Transparent laminate

Abstract

The present invention relates to a cover member comprising: a transparent substrate having a first main surface and a second main surface; and a transparent first functional layer laminated on the first main surface of the substrate.

Description

[0001] This case is filed on December 25, 2020 、Application No. 202080090517.8

[0002] (PCT / JP2020 / 049037) 、The name of the invention is Transparent laminate Divisional application. Technical Field

[0003] The present invention relates to a transparent laminated body. Background Art

[0004] Transparent substrates such as glass plates and resin plates are used for various purposes, and for example, are sometimes used as cover members for protecting articles (Patent Document 1).

[0005] Prior art literature

[0006] Patent Literature

[0007] Patent Document 1: Japanese Patent Application Publication No. 2017-144575 Summary of the invention

[0008] Technical problem to be solved by the invention

[0009] In recent years, such cover members are required to have other functions in addition to protecting articles. The present invention is proposed to solve the above-mentioned problems, and an object of the present invention is to provide a cover member that can be used for purposes other than protecting articles.

[0010] Technical solutions for solving technical problems

[0011] Item 1. A transparent laminate, comprising: a transparent substrate having a first main surface and a second main surface; and a transparent first functional layer laminated on the first main surface of the substrate.

[0012] Item 2. The transparent laminate according to Item 1, wherein the first functional layer has an anti-fogging function.

[0013] Item 3. The transparent laminate according to Item 1 or 2, wherein the surface roughness Ra of the first functional layer is 1 to 1000 nm.

[0014] Item 4. A transparent laminate as described in any one of Items 1 to 3, wherein the first functional layer includes: a base film having a first main surface and a second main surface; an adhesive layer laminated on the second main surface of the base film; and an anti-fog layer laminated on the first main surface of the base film, and the base film is fixed to the first main surface of the substrate via the adhesive layer.

[0015] Item 5. The transparent laminate according to any one of Items 1 to 3, wherein the first functional layer includes an adhesive layer and an antifogging layer, and the antifogging layer is fixed to the first main surface of the substrate via the adhesive layer.

[0016] Item 6. The transparent laminate according to any one of Items 1 to 3, wherein the first functional layer includes an antifogging layer, and the antifogging layer is laminated on the first main surface of the substrate.

[0017] Item 7. The transparent laminate according to any one of Items 4 to 6, wherein the antifogging layer has a moisture absorbing layer containing a moisture absorbing resin material.

[0018] Item 8. The transparent laminate according to Item 7, wherein the anti-fogging layer includes the hygroscopic layer and a hydrophilic layer laminated on the hygroscopic layer and having hydrophilicity.

[0019] Item 9. The transparent laminate according to Item 8, wherein the hydrophilic layer of the anti-fogging layer contains a polyether-modified dimethylsiloxane represented by the following formula (A):

[0020]

[0021] wherein m is an integer greater than or equal to 2, and n, x and y are independently an integer greater than or equal to 1,

[0022] R 1 is a hydrogen atom or a methyl group, R 2 It is an alkyl group having 1 to 3 carbon atoms.

[0023] Item 10. A transparent laminate as described in Item 9, wherein in the above formula (A), m is an integer of 1 to 3, n is an integer of 3 to 600, y / (x+y) is greater than 0.01 and less than 1, and the average molecular weight of the above transparent laminate is 3000 to 300000.

[0024] Item 11. The transparent laminate according to Item 7, wherein in the anti-fogging layer, a hydrophilic agent is dispersed in the moisture absorbing layer.

[0025] Item 12. The transparent laminate according to Item 11, wherein the anti-fogging layer contains a solvent having a boiling point of 100° C. to 300° C.

[0026] Item 13. The transparent laminate according to Item 12, wherein the solvent has an alcohol group.

[0027] Item 14. The transparent laminate according to any one of Items 11 to 13, wherein the antifog layer has an antifog property after being rubbed a predetermined number of times with a cloth impregnated with alcohol.

[0028] Item 15. The transparent laminate according to any one of Items 11 to 14, wherein the antifogging layer has an antifogging property after being subjected to a predetermined constant temperature and humidity test.

[0029] Item 16. The transparent laminate according to any one of Items 11 to 15, wherein the antifogging layer is formed of a single layer.

[0030] Item 17. The transparent laminate according to any one of Items 1 to 6, wherein the first functional layer contains an inorganic compound as a main component.

[0031] Item 18. The transparent laminate according to Item 17, wherein the visible light transmittance is 85% or more and the visible light reflectance is 10% or less.

[0032] Item 19. The transparent laminate according to Item 17 or 18, wherein the minimum value of the transmittance in the visible light wavelength region is within ±5% of the transmittance of the substrate.

[0033] Item 20. The transparent laminate according to any one of Items 17 to 19, wherein the maximum value of the reflectance in the visible light wavelength region is within ±5% of the reflectance of the substrate.

[0034] Item 21. The transparent laminate according to any one of Items 17 to 20, wherein the reflectance in the visible light wavelength region satisfies: 1≤maximum reflectance / minimum reflectance≤1.5.

[0035] Item 22. The transparent laminate according to any one of Items 17 to 21, wherein the first functional layer contains inorganic fine particles and an inorganic binder.

[0036] Item 23. The transparent laminate according to Item 22, wherein the film thickness of the first functional layer is not more than twice the particle diameter of the inorganic fine particles.

