface opposite to the fluorine-containing layer side is brought into contact and fixed with cellophane tape (registered trademark) so that there are no folds or wrinkles, and the URS probe of the resistivity meter is brought into contact with the surface of the laminate on the fluorine-containing layer side.
  • the surface resistance value was measured by The surface resistance value was obtained by measuring the surface resistance value at 10 points at random on the surface of the laminate on the fluorine-containing layer side, and taking the arithmetic mean value of the measured surface resistance values at 10 points.
  • Examples 3-1 to 3-6 wear resistance and bending resistance confirmed to be excellent. It was confirmed that even when a hard coat layer material containing an antistatic agent was used, the abrasion resistance and bending resistance were excellent (Examples 3-7). On the other hand, Comparative Examples 3-1 and 3-2 have good dynamic flexibility and crack elongation, but have poor wear resistance because the content ratio of fluorine atoms in the first inorganic compound layer is high. was confirmed.
  • Example 4-1 to 4-3 Comparative Example 4-1
  • a hard coat layer was formed on the substrate layer in the same manner as in Example 1-1.
  • a coating film was formed by applying the resin composition for the dispersion layer onto the hard coat layer. Then, this coating film was dried and cured to form a dispersion layer having a thickness of 100 nm.
  • a first inorganic compound layer was formed on the dispersion layer.
  • the first inorganic compound layer was formed by a vacuum deposition method using the constituent materials shown in Table 10 at the film formation rate shown in Table 10.
  • Table 10 shows the thickness and refractive index of the first inorganic compound layer.
  • a fluorine-containing layer having a thickness of 7 nm was formed on the first inorganic compound layer in the same manner as in Example 1-1.
  • a laminate having a substrate layer, a hard coat layer, a high refractive index dispersion layer, a first inorganic compound layer, and a fluorine-containing layer in this order was obtained.
  • the relative film densities D4 of the first inorganic compound layer D1 and the high-refractive-index dispersion layer of the obtained laminate for display device were calculated as follows: "A. Laminate for display device I. First embodiment 1. First inorganic compound Layer (3) Relative film density D1” and “A. Laminate for display device I. First embodiment 6. Other configurations (5) Intervening layer (i) Relative film density” were measured.
  • Examples 4-1 to 4-3 in which the relative film density D4 of the high refractive index dispersion layer is 0.10 or more and 0.70 or less are superior to Comparative Example 4-1 in wear resistance and bending It was confirmed that the resistance is excellent.
  • a laminate for a display device having, in this order, a fluorine-containing layer containing fluorine atoms, a first inorganic compound layer, a second inorganic compound layer, and a substrate layer
  • the first inorganic compound layer has a first inorganic compound that is a low refractive index material, and has a relative film density D1 of 0.70 or more and 1.20 or less
  • the second inorganic compound layer has a second inorganic compound that is a high refractive index material, and has a relative film density D2 of 0.50 or more and less than 1.00
  • a laminate for a display device wherein the luminous reflectance of specularly reflected light when light is incident on the fluorine-containing layer side surface of the laminate for a display device at an incident angle of 5° is 2.0% or less.
  • the relative film density D1 of the first inorganic compound layer, the relative film density D2 of the second inorganic compound layer, and the relative film density D3 of the intervening layer satisfy the relationship D3 ⁇ D2 ⁇ D1, from [9] [11]
  • a laminate for a display device having, in this order, a fluorine-containing layer containing fluorine atoms, a first inorganic compound layer, a second inorganic compound layer, and a substrate layer
  • the first inorganic compound layer has a first inorganic compound that is a low refractive index material, and has a fluorine atom content of 6.5 atomic % or less
  • the second inorganic compound layer has a second inorganic compound that is a high refractive index material, and has a relative film density D2 of 0.50 or more and less than 1.00
  • a laminate for a display device wherein the luminous reflectance of specularly reflected light when light is incident on the fluorine-containing layer side surface of the laminate for a display device at an incident angle of 5° is 2.0% or less.
  • a laminate for a display device having, in this order, a fluorine-containing layer containing fluorine atoms, a first inorganic compound layer, and a substrate layer
  • the first inorganic compound layer has a first inorganic compound that is a low refractive index material, and has a relative film density D1 of 0.70 or more and 1.20 or less
  • a high refractive index dispersion layer in which inorganic compound particles having a high refractive index are dispersed in a binder resin,
  • the relative film density D4 of the high refractive index dispersion layer is 0.10 or more and 0.70 or less
  • a laminate for a display device wherein the luminous reflectance of specularly reflected light when light is incident on the fluorine-containing layer side surface of the laminate for a display device at an incident angle of 5° is 2.0% or less.
  • a display device comprising: the laminate for a display device according to any one of [1] to [33], which is arranged on the viewer side of the display panel.
  • SYMBOLS 1a, 1b, 1c Laminate for display devices 2... Fluorine-containing layer 3... First inorganic compound layer 4... Second inorganic compound layer 5... Base material layer 6... Third inorganic compound layer 7... Hard coat layer DESCRIPTION OF SYMBOLS 8... Adhesive layer for sticking 9... Intervening layer 10... High refractive index dispersion layer 20a, 20b, 20c... Flexible display device 21... Display panel

