Optical laminate, method for manufacturing optical laminate, optical member, optical device, method for manufacturing optical member, and method for manufacturing optical device

Abstract

To provide an optical laminate having high strength against tearing a void layer, production method of an optical laminate, an optical member, an optical device, a production method of an optical member, and a production method of an optical device.SOLUTION: An optical laminate 10a or 10b of the invention includes a void layer 12 and a hard layer 13 formed on the void layer 12. The void layer 12 has a void ratio of 30 vol.% or more. The hard layer 13 contains at least one selected from the group consisting of a metal, a metal oxide, silicon, a silicon oxide, and an organic-inorganic hybrid material and has a hardness higher than that of the void layer 12, the hardness measured by pushing an indenter into the hard layer 13 by 20 nm using a nanoindenter.SELECTED DRAWING: Figure 1

Description

[Technical Field]

[0001] The present invention relates to an optical laminate, a method for manufacturing an optical laminate, an optical member, an optical device, a method for manufacturing an optical member, and a method for manufacturing an optical device. [Background technology]

[0002] In optical devices, for example, an air layer with a low refractive index is used as a total reflection layer. Specifically, for example, in a liquid crystal device, optical film components (e.g., a light guide plate and a reflector) are stacked with an air layer between them. However, separating components with an air layer can cause problems such as component warping, especially when the components are large. Furthermore, the trend toward thinner devices demands integration of components. Therefore, components have been integrated with adhesives without an air layer (e.g., Patent Document 1). However, the absence of the air layer that performs the role of total reflection can lead to degradation of optical properties, such as light leakage. Therefore, the use of a low refractive index layer instead of an air layer has been proposed. For example, Patent Document 2 describes a structure in which a layer with a refractive index lower than that of the light guide plate is inserted between the light guide plate and the reflector. For example, a void layer having voids is used as the low refractive index layer to achieve a refractive index as low as possible that is close to that of air. [Prior art documents] [Patent documents]

[0003] [Patent Document 1] Japanese Patent Application Laid-Open No. 2012-156082 [Patent Document 2] Japanese Patent Application Publication No. 10-62626 Summary of the Invention [Problem to be solved by the invention]

[0004] In order to make the refractive index of the porous layer low, close to that of air, it is necessary to increase the porosity of the porous layer relative to the skeleton and reduce the apparent refractive index, but such an increase in porosity may reduce the mechanical strength of the porous layer.

[0005] For example, in order to form a sheet from a porous layer, the sheet containing the porous layer needs to have high web handleability, processability, etc. However, if the strength of the porous layer against peeling is low, the web handleability, processability, etc. of the sheet containing the porous layer may be reduced.

[0006] Therefore, an object of the present invention is to provide an optical laminate having high strength against peeling of the void layer, a method for manufacturing an optical laminate, an optical member, an optical device, a method for manufacturing an optical member, and a method for manufacturing an optical device. [Means for solving the problem]

[0007] In order to achieve the above object, the optical laminate of the present invention is a gap layer and a hard layer formed on the gap layer, The void layer has a porosity of 30% by volume or more, The hard layer contains at least one selected from the group consisting of metal, metal oxide, silicon, silicon oxide, and organic-inorganic hybrid material, and is characterized in that its hardness, measured by pressing an indenter 20 nm in the thickness direction using a nanoindenter, is greater than that of the void layer.

[0008] The method for producing an optical laminate of the present invention includes a hard layer formation step of forming the hard layer on at least one surface of the void layer, and is characterized in that in the hard layer formation step, the hard layer is formed by at least one method selected from the group consisting of vacuum deposition, sputtering, and chemical vapor deposition (CVD).

[0009] The optical member of the present invention is characterized by including the optical laminate of the present invention.

[0010] The optical device of the present invention is characterized by including the optical member of the present invention.

[0011] The method for manufacturing an optical element of the present invention is characterized by including an optical laminate manufacturing step of manufacturing the optical laminate of the present invention by the method for manufacturing an optical laminate of the present invention.

[0012] The method for manufacturing an optical device of the present invention is characterized by including an optical member manufacturing step of manufacturing the optical member of the present invention by the method for manufacturing an optical member of the present invention. [Effects of the Invention]

[0013] According to the present invention, it is possible to provide an optical laminate having high strength against peeling of the air gap layer, a method for manufacturing an optical laminate, an optical member, an optical device, a method for manufacturing an optical member, and a method for manufacturing an optical device. [Brief explanation of the drawings]

[0014] [Figure 1] Fig. 1(a) is a cross-sectional view showing an example of the configuration of the optical laminate of the present invention. Fig. 1(b) is a cross-sectional view showing another example of the configuration of the optical laminate of the present invention. Fig. 1(c) is a cross-sectional view showing an example of the configuration of the optical laminate not including a hard layer. [Figure 2] 2(a) to 2(d) are cross-sectional views showing an example of steps in the method for producing an optical layered body of the present invention. DETAILED DESCRIPTION OF THE INVENTION

[0015] Next, the present invention will be described in more detail with reference to examples, but the present invention is not limited to the following description in any way.

[0016] The optical layered body of the present invention may have a hardness of 0.04 GPa or more, as measured by pressing an indenter into the hard layer by 20 nm using a nanoindenter, for example.

[0017] In the optical laminate of the present invention, for example, the hard layer may contain at least one selected from the group consisting of silicon, aluminum, silicon dioxide, aluminum oxide, zinc tin composite oxide (ZTO), indium tin composite oxide (ITO), indium zinc composite oxide (IZO), gallium zinc composite oxide (GZO), and polysiloxane.

[0018] In the optical layered body of the present invention, for example, the hard layer may have a thickness of 5 nm or more.

[0019] In the optical layered body of the present invention, for example, the hard layer may be a layer formed by at least one method selected from the group consisting of vacuum deposition, sputtering, and chemical vapor deposition (CVD).

[0020] In the optical layered body of the present invention, for example, the porous layer may be a porous body in which microporous particles of a silicon compound are chemically bonded to each other.

[0021] The optical layered body of the present invention may further include, for example, an adhesive layer, and the adhesive layer may be provided on the surface of the hard layer opposite to the porous layer.

[0022] In the present invention, "on" or "on the surface" may refer to a state of being in direct contact with the surface or a state of being via another layer or the like.