[0037] Item 24. The transparent laminate according to Item 22 or 23, wherein the inorganic fine particles are formed of SiO2.

[0038] Item 25. The transparent laminate according to Item 24, wherein the content of the SiO 2 in the first functional layer is 28% by mass or less.

[0039] Item 26. The transparent laminate according to any one of Items 22 to 25, wherein the first functional layer contains photocatalyst fine particles.

[0040] Item 27. The transparent laminate according to Item 26, wherein the photocatalyst particles are formed of an oxide or a nitride oxide having any element selected from titanium, tungsten and iron as a main component.

[0041] Item 28. The transparent laminate according to Item 26 or 27, wherein the content of the photocatalyst particles is 40% by mass or less.

[0042] Item 29. The transparent laminate according to any one of Items 26 to 28, wherein the content of the inorganic binder is 30% by mass or more.

[0043] Item 30. The transparent laminate according to any one of Items 17 to 29, wherein the first functional layer has an anti-fogging property after being immersed in water for a predetermined period of time.

[0044] Item 31. The transparent laminate according to any one of Items 17 to 30, wherein the first functional layer has an anti-fogging property after being rubbed a predetermined number of times with a cloth impregnated with alcohol.

[0045] Item 32. The transparent laminate according to any one of Items 17 to 31, wherein the first functional layer has anti-fogging properties by irradiating the first functional layer with ultraviolet rays after rubbing the first functional layer a predetermined number of times with a cloth impregnated with alcohol.

[0046] Item 33. The transparent laminate according to any one of Items 17 to 32, wherein the first functional layer has an anti-fogging property when irradiated with ultraviolet rays after a predetermined constant temperature and humidity test.

[0047] Item 34. The transparent laminate according to any one of Items 17 to 33, wherein the transparent laminate is used as a cover member of a surveillance camera placed outdoors.

[0048] Item 35. The transparent laminate as described in Item 34, wherein the monitoring camera has an ultraviolet irradiation device.

[0049] Item 36. The transparent laminate body as described in Item 34 or 35, wherein the first functional layer is arranged to face the monitoring camera side.

[0050] Item 37. The transparent laminate according to Item 34, wherein the first functional layer is configured to face the opposite side to the monitoring camera.

[0051] Item 38. The transparent laminate according to any one of Items 2 to 10, further comprising a second functional layer laminated on the first functional layer and having moisture permeability.

[0052] Item 39. The transparent laminate according to Item 38, wherein the first functional layer is formed of an organic-inorganic composite material, and the refractive index of the second functional layer is smaller than that of the first functional layer.

[0053] Item 40. The transparent laminate according to Item 38 or 39, wherein the second functional layer is a single layer.

[0054] Item 41. The transparent laminate according to Item 40, wherein the refractive index of the second functional layer is 1.10 to 1.45.

[0055] Item 42. The transparent laminate according to Item 41, wherein when the refractive index of the first functional layer is set to X, the refractive index of the second functional layer is

[0056] Item 43. The transparent laminate according to Item 42, wherein the second functional layer contains hollow particles and a binder for bonding the hollow particles.

[0057] Item 44. The transparent laminate according to Item 43, wherein the refractive index of the hollow particles is 1.15 to 2.70.

[0058] Item 45. The transparent laminate according to Item 43 or 44, wherein the average particle size of the hollow particles is 20 to 100 nm.

[0059] Item 46. The transparent laminate according to any one of Items 43 to 45, wherein the hollow particles are selected from the group consisting of silicon dioxide, magnesium fluoride, aluminum oxide, aluminosilicate, titanium oxide, and zirconium oxide.

[0060] Item 47. The transparent laminate according to any one of Items 38 to 46, wherein the second functional layer contains a solvent having a boiling point of 100° C. to 300° C.

[0061] Item 48. The transparent laminate according to Item 47, wherein the solvent contains 3-methoxy-3-methyl-1-butanol as a main component.

[0062] Item 49. The transparent laminate according to Item 47 or 48, wherein the second functional layer contains 1 ppb or more and 5 g / cm 3 The above solvents are as follows.

[0063] Item 50. The transparent laminate according to any one of Items 43 to 49, wherein the binder contains at least one of polysilsesquioxane and silica.

[0064] Item 51. The transparent laminate according to any one of Items 43 to 50, wherein the porosity of the second functional layer is 0 to 70% by volume.

[0065] Item 52. A transparent laminate as described in Item 38 or 39, wherein the second functional layer includes: a first layer laminated on the first functional layer; and a second layer laminated on the first layer and having a lower refractive index than the first layer.

[0066] Item 53. The transparent laminate according to Item 52, wherein the refractive index of the first layer is 1.35 to 1.55, and the refractive index of the second layer is 1.10 to 1.25.

[0067] Item 54. The transparent laminate according to Item 53, wherein the second layer contains hollow particles and a binder for bonding the hollow particles.

[0068] Item 55. The transparent laminate according to Item 54, wherein the refractive index of the hollow particles is 1.15 to 2.70.

[0069] Item 56. The transparent laminate according to Item 54 or 55, wherein the average particle size of the hollow particles is 20 to 100 nm.

[0070] Item 57. The transparent laminate according to any one of Items 54 to 56, wherein the hollow particles are selected from the group consisting of silicon dioxide, magnesium fluoride, aluminum oxide, aluminosilicate, titanium oxide, and zirconium oxide.