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  • Inorganic Chemistry (AREA)
  • Laminated Bodies (AREA)

Abstract

La présente divulgation concerne un corps multicouche pour dispositifs d'affichage, le corps multicouche comprenant séquentiellement une couche contenant du fluor, une première couche de composé inorganique, une seconde couche de composé inorganique et une couche de matériau de base dans cet ordre. Par rapport à ce corps multicouche pour dispositifs d'affichage, la première couche de composé inorganique contient un premier composé inorganique qui sert de matériau à faible indice de réfraction, tout en ayant une densité de film relative D1 de 0,70 à 1,20; la seconde couche de composé inorganique contient un second composé inorganique qui sert de matériau à indice de réfraction élevé, tout en ayant une densité de film relative D2 supérieure ou égale à 0,50 mais inférieure à 1,00; et si la lumière est incidente sur la surface côté couche contenant du fluor de ce corps multicouche pour des dispositifs d'affichage à un angle incident de 5°, la réflectance lumineuse de la lumière réfléchie de manière spéculaire est inférieure ou égale à 2,0 %.
PCT/JP2022/036159 2021-09-30 2022-09-28 Corps multicouche pour dispositifs d'affichage, et dispositif d'affichage WO2023054468A1 (fr)

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JP2005017544A (ja) * 2003-06-25 2005-01-20 Dainippon Printing Co Ltd 反射防止フィルム、および画像表示装置
JP2009139925A (ja) * 2007-11-16 2009-06-25 Epson Toyocom Corp 光学多層膜フィルタ、光学多層膜フィルタの製造方法および電子機器装置
JP2012522259A (ja) * 2009-03-27 2012-09-20 エシロール アテルナジオナール カンパニー ジェネラーレ デ オプティック 酸化スズに基づく導電膜を有する反射防止または反射コーティングを塗膜した光学物品、および製造方法
JP2012208448A (ja) * 2011-03-30 2012-10-25 Gunze Ltd 光反射防止シートとその製造方法およびその光反射防止シートを用いたタッチパネルおよびディスプレイ
WO2021111813A1 (fr) * 2019-12-03 2021-06-10 コニカミノルタ株式会社 Élément optique et son procédé de production
JP2021184032A (ja) * 2020-05-21 2021-12-02 デクセリアルズ株式会社 反射防止フィルム

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WO2018179757A1 (fr) 2017-03-27 2018-10-04 富士フイルム株式会社 Stratifié antireflet, et plaque polarisante et dispositif d'affichage d'image comprenant celui-ci

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Publication number Priority date Publication date Assignee Title
JP2005017544A (ja) * 2003-06-25 2005-01-20 Dainippon Printing Co Ltd 反射防止フィルム、および画像表示装置
JP2009139925A (ja) * 2007-11-16 2009-06-25 Epson Toyocom Corp 光学多層膜フィルタ、光学多層膜フィルタの製造方法および電子機器装置
JP2012522259A (ja) * 2009-03-27 2012-09-20 エシロール アテルナジオナール カンパニー ジェネラーレ デ オプティック 酸化スズに基づく導電膜を有する反射防止または反射コーティングを塗膜した光学物品、および製造方法
JP2012208448A (ja) * 2011-03-30 2012-10-25 Gunze Ltd 光反射防止シートとその製造方法およびその光反射防止シートを用いたタッチパネルおよびディスプレイ
WO2021111813A1 (fr) * 2019-12-03 2021-06-10 コニカミノルタ株式会社 Élément optique et son procédé de production
JP2021184032A (ja) * 2020-05-21 2021-12-02 デクセリアルズ株式会社 反射防止フィルム

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