[0023] In the present invention, the term "adhesive layer" refers to a layer formed of at least one of a pressure-sensitive adhesive and an adhesive. In addition, in the present invention, a pressure-sensitive adhesive and an adhesive may be collectively referred to as a "pressure-sensitive adhesive." Generally, a distinction is made between an agent having relatively weak adhesive or bonding strength (e.g., an agent that allows the adherend to be removably attached) and an agent having relatively strong adhesive or bonding strength (e.g., an agent that makes it impossible or extremely difficult to removably attach the adherend) and being called an "adhesive." In the present invention, there is no clear distinction between a pressure-sensitive adhesive and an adhesive. In the present invention, there is no clear distinction between "adhesive strength" and "adhesive strength."

[0024] In the present invention, there is no clear distinction between a "sheet" and a "film." Generally, a relatively thick material is called a "sheet" and a relatively thin material is called a "film," but in the present invention, there is no clear distinction between a "sheet" and a "film."

[0025] [1. Optical laminate, optical member, and optical device] As described above, the optical laminate of the present invention comprises a void layer and a hard layer formed on the void layer, wherein the void layer has a porosity of 30% by volume or more, the hard layer comprises at least one selected from the group consisting of metal, metal oxide, silicon, silicon oxide, and organic-inorganic hybrid material, and the hardness of the hard layer, measured by pressing an indenter 20 nm in the thickness direction using a nanoindenter, is greater than that of the void layer.

[0026] The cross-sectional view of Figure 1(a) shows an example of the configuration of an optical laminate of the present invention. As shown in the figure, this optical laminate 10a has a substrate 11 on which a voided layer 12 is formed, and a hard layer 13 is further formed on the voided layer 12. The voided layer 12 has a porosity of 30% by volume or more. The hard layer 13 contains at least one material selected from the group consisting of metal, metal oxide, silicon, silicon oxide, and organic-inorganic hybrid material.

[0027] 1(b) shows another example of the configuration of the optical laminate of the present invention. As shown in the figure, this optical laminate 10b is the same as the optical laminate 10a of FIG. 1(a) except that a tacky adhesive layer 14 is further provided on the surface of the hard layer 13 opposite to the void layer 12.

[0028] 1(c) shows an example of the configuration of an optical laminate 20 that does not include a hard layer. As shown in the figure, this optical laminate 20 is the same as the optical laminate 10b in FIG. 1(b) except that it does not include a hard layer 13 and that an adhesive layer 14 is provided on the void layer 12 in a state of direct contact with the void layer 12.

[0029] For example, in an optical laminate, if a pressure-sensitive adhesive layer is provided in direct contact with a void layer as shown in Fig. 1(c), the void layer may be damaged due to its low strength against peeling. In response to this, the present inventors have found that providing a hard layer on the void layer increases the strength against peeling of the void layer, and have arrived at the present invention.

[0030] As described above, the optical laminate of the present invention includes the void layer and a hard layer formed on the void layer. The optical laminate of the present invention may or may not include the void layer and layers other than the void layer. For example, the other layer may or may not include a substrate 11 as shown in FIGS. 1(a) and 1(b). For example, the other layer may or may not include a pressure-sensitive adhesive layer 14 as shown in FIG. 1(b). Furthermore, other layers may or may not be included between the substrate 11, the void layer 12, the hard layer 13, and the pressure-sensitive adhesive layer 14.

[0031] 1(a) and 1(b), the substrate 11 is not particularly limited and may be, for example, a substrate such as a film. Examples of suitable substrates include, but are not limited to, substrates made of thermoplastic resins, glass substrates, inorganic substrates such as silicon, plastics molded from thermosetting resins, semiconductor elements, and carbon fiber materials such as carbon nanotubes. Examples of the substrate include films and plates. Examples of thermoplastic resins include polyethylene terephthalate (PET), acrylic, cellulose acetate propionate (CAP), cycloolefin polymer (COP), triacetyl cellulose (TAC), polyethylene naphthalate (PEN), polyethylene (PE), and polypropylene (PP). The thickness of the substrate 11 is not particularly limited, and may be, for example, 10 μm or more, 20 μm or more, or 30 μm or more, and may be, for example, 1000 μm or less, 500 μm or less, 400 μm or less, 300 μm or less, 200 μm or less, or 100 μm or less, and may be, for example, 10 μm to 1000 μm, 10 μm to 500 μm, or 10 μm to 100 μm. From the viewpoint of a thin optical laminate, it is preferable that the thickness of the substrate 11 is not too large. On the other hand, from the viewpoint of the strength of the optical laminate, it is preferable that the thickness of the substrate 11 is not too small.

[0032] 1(a) and 1(b), the void layer 12 has a porosity of 30% by volume or more, as described above. The void layer in the optical laminate of the present invention (hereinafter, sometimes referred to as the "void layer of the present invention") will be described below using examples. However, the void layer of the present invention is not limited thereto.

[0033] The porous layer of the present invention may have a porosity of 35% by volume or more, for example. The porous layer of the present invention may have a peak pore size of 50 nm or less, for example. However, this is merely an example, and the porous layer of the present invention is not limited thereto.

[0034] The porosity may be, for example, 35% by volume or more, 38% by volume or more, or 40% by volume or more, or 90% by volume or less, 80% by volume or less, or 75% by volume or less. The porous layer of the present invention may be, for example, a highly porous layer having a porosity of 60% by volume or more.

[0035] The porosity can be measured, for example, by the following measurement method.

[0036] (Method for measuring void ratio) If the layer to be measured for porosity is a single layer containing only voids, the ratio (volume ratio) of the layer's constituent material to air can be calculated using standard methods (e.g., measuring weight and volume to calculate density), allowing the porosity (volume %) to be calculated. Furthermore, since there is a correlation between refractive index and porosity, the porosity can also be calculated from the refractive index value of the layer. Specifically, the porosity can be calculated using the Lorentz-Lorenz formula from the refractive index value measured with an ellipsometer, for example.

[0037] The porous layer of the present invention can be produced, for example, by chemically bonding pulverized gel (microporous particles) as described below. In this case, the pores in the porous layer can be conveniently divided into the following three types (1) to (3). (1) The voids in the raw gel itself (within the particles) (2) Possibility of voids in the gel pulverized material units (3) Voids between the crushed gel particles due to accumulation of the crushed gel particles

[0038] The voids (2) are voids formed during pulverization, separate from the voids (1) that can be formed within each block when each particle group produced by pulverizing the gel is considered as a single block, regardless of the size, dimensions, etc., of the pulverized gel (microporous particles). The voids (3) are voids that arise during pulverization (e.g., medialess pulverization) due to the uneven size, dimensions, etc., of the pulverized gel (microporous particles). The porous layer of the present invention has, for example, the voids (1) to (3) described above, and thereby has an appropriate porosity and peak pore diameter.