[0071] Item 58. The transparent laminate according to any one of Items 54 to 57, wherein the binder contains at least one of polysilsesquioxane and silica.

[0072] Item 59. The transparent laminate according to any one of Items 54 to 58, wherein the porosity of the second layer is 0 to 70% by volume.

[0073] Item 60. The transparent laminate according to any one of Items 54 to 59, wherein the first layer contains the binder of the second layer.

[0074] Item 61. The transparent laminate according to any one of Items 38 to 60, wherein the bending modulus of elasticity of the second functional layer is 1 to 10 GPa.

[0075] Item 62. The transparent laminate according to any one of Items 38 to 61, wherein the bending modulus of elasticity of the second functional layer overlaps the bending modulus of elasticity of the first functional layer.

[0076] Item 63. The transparent laminate according to any one of Items 38 to 62, wherein a difference between a linear expansion coefficient of the first functional layer and a linear expansion coefficient of the second functional layer is 50 ppm / °C or less.

[0077] Item 64. The transparent laminate according to Item 1, wherein the first functional layer has an anti-reflection function.

[0078] Item 65. The transparent laminate according to Item 64, wherein the first functional layer is formed of a film in which an adhesive layer, a base sheet, and an antireflection layer are laminated in this order.

[0079] Item 66. The transparent laminate according to Item 65, wherein the refractive index of the antireflection layer of the first functional layer is 1.10 to 1.45.

[0080] Item 67. The transparent laminate according to Item 65 or 66, wherein the antireflection layer of the first functional layer contains hollow particles and a binder for bonding the hollow particles.

[0081] Item 68. The transparent laminate according to Item 67, wherein the refractive index of the hollow particles is 1.15 to 2.70.

[0082] Item 69. The transparent laminate according to Item 67 or 68, wherein the average particle size of the hollow particles is 20 to 100 nm.

[0083] Item 70. The transparent laminate according to any one of Items 65 to 69, wherein the antireflection layer contains a second solvent having a boiling point higher than that of water and not higher than a heat resistance temperature of the substrate.

[0084] Item 71. The transparent laminate according to Item 70, wherein the second solvent contains 3-methoxy-3-methyl-1-butanol as a main component.

[0085] Item 72. The transparent laminate according to Item 70 or 71, wherein the first functional layer contains 1 ppb or more and 5 g / cm 3 % or less of the above-mentioned second solvent.

[0086] Item 73. The transparent laminate according to any one of Items 2 to 72, wherein the substrate is glass.

[0087] Item 74. The transparent laminate according to any one of Items 2 to 73, wherein the substrate is a float glass produced by a float process, and a concentration of tin oxide in the first main surface is lower than a concentration of tin oxide in the second main surface.

[0088] Item 75. The transparent laminate according to any one of Items 2 to 73, wherein the substrate is a float glass produced by a float process, and a concentration of tin oxide in the first main surface is higher than a concentration of tin oxide in the second main surface.

[0089] Item 76. The transparent laminate according to any one of Items 1 to 75, further comprising a third functional layer laminated on the second main surface of the substrate.

[0090] Item 77. An aircraft, which is a wirelessly controlled aircraft, comprising: a camera device having a lens; and a cover component covering the lens and formed by a transparent laminate body described in any one of Items 1 to 76, wherein the anti-fog layer in the cover component is configured to face the lens side.

[0091] Item 78. An aircraft as described in Item 77, which is configured to be able to move in water.

[0092] Item 79. A cover component provided on a wirelessly controlled aircraft equipped with a camera device having a lens, wherein the cover component is formed by the transparent laminated body described in any one of Items 1 to 76, and the anti-fog layer is configured to face the lens side.

[0093] Item 80. A mobile device, which is an unmanned mobile device or a manned mobile device, comprising: a camera device having a lens; and a cover component covering the above-mentioned lens and formed by a transparent laminate body described in any one of Items 1 to 76, wherein the anti-fog layer in the above-mentioned cover component is configured to face the above-mentioned lens side, and the control method is selected from wireless control, autonomous control, direct control by a person, or a combination thereof, and the above-mentioned mobile device is at least any one of an aircraft, a ground mobile device, a water mobile device, and an underwater mobile device, which does not include existing automobiles, airplanes, helicopters, ships, and submarines.

[0094] Effects of the Invention

[0095] According to the present invention, since the transparent functional layer is laminated on the surface of the substrate, the functional layer can be used for purposes other than protecting articles by providing functions to the functional layer. BRIEF DESCRIPTION OF THE DRAWINGS

[0096] Figure 1 It is a cross-sectional view showing a first embodiment of the cover member according to the present invention.

[0097] Figure 2 This is a schematic diagram showing an example in which a cover member is provided in front of the lens of the imaging device.

[0098] Figure 3 This is a schematic diagram of an example in which a cover member is provided in front of a lens in which an imaging device is housed in a housing.

[0099] Figure 4 This is a graph showing the transmittance of Examples 1 to 3 and the substrate.

[0100] Figure 5 This is a graph showing the reflectance of Examples 1 to 3 and the substrate.

[0101] Figure 6 It is a cross-sectional view showing a second embodiment of the cover member of the present invention.

[0102] Figure 7 It is a cross-sectional view showing a schematic structure of the second functional layer as an antireflection layer.

[0103] Figure 8 It is a cross-sectional view showing another example of the cover member according to the second embodiment.

[0104] Fig. 9 It is a cross-sectional view showing another example of the cover member according to the second embodiment.

[0105] Fig.10 It is a cross-sectional view showing another example of the cover member according to the second embodiment.

[0106] Fig.11 This is a graph showing the single-surface reflectance of Examples 23 and 26.

[0107] Fig.12 The single-side reflectance at 400 to 700 nm of the films on which the antireflection films of Examples 28 to 30 were formed is shown.

[0108] Fig.13 This is a side view showing the schematic structure of the drone.

[0109] Explanation of symbols

[0110] 1: substrate; 11: first main surface; 12: second main surface; 2: first functional layer; 3: second functional layer. DETAILED DESCRIPTION

[0111] <A. First embodiment>

[0112] Next, a first embodiment in which the transparent laminate of the present invention is applied to a cover member will be described with reference to the drawings. Figure 1 It is a cross-sectional view of the cover component.

[0113] <1. Overview of Cover Parts>

[0114] The cover member of this embodiment is a member that is disposed in front of a lens of an imaging device such as a camera to protect the lens, etc., as described below. Figure 1 As shown, the cover component 10 includes: a transparent substrate 1 having a first main surface 11 and a second main surface 12; and a first functional layer 2 laminated on the first main surface 11 of the substrate 1. Each component will be described in detail below.

[0115] <2. Base material>

[0116] The substrate 1 can be formed of a light-transmitting resin material (organic polymer material), a glass plate, etc. In addition, the shape of the substrate is not particularly limited and can be appropriately determined to be circular, rectangular, polygonal, or irregular in shape according to various uses as described later. Specific examples are given below for illustration.

[0117] <2-1. Resin material>

[0118] The resin material is not particularly limited as long as it is a light-transmitting material as described above, and may be, for example, polycarbonate (PC), acrylonitrile / styrene resin (AS), acrylonitrile / butadiene / styrene resin (ABS), methyl methacrylate resin (PMMA), polyvinyl chloride (PVC), triacetyl cellulose (TAC), etc., or a material containing multiple thereof.

[0119] <2-2. Glass plate>

[0120] The glass plate 1 is not particularly limited, and a known transparent glass plate can be used. For example, various glass plates such as float glass, heat-absorbing glass, clear glass, green glass, UV green glass, and soda-lime glass can be used.

[0121] An example of the composition of transparent glass, heat-absorbing glass, soda-lime glass, and float glass is shown below.

[0122] <2-2-1. Transparent glass>

[0123] SiO2: 70-73% by mass

[0124] Al2O3: 0.6-2.4% by mass

[0125] CaO: 7-12 mass%

[0126] MgO: 1.0-4.5% by mass

[0127] R2O: 13-15 mass% (R is an alkali metal)

[0128] Total iron oxide converted to Fe2O3 (T-Fe2O3): 0.08-0.14 mass%

[0129] <2-2-2. Heat-absorbing glass>

[0130] The composition of the heat-absorbing glass can be set, for example, as follows: based on the composition of the transparent glass, the ratio of total iron oxide (T-Fe2O3) converted to Fe2O3 is 0.4 to 1.3 mass %, the ratio of CeO2 is 0 to 2 mass %, the ratio of TiO2 is 0 to 0.5 mass %, and the skeleton components of the glass (mainly SiO2 and Al2O3) are reduced accordingly with the increase in the amount of T-Fe2O3, CeO2 and TiO2.

[0131] <2-2-3. Soda-lime glass>

[0132] SiO2: 65-80% by mass

[0133] Al2O3: 0-5% by mass

[0134] CaO: 5-15% by mass

[0135] MgO: 2 mass% or more

[0136] NaO: 10-18% by mass

[0137] K2O: 0-5% by mass

[0138] MgO+CaO: 5-15% by mass

[0139] Na2O+K2O: 10-20% by mass

[0140] SO3: 0.05-0.3% by mass

[0141] B2O3: 0-5% by mass

[0142] Total iron oxide converted to Fe2O3 (T-Fe2O3): 0.02-0.03 mass%

[0143] <2-2-4. Float glass>

[0144] SiO2: 65~80%

[0145] Al2O3: 0~5%

[0146] MgO: 0~20%

[0147] CaO: 0~20%

[0148] Na2O: 10-20%

[0149] K2O: 0~5%

[0150] <2-2-4-1. High transmittance float glass>

[0151] contain:

[0152] SiO2: 66~72%

[0153] Al2O3: 2~4%

[0154] MgO: 8-15%

[0155] CaO: 1~8%

[0156] Na2O: 12-16%

[0157] K2O: 0~1%,

[0158] MgO+CaO is in the range of 12-17%, and the molar ratio CaO / (MgO+CaO) is 0.1-0.4.

[0159] Next, each component constituting the composition of the float glass will be described.

[0160] (SiO2)

[0161] SiO2 is a main component of the glass plate 1. When the content of SiO2 is too low, the chemical durability and heat resistance of the glass such as water resistance are reduced. On the other hand, when the content of SiO2 is too high, the viscosity of the glass plate 1 at high temperature increases, and melting and molding become difficult. Therefore, the content of SiO2 is preferably in the range of 66 to 72 mol%, preferably 67 to 70 mol%.