[0039] The peak pore diameter may be, for example, 5 nm or more, 10 nm or more, or 20 nm or more, or 50 nm or less, 40 nm or less, or 30 nm or less. If the peak pore diameter is too large in a porous layer when the porosity is high, light will be scattered and the layer will become opaque. In the present invention, the lower limit of the peak pore diameter of the porous layer is not particularly limited, but if the peak pore diameter is too small, it will be difficult to increase the porosity, so it is preferable that the peak pore diameter is not too small. In the present invention, the peak pore diameter can be measured, for example, by the following method.

[0040] (Method for measuring peak pore diameter) A pore size distribution / specific surface area measuring device (BELLSORP MINI, trade name of Microtrack Bell Co.) is used to calculate the peak pore size from the results of calculating the BJH plot and BET plot by nitrogen adsorption and the isothermal adsorption curve.

[0041] The thickness of the porous layer of the present invention is not particularly limited, and may be, for example, 100 nm or more, 200 nm or more, or 300 nm or more, or 10,000 nm or less, 5,000 nm or less, or 2,000 nm or less.

[0042] As described below, the porous layer of the present invention uses a pulverized porous gel, destroying the three-dimensional structure of the porous gel and forming a new three-dimensional structure different from the porous gel. Thus, the porous layer of the present invention is a layer having a new pore structure (new void structure) that cannot be obtained in a layer formed from the porous gel, thereby forming a nanoscale void layer with high porosity. Furthermore, when the porous layer of the present invention is a silicone porous body, the pulverized materials are chemically bonded together while adjusting the number of siloxane bond functional groups in the silicon compound gel. Here, "silicone porous body" refers to a polymeric porous body containing siloxane bonds, including, for example, a porous body containing silsesquioxane as a structural unit. Furthermore, after a new three-dimensional structure is formed as a precursor of the porous layer, the void layer is chemically bonded (e.g., crosslinked) in a bonding process. Therefore, when the porous layer of the present invention is a functional porous body, the void layer has a voided structure but maintains sufficient strength and flexibility. Therefore, according to the present invention, a porous layer can be easily and simply applied to various objects.

[0043] The porous layer of the present invention contains, for example, pulverized porous gel, and the pulverized materials are chemically bonded together, as described below. In the porous layer of the present invention, the form of chemical bonding (chemical bonding) between the pulverized materials is not particularly limited, and specific examples of the chemical bonding include cross-linking. The method for chemically bonding the pulverized materials together is, for example, as described in detail in the method for manufacturing the porous layer described above.

[0044] The crosslinked bond is, for example, a siloxane bond. Examples of siloxane bonds include the T2 bond, T3 bond, and T4 bond shown below. When the silicone porous body of the present invention has siloxane bonds, it may have, for example, any one type of bond, any two types of bonds, or all three types of bonds. The higher the ratio of T2 and T3 among the siloxane bonds, the greater the flexibility and the gel's inherent properties can be expected, but the film strength will be weaker. On the other hand, if the ratio of T4 among the siloxane bonds is high, the film strength will be easily achieved, but the void size will be small and the flexibility will be weaker. For this reason, it is preferable to change the ratios of T2, T3, and T4 depending on the application, for example.

[0045] [ka]

[0046] When the porous layer of the present invention has the siloxane bond, the ratio of T2, T3 and T4, when expressed relatively with T2 set to "1", is, for example, T2:T3:T4=1:[1-100]:[0-50], 1:[1-80]:[1-40], 1:[5-60]:[1-30].

[0047] In addition, in the porous layer of the present invention, the silicon atoms contained therein are preferably siloxane-bonded. Specifically, the proportion of unbonded silicon atoms (i.e., residual silanols) among all silicon atoms contained in the silicone porous body is, for example, less than 50%, 30% or less, or 15% or less.

[0048] The porous layer of the present invention has, for example, a pore structure. In the present invention, the pore size of the pores refers to the diameter of the major axis of the pores (pores) out of the diameter of the major axis and the diameter of the minor axis. The pore size is, for example, 5 nm to 50 nm. The pore size has a lower limit of, for example, 5 nm or more, 10 nm or more, or 20 nm or more, and an upper limit of, for example, 50 nm or less, 40 nm or less, or 30 nm or less, and the range is, for example, 5 nm to 50 nm, or 10 nm to 40 nm. The preferred pore size is determined depending on the application of the pore structure, and therefore, it is necessary to adjust the pore size to a desired size depending on, for example, the purpose. The pore size can be evaluated, for example, by the following method.

[0049] (Cross-sectional SEM observation of void layer) In the present invention, the morphology of the void layer can be observed and analyzed using a scanning electron microscope (SEM). Specifically, for example, the void layer is subjected to FIB processing (acceleration voltage: 30 kV) under cooling, and a cross-sectional sample obtained is subjected to FIB-SEM (manufactured by FEI: product name Helios NanoLab600, acceleration voltage: 1 kV) to obtain a cross-sectional electron image at a magnification of 100,000 times.

[0050] (Evaluation of void size) In the present invention, the pore size can be quantified by the BET test method. Specifically, 0.1 g of a sample (the porous layer of the present invention) is placed in the capillary of a pore distribution / specific surface area analyzer (BELLSORP MINI, a product name of Microtrack Bell), and then dried under reduced pressure at room temperature for 24 hours to remove gas from the pore structure. Nitrogen gas is then adsorbed onto the sample, and a BET plot, a BJH plot, and an adsorption isotherm are plotted to determine the pore distribution. This allows the pore size to be evaluated.