[0162] (Al2O3)

[0163] Al2O3 is a component that improves the chemical durability of the glass sheet 1, such as water resistance, and increases the surface compressive stress after chemical strengthening by making it easier for alkali metal ions to move in the glass, and is used to deepen the stress layer depth. On the other hand, if the content of Al2O3 is too high, the viscosity of the molten glass will increase, T2 and T4 will increase, and the clarity of the molten glass will deteriorate, making it difficult to produce high-quality glass sheets. In addition, in the float process, the working temperature is when the glass viscosity reaches 10 4 dPa·s, hereinafter referred to as T4. In addition, the melting temperature is the temperature at which the glass viscosity reaches 10 2 The temperature of dPa·s is referred to as T2 below.

[0164] Therefore, the content of Al2O3 is preferably in the range of 1 to 4 mol%. The content of Al2O3 is preferably 3 mol% or less, and preferably 2 mol% or more.

[0165] (MgO)

[0166] MgO is an essential component for improving the meltability of glass. From the viewpoint of fully obtaining this effect, the content of MgO in the glass plate 1 is 8 mol% or more. In addition, when the content of MgO is lower than 8 mol%, the surface compressive stress after chemical strengthening decreases, and there is a tendency for the depth of the stress layer to become shallower. On the other hand, when the content increases to exceed an appropriate amount, the strengthening performance obtained by chemical strengthening decreases, and in particular, the depth of the surface compressive stress layer becomes shallower sharply. Although this adverse effect of MgO is the smallest among alkaline earth metal oxides, the content of MgO in the glass plate 1 is less than 15 mol%. In addition, when the content of MgO is high, T2 and T4 increase, and the clarity of the glass melt deteriorates, making it difficult to manufacture high-quality glass plates.

[0167] Therefore, in the glass plate 1, the content of MgO is within a range of 8 to 15 mol%, and is preferably 12 mol% or less.

[0168] (CaO)

[0169] CaO has the effect of reducing viscosity at high temperatures. When the content is too high and exceeds the appropriate range, the glass plate 1 is prone to devitrification, and the movement of sodium ions in the glass plate 1 is hindered. When CaO is not contained, there is a tendency for the surface compressive stress after chemical strengthening to decrease. On the other hand, when CaO is contained in an amount exceeding 8 mol%, the surface compressive stress after chemical strengthening is significantly reduced, the depth of the compressive stress layer is significantly shallowed, and the glass plate 1 is prone to devitrification.

[0170] Therefore, the CaO content is preferably in the range of 1 to 8 mol %. The CaO content is preferably 7 mol % or less, and preferably 3 mol % or more.

[0171] (SrO, BaO)

[0172] SrO and BaO significantly reduce the viscosity of the glass plate 1. When contained in a small amount, the liquidus temperature T L However, even if SrO and BaO are added in small amounts, the movement of sodium ions in the glass sheet 1 is significantly hindered, the surface compressive stress is greatly reduced, and the depth of the compressive stress layer becomes quite shallow.

[0173] Therefore, it is preferred that the glass plate 1 contains substantially no SrO or BaO.

[0174] (RO)

[0175] In this embodiment, RO represents the sum of MgO and CaO. When the content of RO is too low, the component that reduces the viscosity of the glass plate 1 is insufficient, and melting becomes difficult. On the other hand, when the content of RO is too high, the surface compressive stress is greatly reduced, and the depth of the compressive stress layer becomes quite shallow, and there is a liquidus temperature T L A sharp upward trend.

[0176] Therefore, the RO content is preferably in the range of 12 to 17 mol %. The RO content is preferably 14 mol % or more and preferably 16 mol % or less.

[0177] Moreover, when the molar ratio CaO / RO of the CaO content to the RO content is in the range of 0.1 to 0.4, there is a tendency that the liquidus temperature is particularly low. Therefore, it is appropriate that the molar ratio is 0.1 to 0.4. In addition, if the molar ratio is reduced, the surface compressive stress and the depth of the compressive stress layer can be increased, but on the other hand, T2 and T4 become higher, which is far away from the narrow sense of SL, and the manufacture of glass articles becomes difficult. Therefore, the molar ratio is preferably 0.2 or more and preferably 0.3 or less.

[0178] (Na2O)

[0179] Na2O is a component used to increase the surface compressive stress by replacing sodium ions with potassium ions, and to deepen the depth of the surface compressive stress layer. However, when the content exceeds an appropriate amount, the stress relaxation during the chemical strengthening treatment becomes greater than the surface compressive stress generated by the ion exchange during the chemical strengthening treatment, and as a result, there is a tendency for the surface compressive stress to decrease.

[0180] In addition, Na2O is a component for improving melting property and reducing T4 and T2. On the other hand, when the content of Na2O is too high, the water resistance of glass is significantly reduced. In the glass plate 1, as long as the content of Na2O is 12 mol% or more, the effect of reducing T4 and T2 can be fully obtained. When it exceeds 16 mol%, the reduction of surface compressive stress due to stress relaxation becomes significant.

[0181] Therefore, the content of Na2O in the glass plate 1 of the present embodiment is preferably in the range of 12 to 16 mol%. The content of Na2O is preferably 13 mol% or more, and more preferably 15 mol% or less.

[0182] (K2O)

[0183] K2O is a component that improves the melting property of glass, similarly to Na2O. In addition, within the range where the content of K2O is low, the ion exchange rate in chemical strengthening increases, and the depth of the surface compressive stress layer becomes deeper, but on the other hand, the liquidus temperature T L Therefore, it is preferred to contain K2O at a low content.