[0051] The void layer of the present invention may have, for example, a pore structure (porous structure) as described above, and may be, for example, an open-cell structure in which the pore structure is continuous. The open-cell structure means, for example, that the pore structure in the void layer is connected three-dimensionally, and can also be described as a state in which the internal voids of the pore structure are continuous. When a porous material has an open-cell structure, it is possible to increase the porosity in the bulk, but an open-cell structure cannot be formed when closed-cell particles such as hollow silica are used. In contrast, the void layer of the present invention has a three-dimensional dendritic structure in which the sol particles (pulverized porous gel forming the sol) have a three-dimensional dendritic structure, and therefore, the dendritic particles can easily form an open-cell structure in a coating film (a coating film of a sol containing the pulverized porous gel). Furthermore, the void layer of the present invention preferably forms a monolithic structure in which the open-cell structure has a plurality of pore distributions. The monolithic structure refers to, for example, a structure in which nano-sized fine voids exist and a hierarchical structure in which the nano-voids exist as an open-cell structure. When forming the monolithic structure, for example, it is possible to achieve both membrane strength with fine pores and high porosity with coarse open-cell pores. To form such a monolithic structure, for example, it is important to first control the pore distribution of the pore structure to be generated in the porous gel prior to pulverization into the pulverized material. Furthermore, for example, when pulverizing the porous gel, the particle size distribution of the pulverized material can be controlled to a desired size, thereby forming the monolithic structure.

[0052] In the air-voided layer of the present invention, the haze indicating transparency is not particularly limited, and its lower limit is, for example, 0.1% or more, 0.2% or more, or 0.3% or more, and its upper limit is, for example, 10% or less, 5% or less, or 3% or less, and its range is, for example, 0.1 to 10%, 0.2 to 5%, or 0.3 to 3%.

[0053] The haze can be measured, for example, by the following method.

[0054] (Hayes's review) The porous layer (porous layer of the present invention) is cut to a size of 50 mm x 50 mm, and is set in a haze meter (HM-150 manufactured by Murakami Color Research Laboratory Co., Ltd.) to measure the haze. The haze value is calculated using the following formula. Haze (%) = [Diffuse transmittance (%) / Total light transmittance (%)] x 100 (%)

[0055] The refractive index of a medium is generally defined as the ratio of the propagation velocity of a wavefront of light in a vacuum to the propagation velocity within the medium. The refractive index of the air-gap layer of the present invention is not particularly limited, and its upper limit is, for example, 1.3 or less, less than 1.3, 1.25 or less, 1.2 or less, or 1.15 or less, and its lower limit is, for example, 1.05 or more, 1.06 or more, or 1.07 or more, and its range is, for example, 1.05 or more to 1.3 or less, 1.05 or more to 1.3 or less, 1.05 or more to 1.25 or less, 1.06 or more to 1.25 or less, or 1.07 or more to 1.15 or less.

[0056] In the present invention, the refractive index is measured at a wavelength of 550 nm unless otherwise specified. The method for measuring the refractive index is not particularly limited, and can be measured, for example, by the following method.

[0057] (Refractive index evaluation) After forming a void layer (void layer of the present invention) on an acrylic film, it was cut to a size of 50 mm x 50 mm and attached to the surface of a glass plate (thickness: 3 mm) using an adhesive layer. The center of the back surface of the glass plate (diameter: approximately 20 mm) was painted with black ink to prepare a sample that was not reflective on the back surface of the glass plate. The sample was placed in an ellipsometer (JA Woollam Japan: VASE) and the refractive index was measured at a wavelength of 550 nm and an incident angle of 50 to 80 degrees, and the average value was taken as the refractive index.

[0058] The thickness of the porous layer of the present invention is not particularly limited, and the lower limit is, for example, 0.05 μm or more, 0.1 μm or more, and the upper limit is, for example, 1000 μm or less, 100 μm or less, and the range is, for example, 0.05 to 1000 μm, 0.1 to 100 μm.

[0059] The form of the void layer of the present invention is not particularly limited, and for example, it may be in the form of a film or a block shape or the like.

[0060] In FIGS. 1(a) and 1(b), the hard layer 13 contains at least one selected from the group consisting of a metal, a metal oxide, silicon, a silicon oxide, and an organic-inorganic hybrid material. Hereinafter, the hard layer used in the optical laminate of the present invention (hereinafter sometimes referred to as "the hard layer of the present invention") will be described with examples.

[0061] In the hard layer of the present invention, the metal is not particularly limited, and examples thereof include aluminum, zinc, tin, indium, gallium, lead, and the like. The metal oxide is not particularly limited, and examples thereof include, as described above, aluminum oxide (for example, Al2O3), zinc tin composite oxide (ZTO), indium tin composite oxide (ITO), indium zinc composite oxide (IZO), gallium zinc composite oxide (GZO), and the like. In the present invention, the silicon oxide is a compound represented by, for example, SiOx (0 < x ≦ 2). The silicon oxide is not particularly limited, and examples thereof include silicon dioxide (SiO2). The organic-inorganic hybrid material is not particularly limited, and examples thereof include polysiloxane, silsesquioxane, and the like. Here, in the present invention, the "organic-inorganic hybrid material" means a material in which both an organic component and an inorganic component are present in the same molecule.

[0062] The hard layer of the present invention may or may not contain other components other than at least one component selected from the group consisting of a metal, a metal oxide, silicon, a silicon oxide, and an organic-inorganic hybrid material. When the hard layer of the present invention contains the other components, the content thereof is not particularly limited, and for example, it may be 10% by mass or less, 5% by mass or less, or 1% by mass or less, and the lower limit value is not particularly limited, and for example, it is a value exceeding 0% by mass.

[0063] The method for forming the hard layer of the present invention is not particularly limited, but a so-called dry process (a formation method without using a solvent) is preferred. Specifically, for example, as described above, the hard layer may be formed by at least one method selected from the group consisting of vacuum deposition, sputtering, and chemical vapor deposition (CVD). The specific method for performing vacuum deposition, sputtering, and chemical vapor deposition (CVD) is also not particularly limited, and may be, for example, similar to or similar to a general method.

[0064] As described above, the hard layer of the present invention has a higher hardness than the void layer of the present invention, as measured by pressing an indenter 20 nm into the hard layer using a nanoindenter. In the present invention, the hardness of the hard layer is measured by pressing the indenter directly against the surface or side of the hard layer formed on the void layer. The method for forming a hard layer with such hardness is not particularly limited. For example, a hard layer having a higher hardness than the void layer of the present invention can be formed by forming the hard layer using at least one material selected from the group consisting of metal, metal oxide, silicon, silicon oxide, and organic-inorganic hybrid material by at least one method selected from the group consisting of vacuum deposition, sputtering, and chemical vapor deposition (CVD). The thickness of the hard layer of the present invention is not particularly limited, and may be, for example, 3 nm or more, 4 nm or more, 5 nm or more, 10 nm or more, or 40 nm or more, or, for example, 300 nm or less, 250 nm or less, 200 nm or less, 150 nm or less, or 100 nm or less, for example, 3 to 300 nm, 4 to 200 nm, or 5 to 100 nm. From the viewpoint of a thin optical laminate, it is preferable that the thickness of the hard layer of the present invention is not too large. On the other hand, from the viewpoint of improving the strength of the void layer, it is preferable that the thickness of the hard layer of the present invention is not too small.

[0065] As described above, the hardness of the optical laminate of the present invention may be 0.04 GPa or more when measured using a nanoindenter by pressing an indenter 20 nm into the hard layer of the optical laminate. When no other layer is present on the hard layer, the hardness can be measured, for example, by pressing the indenter directly against the surface of the hard layer. When another layer (e.g., the aforementioned adhesive layer) is present on the hard layer, the hardness can be measured, for example, by cutting the optical laminate in the thickness direction using a focused ion beam (FIB) or the like and then pressing the indenter against the hard layer exposed on the side surface of the optical laminate. The hardness may be, for example, 0.04 GPa or more, 0.06 GPa or more, or 0.08 GPa or more. The upper limit of the hardness is not particularly limited, but may be, for example, 70 GPa or less.

[0066] In FIG. 1(b), the adhesive layer 14 is not particularly limited, and may be, for example, an adhesive layer formed from an adhesive (adhesive composition). In the optical laminate of the present invention, the thickness of the adhesive layer is not particularly limited, and may be, for example, 3 μm or more, 5 μm or more, or 10 μm or more, and may be, for example, 100 μm or less, 75 μm or less, or 50 μm or less, and may be, for example, 3 to 100 μm, 3 to 50 μm, or 5 to 25 μm. The adhesive is not particularly limited, and examples thereof include (meth)acrylic polymers. These may be dissolved or dispersed in a solvent to form a solution or dispersion, which may be used as the adhesive (adhesive composition). Examples of the solvent include ethyl acetate, and these may be used alone or in combination. The concentration of the solute or dispersoid (e.g., the acrylic polymer) in the solution or dispersion may be, for example, 10% by mass or more, or 15% by mass or more, and may be, for example, 60% by mass or less, 50% by mass or less, 40% by mass or less, or 25% by mass or less. In the present invention, the term "(meth)acrylic polymer" refers to a polymer or copolymer of at least one monomer selected from the group consisting of (meth)acrylic acid, (meth)acrylic acid esters, and (meth)acrylamide. In the present invention, the term "(meth)acrylic acid" refers to "at least one of acrylic acid and methacrylic acid," and the term "(meth)acrylic acid ester" refers to "at least one of acrylic acid esters and methacrylic acid esters." Examples of the (meth)acrylic acid esters include linear or branched alkyl esters of (meth)acrylic acid. In the linear or branched alkyl ester of (meth)acrylic acid, the number of carbon atoms in the alkyl group may be, for example, 1 or more, 2 or more, 3 or more, or 4 or more, and may be, for example, 18 or less, 16 or less, 14 or less, 12 or less, 10 or less, or 8 or less. The alkyl group may be, for example, unsubstituted or substituted with one or more substituents. Examples of the substituent include a hydroxyl group, and when there are multiple substituents, the substituents may be the same or different. Specific examples of the (meth)acrylic acid ester include 2-ethylhexyl acrylate, 2-hydroxyethyl acrylate, and 4-hydroxybutyl acrylate.The adhesive may be used alone or in combination of two or more types.

[0067] As described above, the optical layered body of the present invention may or may not include a pressure-sensitive adhesive layer.

[0068] The optical laminate of the present invention may have, for example, a light transmittance of 80% or more throughout the optical laminate. Furthermore, for example, the haze of the optical laminate may be 3% or less. Note that, for example, in the case of the optical laminate 10a of FIG. 1(a), the "entire optical laminate" refers to the entire optical laminate including the substrate 11, the void layer 12, and the hard layer 13. In the case of the optical laminate 10b of FIG. 1(b), the "entire optical laminate" refers to the entire optical laminate including the substrate 11, the void layer 12, the hard layer 13, and the adhesive layer 14. The light transmittance may be, for example, 82% or more, 84% or more, 86% or more, or 88% or more. The upper limit is not particularly limited, but is ideally 100%, and may be, for example, 95% or less, 92% or less, 91% or less, or 90% or less. The haze of the optical laminate may be measured, for example, by the same method as used to measure the haze of the void layer described above. The light transmittance is the transmittance of light at a wavelength of 550 nm and can be measured, for example, by the following measurement method.

[0069] (Method for measuring light transmittance) The laminate was used as a sample to be measured using a spectrophotometer U-4100 (trade name of Hitachi, Ltd.). The total light transmittance (light transmittance) of the sample was measured, assuming that the total light transmittance of air was 100%. The total light transmittance (light transmittance) value was measured at a wavelength of 550 nm.

[0070] In the optical laminate of the present invention, the adhesive strength or adhesion of the adhesive layer is not particularly limited, and may be, for example, 0.7 N / 25 mm or more, 0.8 N / 25 mm or more, 1.0 N / 25 mm or more, or 1.5 N / 25 mm or more, or 50 N / 25 mm or less, 30 N / 25 mm or less, 10 N / 25 mm or less, 5 N / 25 mm or less, or 3 N / 25 mm or less. From the viewpoint of the risk of peeling during handling when the optical laminate of the present invention is bonded to another layer, it is preferable that the adhesive strength or adhesion of the adhesive layer is not too low. Furthermore, from the viewpoint of rework when re-bonding, it is preferable that the adhesive strength or adhesion of the adhesive layer is not too high. The adhesive strength or adhesion of the adhesive layer can be measured, for example, as follows.

[0071] (Method for measuring adhesive strength or adhesion) The laminate film of the present invention (a resin film substrate on which the optical laminate of the present invention is formed) is sampled into a 50 mm x 140 mm strip, and the sample is fixed to a stainless steel plate with double-sided tape. An acrylic adhesive layer (20 μm thick) is attached to a PET film (T100: manufactured by Mitsubishi Plastics Film Co., Ltd.), and a piece of adhesive tape cut to 25 mm x 100 mm is attached to the side of the laminate film of the present invention opposite the resin film, thereby laminating it with the PET film. The sample is then chucked in an autograph tensile tester (Shimadzu Corporation: AG-Xplus) with a chuck distance of 100 mm, and a tensile test is performed at a tensile speed of 0.3 m / min. The average test force after a 50 mm peel test is taken as the adhesive peel strength, i.e., adhesive strength. Adhesion strength can also be measured using the same measurement method. In the present invention, there is no clear distinction between "adhesive strength" and "adhesive strength."