[0184] On the other hand, K2O has a smaller effect on reducing T4 and T2 than Na2O, but when K2O is contained in large amounts, it will hinder the clarification of the glass melt. In addition, the higher the content of K2O, the lower the surface compressive stress after chemical strengthening. Therefore, the content of K2O is suitable in the range of 0 to 1 mol%.

[0185] (Li2O)

[0186] Even if only a small amount of Li2O is contained, the depth of the compressive stress layer is significantly reduced. In addition, when a glass article containing Li2O is chemically strengthened with potassium nitrate alone, the molten salt deteriorates significantly faster than a glass article not containing Li2O. Specifically, when the chemical strengthening treatment is repeatedly performed with the same molten salt, the surface compressive stress formed on the glass surface is reduced with fewer times. Therefore, in the glass plate 1 of this embodiment, Li2O may be contained in an amount of less than 1 mol%, but preferably substantially no Li2O is contained.

[0187] (B2O3)

[0188] B2O3 is a component that reduces the viscosity of the glass plate 1 and improves its solubility. However, when the content of B2O3 is too high, the glass plate 1 is easily separated into phases, and the water resistance of the glass plate 1 is reduced. In addition, the compound formed by B2O3 and alkali metal oxides may volatilize, thereby damaging the refractory of the glass melting chamber. In addition, the inclusion of B2O3 reduces the depth of the compressive stress layer in chemical strengthening. Therefore, it is appropriate that the content of B2O3 is 0.5 mol% or less. In the present invention, a glass plate 1 substantially free of B2O3 is more preferred.

[0189] (Fe2O3)

[0190] Usually, Fe is expressed as Fe 2+ or Fe 3+ Fe exists in the glass and acts as a colorant. 3+ It is a component that improves the ultraviolet absorption performance of glass. 2+ It is a component that improves the heat ray absorption performance. When the glass plate 1 is used as a cover glass for a display, since the coloring is required to be inconspicuous, it is preferred that the Fe content is low. However, in most cases, Fe is inevitably mixed in from industrial raw materials. Therefore, regarding the content of iron oxide converted to Fe2O3, when the entire glass plate 1 is expressed as 100 mass%, it is preferably 0.15 mass% or less, more preferably 0.1 mass% or less, and further preferably 0.02 mass% or less. In particular, in the above-mentioned high-transmittance float glass, high transmittance can be achieved due to the low Fe content. For example, when the thickness is 0.55 mm, the transmittance of light with a wavelength of 550 nm can reach 91% or more and 100% or less.

[0191] (TiO2)

[0192] TiO2 is a component that reduces the viscosity of the glass plate 1 and increases the surface compressive stress caused by chemical strengthening, but sometimes the glass plate 1 is colored yellow. Therefore, the content of TiO2 is preferably 0 to 0.2 mass%. In addition, it is usually inevitably mixed from industrial raw materials, and sometimes about 0.05 mass% is contained in the glass plate 1. If the content is at this level, the glass will not be colored, so it can be included in the glass plate 1 of this embodiment.

[0193] (ZrO2)

[0194] ZrO2 may be mixed into the glass sheet 1 from the refractory bricks constituting the glass melting furnace, especially when the glass sheet is manufactured by the float process, and its content is known to be about 0.01 mass %. On the other hand, ZrO2 is a component that improves the water resistance of glass and increases the surface compressive stress caused by chemical strengthening. However, a high content of ZrO2 sometimes causes an increase in the working temperature T4 and a decrease in the liquidus temperature T4. LMoreover, when a glass sheet is manufactured by a float process, crystals containing precipitated Zr are likely to remain as impurities in the manufactured glass. Therefore, the content of ZrO2 is preferably 0 to 0.1 mass %.

[0195] (SO3)

[0196] In the float process, sulfates such as sodium sulfate (Na2SO4) are widely used as clarifiers. Sulfate decomposes in molten glass to produce gas components, thereby promoting the defoaming of the glass melt, and part of the gas components melt as SO3 and remain in the glass plate 1. In the glass plate 1 of the present invention, SO3 is preferably 0 to 0.3 mass%.

[0197] (CeO2)

[0198] CeO2 is used as a clarifier. CeO2 generates O2 gas in the molten glass, so CeO2 helps to defoam. On the other hand, when CeO2 is too much, the glass will be colored yellow. Therefore, the content of CeO2 is preferably 0 to 0.5% by mass, more preferably 0 to 0.3% by mass, and further preferably 0 to 0.1% by mass.

[0199] (SnO2)

[0200] It is known that in a glass sheet formed by a float process, tin diffuses from the tin bath in the surface contacting the tin bath during forming and the tin exists in the form of SnO2. In addition, SnO2 mixed in the glass raw material contributes to defoaming. In the glass sheet 1 of the present invention, SnO2 is preferably 0 to 0.3 mass%.

[0201] (Other ingredients)

[0202] The glass plate 1 according to the present embodiment is preferably substantially composed of the above-mentioned components. However, the glass plate 1 according to the present embodiment may contain components other than the above-mentioned components in a range where the content of each component is preferably less than 0.1% by mass.

[0203] As components allowed to be contained, in addition to the above-mentioned SO3 and SnO2, As2O5, Sb2O5, Cl, and F added for the purpose of defoaming the molten glass can be exemplified. However, due to the large adverse impact on the environment, As2O5, Sb2O5, Cl, and F are preferably not added. In addition, as other examples allowed to be contained, ZnO, P2O5, GeO2, Ga2O3, Y2O3, and La2O3 are allowed to be contained even if the components other than the above-mentioned components are derived from raw materials used in industry, as long as they do not exceed the range of 0.1 mass %. These components are components that are appropriately added as needed, or components that are inevitably mixed, and therefore, the glass plate 1 of this embodiment mode may not substantially contain these components.

[0204] (Density (specific gravity): d)

[0205] According to the above composition, in the present embodiment, the density of the glass plate 1 can be reduced to 2.53 g·cm -3 Below, further 2.51 g·cm -3 Below, reduced to 2.50 g·cm depending on the situation -3 the following.

[0206] In float process, if the density difference between glass types is large, when switching the glass type to be manufactured, the molten glass with high density will stay at the bottom of the melting furnace, which may hinder the switching of types. At present, the density of soda-lime glass mass-produced by float process is about 2.50g·cm -3 Therefore, considering mass production by the float process, the density of the glass sheet 1 is preferably close to the above value.

[0207] Specifically, it is preferably 2.45 to 2.55 g·cm -3 , particularly preferably 2.47 to 2.53 g·cm -3 , more preferably 2.47 to 2.50 g·cm -3 .

[0208] (Elastic modulus: E)

[0209] If chemical strengthening accompanied by ion exchange is performed, the glass substrate may warp. In order to suppress the warping, the elastic modulus of the glass plate 1 is preferably high. According to the present invention, the elastic modulus (Young's modulus: E) of the glass plate 1 can be increased to 70 GPa or more, and further increased to 72 GPa or more.

[0210] (Coefficient of thermal expansion)

[0211] In particular, in the above-mentioned high transmittance float glass, a thermal expansion coefficient of 50×10 -7 ~100×10 -7 / K% or less.

[0212] <2-2-5. Orientation of glass plate>

[0213] In a glass sheet manufactured by a float process, the surface in contact with the molten metal is called a bottom surface, and the surface opposite thereto is called a top surface. The bottom surface and the top surface may be unpolished surfaces. Since the bottom surface is in contact with the molten metal, when the molten metal is tin, the concentration of tin oxide contained in the bottom surface is greater than the concentration of tin oxide contained in the top surface.

[0214] In this way, since the tin oxide concentration on the bottom surface is high, it has the effect of suppressing the dissolution of the alkali components contained in the glass plate. In the case where it is necessary to suppress the reduction in durability caused by alkali dissolution, the above-mentioned first functional layer 2 can be laminated on the bottom surface. On the other hand, since the tin oxide concentration on the top surface is low, the concentration of SiOH groups on the surface is relatively high. Therefore, in the case where it is necessary to increase the adhesion by utilizing the chemical bond between the OH group of the first functional layer 2 and the surface SiOH group, the first functional layer 2 can be laminated on the top surface. In addition, in the case where it is necessary to avoid the influence of trace metals (tin), the bottom surface can be polished using abrasives such as cerium oxide, and the first functional layer 2 can be laminated on the bottom surface or the top surface, or on both the bottom surface and the top surface. In addition, the above content is not only applicable to the first functional layer 2, but also to other functional layers described in this specification.

[0215] <2-2-6. Thickness of glass plate>

[0216] The thickness of the glass plate 1 is not particularly limited, and is preferably 0.2 mm to 10 mm, and more preferably 0.5 mm to 4 mm. When the thickness of the glass plate 1 is less than 0.2 mm, the rigidity may be reduced, and when the thickness of the glass plate 1 is greater than 10 mm, the weight may be increased. In addition, as described above, when the substrate 1 is formed of a resin material, the same thickness as the glass plate can be adopted.

[0217] <3. First functional layer>

[0218] The first functional layer 2 can be composed of films with various functions. For example, a heat-insulating film (heat-reflecting film) or an anti-fog layer (or an anti-fog sheet) can be used. In order to suppress the temperature rise of the camera device, the heat-insulating film is a known film that is formed in a manner of reflecting infrared rays or absorbing infrared rays. Moreover, such a film can be pasted on the first main surface 11 of the substrate 1 using an adhesive material, or a film having a heat-insulating function can be laminated on the first main surface 11 by coating. In addition, the following is another example of the first functional layer 2. The anti-fog layer is described in detail.

[0219] <3-1. Anti-fog layer>

[0220] The anti-fog layer is not particularly limited as long as it has the anti-fog effect of the substrate 1, and a known anti-fog layer can be used. Generally speaking, there are: a hydrophilic type in which water generated from water vapor forms a water film on the surface; a water-absorbing type that absorbs water vapor; a water-repellent and water-absorbing type in which water droplets are not easily condensed on the surface; and a water-repellent type that repels water droplets generated from water vapor. Any type of anti-fog layer can be applied. As an example, an example of a water-repellent and water-absorbing type anti-fog layer is described below.

[0221] [Organic-inorganic composite anti-fog layer]

[0222] The organic-inorganic composite anti-fog layer is a monolayer film or a laminated multilayer film formed on the surface of any functional layer. The organic-inorganic composite anti-fog layer contains at least a water-absorbent resin, a hydrophobic group and a metal oxide component. As required, the anti-fog layer may also contain other functional components. As long as the water-absorbent resin is a resin that can absorb and retain water, its type is not limited. The hydrophobic group can be supplied to the anti-fog layer from a metal compound with a hydrophobic group (a metal compound containing a hydrophobic group). The metal oxide component can be supplied to the anti-fog layer from a metal compound other than the metal compound containing a hydrophobic group, metal oxide particles, etc. Each component is described below.