[0072] The use of the optical laminate of the present invention is not particularly limited, but it can be used, for example, in the optical member of the present invention and the optical device of the present invention.

[0073] The optical member of the present invention is not particularly limited, and may be, for example, an optical film containing the optical laminate of the present invention.

[0074] The optical apparatus (optical device) of the present invention is not particularly limited, and may be, for example, an image display apparatus or a lighting apparatus. Examples of image display apparatuses include liquid crystal displays, organic EL (Electro Luminescence) displays, and micro LED (Light Emitting Diode) displays. Examples of lighting apparatuses include organic EL lighting.

[0075] The uses and methods of using the optical element and the optical device of the present invention are not particularly limited, but may be the same as those of a general optical element or a general optical device (e.g., the image display device or lighting device).

[0076] [2. Methods for manufacturing optical laminates, methods for manufacturing optical members, and methods for manufacturing optical devices] The method for producing the optical layered body of the present invention is not particularly limited, but it can be produced, for example, as follows.

[0077] 2(a) to 2(d) are cross-sectional views showing an example of steps in the method for producing an optical laminate of the present invention. First, as shown in FIG. 2(a), a substrate 11 is prepared. The substrate 11 is not particularly limited, but may be, for example, as described above.

[0078] Next, as shown in FIG. 2(b), a void layer 12 is formed on one surface of the substrate 11 (void layer forming step). The method for forming (manufacturing) the void layer 12 is not particularly limited, but the void layer 12 can be manufactured by, for example, the methods described in International Publication Nos. 2019 / 065999 and 2019 / 065803. The disclosures of these publications are incorporated herein by reference. More specifically, the method for forming the void layer 12 may involve, for example, applying a coating liquid for forming the void layer to one surface of the substrate 11, drying the coating liquid, and, if necessary, curing or crosslinking the coating liquid by light irradiation or chemical treatment (e.g., crosslinking treatment). The coating liquid may be, for example, a sol particle liquid of a pulverized gel-like compound. The gel-like compound may be, for example, a silicon oxide (e.g., silica gel). The method for producing the sol particle liquid of the pulverized gel compound is not particularly limited, and can be produced, for example, by the method described in WO 2019 / 065999 or WO 2019 / 065803. The sol particle liquid can also be produced, for example, by the method described in "Reference Example 1" of the Examples of the present application, which will be described later. The coating method for the coating liquid is not particularly limited, and a general coating method can be used. Examples of the coating method include a slot die method, a reverse gravure coating method, a microgravure method (microgravure coating method), a dip method (dip coating method), a spin coating method, a brush coating method, a roll coating method, a flexographic printing method, a wire bar coating method, a spray coating method, an extrusion coating method, a curtain coating method, and a reverse coating method. Among these, from the viewpoints of productivity, the smoothness of the coating film, and the like, the extrusion coating method, the curtain coating method, the roll coating method, the microgravure coating method, and the like are preferred.

[0079] Next, as shown in FIG. 2(c), a hard layer 13 is formed on the surface of the void layer 12 opposite the substrate 11 (hard layer formation step). In this hard layer formation step, the hard layer 13 is formed by at least one method selected from the group consisting of vacuum deposition, sputtering, and chemical vapor deposition (CVD). This method is not particularly limited, and may be similar to or equivalent to general vacuum deposition, sputtering, and chemical vapor deposition (CVD), as described above. The material, thickness, etc. of the hard layer 13 are, for example, as described above. In this way, as shown in FIG. 2(c), an optical laminate 10a can be produced in which the void layer 12 is formed on the substrate 11 and the hard layer 13 is further formed on the void layer 12. Note that the optical laminate 10a in FIG. 2(c) is the same as the optical laminate 10a in FIG. 1(a).

[0080] Furthermore, as shown in FIG. 2(d), an adhesive layer 14 may be further formed on the surface of the hard layer 13 in the optical laminate 10a in FIG. 2(c) opposite to the void layer 12 to form an optical laminate 10b. The method for forming (manufacturing) the adhesive layer 14 is not particularly limited, but may be the same as or equivalent to a general method for forming an adhesive layer. Specifically, for example, an adhesive or a adhesive may be applied to the surface of the hard layer 13, and then heated, if necessary. The adhesive or the adhesive is not particularly limited, but may be, for example, as described above.

[0081] In addition, the method for manufacturing the optical laminate 10a of FIG. 1(a) or the optical laminate 10b of FIG. 1(b) may involve, for example, continuously carrying out the above-mentioned steps while continuously feeding out the long film-like substrate 11.

[0082] The manufacturing method of the optical member of the present invention and the manufacturing method of the optical device of the present invention are not particularly limited. For example, the optical member of the present invention can be manufactured by the same manufacturing method as that of a general optical member, except that the optical laminate of the present invention is manufactured by any manufacturing method (for example, the manufacturing method described above). Furthermore, the optical device of the present invention can be manufactured by the same manufacturing method as that of a general optical device, except that the optical laminate of the present invention is manufactured by any manufacturing method (for example, the manufacturing method described above). [Example]

[0083] Next, examples of the present invention will be described, but the present invention is not limited to the following examples.

[0084] In the following Reference Examples, Examples, and Comparative Examples, the number of parts (relative amount used) of each substance is in parts by mass (parts by weight) unless otherwise specified.

[0085] [Reference example 1] A coating liquid for forming a porous layer (low refractive index layer) was prepared as follows.

[0086] (1) Gelation of silicon compounds Mixture A was prepared by dissolving 0.95 g of methyltrimethoxysilane (MTMS), a precursor of a silicon compound, in 2.2 g of dimethyl sulfoxide (DMSO). 0.5 g of a 0.01 mol / L aqueous solution of oxalic acid was added to this mixture A, and the mixture was stirred at room temperature for 30 minutes to hydrolyze the MTMS, producing mixture B containing tris(hydroxy)methylsilane.

[0087] To 5.5 g of DMSO, 0.38 g of 28 wt % aqueous ammonia and 0.2 g of pure water were added, and then mixed solution B was further added and stirred at room temperature for 15 minutes to gel tris(hydroxy)methylsilane, thereby obtaining mixed solution C containing a gel-like silicon compound.

[0088] (2) Aging treatment The mixed solution C containing the gel-like silicon compound prepared in the above "(1) Gelation of silicon compound" was incubated as is at 40°C for 20 hours for aging treatment.

[0089] (3) Crushing The gel-like silicon compound in the mixed solution C, which had been aged in the "(2) Aging Treatment" section, was crushed using a spatula into granules of several millimeters to several centimeters in size. Next, 40 g of isopropyl alcohol (IPA) was added to the mixed solution C, and after light stirring, the mixture was left to stand at room temperature for 6 hours, and the solvent and catalyst in the gel were decanted. The same decantation process was repeated three times to replace the solvent, yielding mixed solution D. The gel-like silicon compound in the mixed solution D was then crushed (high-pressure media-less crushing). The crushing process (high-pressure media-less crushing) was carried out using a homogenizer (manufactured by SMT Corporation, trade name "UH-50"), with 1.85 g of the gel-like compound in the mixed solution D and 1.15 g of IPA weighed into a 5 cc screw bottle, and crushed for 2 minutes at 50 W and 20 kHz.

[0090] By this grinding process, the gel-like silicon compound in the mixed solution D was ground, and the mixed solution D was converted into a sol solution of the ground material, mixed solution D'. The volume average particle size, which indicates the particle size variation of the ground material contained in this mixed solution D', was confirmed to be 0.50 to 0.70 using a dynamic light scattering Nanotrac particle size analyzer (manufactured by Nikkiso Co., Ltd., UPA-EX150 type) and was found to be 0.50 to 0.70. Furthermore, 0.062 g of a 1.5 wt% MEK (methyl ethyl ketone) solution of a photobase generator (Wako Pure Chemical Industries, Ltd.: product name WPBG266) and 0.036 g of a 5% MEK solution of bis(trimethoxysilyl)ethane were added to 0.75 g of this sol solution (mixed solution D') in a ratio of 0.062 g and 0.036 g, respectively, to obtain the target coating solution for forming a porous layer.

[0091] [Reference example 2] A laminate of an acrylic pressure-sensitive adhesive layer and a PET film was prepared as follows. First, a four-necked flask equipped with a stirring blade, a thermometer, a nitrogen gas inlet tube, and a condenser was charged with 90.7 parts of butyl acrylate, 6 parts of N-acryloylmorpholine, 3 parts of acrylic acid, 0.3 parts of 2-hydroxybutyl acrylate, and 0.1 parts by weight of 2,2'-azobisisobutyronitrile as a polymerization initiator, along with 100 g of ethyl acetate. Nitrogen gas was introduced while gently stirring to replace the atmosphere. The liquid temperature in the four-necked flask was then maintained at around 55°C, allowing the polymerization reaction to proceed for 8 hours, yielding an acrylic polymer solution. An acrylic adhesive solution was prepared by blending 0.2 parts of an isocyanate crosslinker (trade name "Coronate L" manufactured by Nippon Polyurethane Industry Co., Ltd., an adduct of trimethylolpropane and tolylene diisocyanate), 0.3 parts of benzoyl peroxide (Niper BMT manufactured by NOF Corporation), and 0.2 parts of γ-glycidoxypropyl methoxysilane (KBM-403 manufactured by Shin-Etsu Chemical Co., Ltd.) per 100 parts of the solids content of the resulting acrylic polymer solution. The acrylic adhesive solution was then applied to one side of a silicone-treated polyethylene terephthalate (PET) film (manufactured by Mitsubishi Chemical Polyester Film Corporation, thickness: 38 μm) so that the adhesive layer would have a predetermined thickness after drying, and the coating was dried at 150°C for 3 minutes to produce a laminate of the adhesive layer and PET film.

[0092] [Example 1] The void layer-forming coating liquid prepared in Reference Example 1 was applied to a 30 μm-thick acrylic film (substrate) and then dried by heating at 100° C. for 2 minutes to form a void layer. The formed void layer was an ultra-low refractive index layer with a refractive index of 1.18. The porosity was 60% by volume. A 40 nm-thick SiO layer was then formed on the formed void layer by sputtering to obtain the desired optical laminate of the present invention. The SiO layer corresponds to the "hard layer" in the optical laminate of the present invention. The sputtering method was performed using a known sputtering device. The same applies to the sputtering method in each of the following examples. In this example, each of the following examples, and each of the comparative examples, the refractive index of the void layer was measured by the above-mentioned measurement method.

[0093] [Example 2] The optical laminate of this example was obtained in the same manner as in Example 1, except that a 40 nm thick Si layer was formed by sputtering as the hard layer instead of the 40 nm thick SiO2 layer.

[0094] [Example 3] The intended optical laminate of the present invention was produced by the same production method as in Example 1, except that the thickness of the SiO2 layer (hard layer) was changed from 40 nm to 5 nm.

[0095] [Example 4] The optical laminate of this example was obtained in the same manner as in Example 1, except that a 5 nm thick Si layer was formed by sputtering as the hard layer instead of the 40 nm thick SiO2 layer.

[0096] [Example 5] The optical laminate of this example was obtained in the same manner as in Example 1, except that a ZTO layer having a thickness of 50 nm was formed by sputtering as the hard layer instead of the SiO2 layer having a thickness of 40 nm.

[0097] [Example 6] The optical laminate of this example was obtained in the same manner as in Example 1, except that an 8 nm thick polysiloxane layer was formed as the hard layer instead of the 40 nm thick SiO layer. In this example, the polysiloxane layer was formed by vapor deposition using a solution prepared by dissolving octadecyltrichlorosilane (manufactured by Tokyo Chemical Industry Co., Ltd.) in a fluorine-based solvent (manufactured by 3M Company, trade name "Novec7100").

[0098] [Comparative Example 1] Except for not forming the hard layer (40 nm thick SiO layer), the optical laminate of this comparative example was produced in the same manner as in Example 1. That is, the optical laminate of this comparative example was an optical laminate in which a void layer was formed on a substrate, and nothing was formed on the void layer.

[0099] Comparative Example 2 The optical laminate of this comparative example was produced by directly attaching the laminate (adhesive layer thickness 10 μm) produced in Reference Example 2 onto the void layer of the optical laminate produced in Comparative Example 1 without forming a hard layer, and then peeling the PET film from the adhesive layer.

[0100] The indentation hardness and tensile strength of the optical laminates of each example and comparative example produced as described above were measured. The tensile strength corresponds to the strength against peeling of the porous layer. The indentation hardness and tensile strength were measured by the following test method (measurement method). The test results (measurement results) are summarized in Table 1 below.

[0101] [Indentation hardness test method] <Measurement method> The measurement was carried out using a nanoindenter "TI950 Triboindenter (product name)" manufactured by Hysitron Inc. The specific measurement method is as follows. First, the optical laminate of each of the Examples or Comparative Examples, which is a measurement sample, was fixed to a sample table with the substrate (acrylic film) side facing downward. Next, the indentation hardness (HIT (N / mm 2 )) was measured under the following conditions by pressing a triangular pyramidal diamond indenter (Berkovich indenter) with an inter-edge angle of 142° into the upper surface of the uppermost layer of the measurement sample (the hard layer in each of the above examples, the porous layer in Comparative Example 1, and the adhesive layer in Comparative Example 2). The measurement data was processed using dedicated analysis software (version 9.4.0.1) for Bruker's "TI950 Triboindenter (trade name)." Measurement mode: Single indentation test Hold time when reaching maximum displacement: 0 seconds Push-pull depth speed: 5nm / sec Indentation depth: 20 nm Measurement environment: 24°C ± 1°C (laboratory temperature set at 24°C), relative humidity 35% ± 10%

[0102] [Tensile strength test (peel test) method] <Measurement configuration> A laminate of the pressure-sensitive adhesive layer and PET film (adhesive layer thickness: 10 μm) prepared in Reference Example 2 was attached to the upper surface of the uppermost layer (hard layer in each of the Examples, and void layer in Comparative Example 1) of the optical laminate of each of the Examples or Comparative Example 1, which served as a measurement sample. The PET film was then peeled from the adhesive layer, and a 38 μm thick PET film was attached thereto. Since the uppermost layer of the optical laminate of Comparative Example 2, which served as a measurement sample, was the adhesive layer, the adhesive film was directly attached thereto. Furthermore, the laminate prepared in Reference Example 2 (adhesive layer thickness: 15 μm) was attached to the lower surface of the substrate of each of the measurement samples. The PET film was then peeled from the adhesive layer, and a 2 mm thick alkali glass was attached to the adhesive layer. A roller weighing 2 kg was then moved back and forth once on the upper surface of the adhesive film, thereby pressing the adhesive film and the alkali glass film against the measurement sample. The width of each measurement sample was 25 mm. <Measurement method> The alkali glass was chucked, the kick was set so that the peel angle was 180°, and the kick was pulled for 8 seconds at a pulling speed of 300 mm / min. As a result, measurement samples (optical laminates) with a tensile strength of 4.0 N / 25 mm or more were evaluated as ○, and measurement samples (optical laminates) with a tensile strength of less than 4.0 N / 25 mm were evaluated as ×.

[0103] [Table 1]

[0104] As shown in Table 1, in each example in which a hard layer was laminated on a porous layer, the porous layer was not peeled off in the tensile test (peel test), confirming that the strength against peeling of the porous layer was high. In contrast, in each comparative example in which a hard layer was not laminated on a porous layer, the porous layer was peeled off in the tensile test (peel test), confirming that the strength against peeling of the porous layer was low. [Industrial Applicability]

[0105] As described above, the present invention can provide an optical laminate having high strength against peeling of the void layer, a method for manufacturing an optical laminate, an optical member, an optical device, a method for manufacturing an optical member, and a method for manufacturing an optical device. The applications of the present invention are not particularly limited. For example, the optical device of the present invention is not particularly limited, and examples thereof include image display devices and lighting devices. Examples of the image display devices include liquid crystal displays, organic EL displays, and micro LED displays. Examples of the lighting devices include organic EL lighting. Furthermore, the applications of the optical laminate of the present invention are not limited to the optical members and optical devices of the present invention, and are arbitrary, and the optical laminate can be used for a wide range of applications. [Explanation of symbols]

[0106] 10a, 10b, 20 Optical laminate 11 Base material 12 void layer 13 Hard layer 14 Adhesive

Claims

1. a gap layer and a hard layer formed on the gap layer, The void layer has a porosity of 30% by volume or more, the hard layer contains at least one selected from the group consisting of a metal, a metal oxide, silicon, a silicon oxide, and an organic-inorganic hybrid material, and the hardness of the hard layer, as measured by pressing an indenter 20 nm into the hard layer using a nanoindenter, is greater than that of the void layer; An optical laminate characterized by being disposed between layers of components constituting an optical member for the purpose of total reflection of light.

2. An optical laminate as described in claim 1, wherein the refractive index of the void layer at a wavelength of 550 nm is 1.25 or less.

3. 3. The optical laminate according to claim 1, wherein the hardness measured by pressing an indenter 20 nm into the hard layer using a nanoindenter is 0.04 GPa or more.

4. 4. The optical laminate according to claim 1, wherein the hard layer comprises at least one selected from the group consisting of silicon, aluminum, silicon dioxide, aluminum oxide, zinc tin composite oxide (ZTO), indium tin composite oxide (ITO), indium zinc composite oxide (IZO), gallium zinc composite oxide (GZO), and polysiloxane.

5. The optical laminate according to claim 1 , wherein the hard layer has a thickness of 5 nm or more.

6. The optical laminate according to any one of claims 1 to 5, wherein the hard layer is formed by at least one method selected from the group consisting of vacuum deposition, sputtering, and chemical vapor deposition (CVD).

7. The optical laminate according to claim 1 , wherein the porous layer is a porous body in which microporous particles of a silicon compound are chemically bonded to each other.

8. Further, it includes an adhesive layer, The optical laminate according to claim 1 , wherein the adhesive layer is provided on a surface of the hard layer opposite to the porous layer.

9. a hard layer forming step of forming the hard layer on at least one surface of the porous layer, 9. The method for producing an optical laminate according to claim 1, wherein in the hard layer forming step, the hard layer is formed by at least one method selected from the group consisting of a vacuum deposition method, a sputtering method, and a chemical vapor deposition (CVD) method.

10. An optical member comprising the optical laminate according to claim 1 .

11. An optical device comprising the optical member according to claim 10.

12. A method for producing an optical member according to claim 10, comprising an optical laminate production step of producing the optical laminate according to any one of claims 1 to 8 by the production method according to claim 9.

13. 12. The method for manufacturing an optical device according to claim 11, further comprising the step of manufacturing the optical element according to claim 10 by the manufacturing method according to claim 12.

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