[0223] (Water-absorbent resin)

[0224] The water-absorbing resin is not particularly limited, and examples thereof include polyethylene glycol, polyether resins, polyurethane resins, starch resins, cellulose resins, acrylic resins, epoxy resins, polyester polyols, hydroxyalkyl cellulose, polyvinyl alcohol, polyvinyl pyrrolidone, polyvinyl acetal resins, polyvinyl acetate, etc. Among them, hydroxyalkyl cellulose, polyvinyl alcohol, polyvinyl pyrrolidone, polyvinyl acetal resins, polyvinyl acetate, epoxy resins, and polyurethane resins are preferred, polyvinyl acetal resins, epoxy resins, and polyurethane resins are more preferred, and polyvinyl acetal resins are particularly preferred.

[0225] The polyvinyl acetal resin can be obtained by acetalizing polyvinyl alcohol with an aldehyde through a condensation reaction. The acetalization of polyvinyl alcohol can be carried out by a known method such as a precipitation method using an aqueous medium in the presence of an acid catalyst, a dissolution method using a solvent such as an alcohol, etc. The acetalization can also be carried out in parallel with the saponification of polyvinyl acetate. The degree of acetalization is preferably 2 to 40 mol%, more preferably 3 to 30 mol%, particularly preferably 5 to 20 mol%, and preferably 5 to 15 mol% depending on the situation. The degree of acetalization can be based on, for example 13 The polyvinyl acetal resin with the acetalization degree within the above range is suitable for forming an organic-inorganic composite anti-fogging layer with good water absorption and water resistance.

[0226] The average polymerization degree of polyvinyl alcohol is preferably 200 to 4500, more preferably 500 to 4500. A high average polymerization degree is conducive to forming an organic-inorganic composite anti-fog layer with good water absorption and water resistance, but when the average polymerization degree is too high, the solution viscosity also becomes too high, which may hinder film formation. The saponification degree of polyvinyl alcohol is preferably 75 to 99.8 mol%.

[0227] As aldehydes that undergo condensation reactions with polyvinyl alcohol, aliphatic aldehydes such as formaldehyde, acetaldehyde, butyraldehyde, hexyl formaldehyde, octyl formaldehyde, and decyl formaldehyde can be listed. In addition, benzaldehyde, 2-methylbenzaldehyde, 3-methylbenzaldehyde, 4-methylbenzaldehyde, and other alkyl-substituted benzaldehydes; chlorobenzaldehyde, other halogen-substituted benzaldehydes; substituted benzaldehydes in which hydrogen atoms are replaced by functional groups other than alkyl groups such as hydroxyl, alkoxy, amino, and cyano groups; aromatic aldehydes such as condensed aromatic ring aldehydes such as naphthaldehyde and anthracene formaldehyde. Aromatic aldehydes with strong hydrophobicity are advantageous in forming an organic-inorganic composite anti-fog layer with excellent water resistance at a low degree of acetalization. The use of aromatic aldehydes is also advantageous in leaving a large amount of hydroxyl groups and forming a highly water-absorbent film. The polyvinyl alcohol acetal resin is preferably an aromatic aldehyde, and particularly preferably an aldehyde structure containing benzaldehyde.

[0228] Examples of the epoxy resin include glycidyl ether epoxy resins, glycidyl ester epoxy resins, glycidyl amine epoxy resins, and cycloaliphatic epoxy resins, among which cycloaliphatic epoxy resins are preferred.

[0229] Examples of the polyurethane resin include polyurethane resins composed of polyisocyanate and polyol. As the polyol, acrylic polyol and polyoxyalkylene polyol are preferred.

[0230] As a cellulose resin, it can also be TAC (triacetyl cellulose) with a modified surface. As a modification method, physical modification method and chemical modification method can be exemplified. As a physical modification method, active ray irradiation method, plasma treatment method and corona discharge treatment method can be exemplified. As a chemical modification method, the acyl group in the TAC structure can be replaced by a hydroxyl group to make the surface hydrophilic (for example, refer to Japanese Patent Laid-Open No. 2017-57370 and Japanese Patent Laid-Open No. 2017-57242). Specifically, the acyl group in the TAC structure can be replaced by a hydroxyl group by swelling TAC in alcohol, saponifying it with KOH water, heat treating it, and neutralizing and washing it. Through such a saponification treatment, a TAC with a thickness of 10 to 200 μm and a surface-modified TAC with a thickness of 1 to 6 μm as the thickness of the modified layer of TAC can be obtained. The modified layer of TAC functions as an anti-fog layer. On the modified layer (anti-fog layer) of TAC, the anti-reflection layer of the present invention can also be formed. The thickness of TAC can be evaluated according to Japanese Industrial Standards (JIS.K7130:1999. Plastics-Films and Sheets-Thickness Determination Method). In the case where the modified layer is a saponified layer obtained by saponification, the thickness of the saponified layer can be obtained by the following method. The sample sampled from the anti-fog film is immersed in dichloromethane for 24 hours. The remaining sample after dissolution by the immersion is dried, and the thickness of the dried sample is measured 3 times, and the average of the 3 measured values ​​is used as the thickness of the saponified layer (for example, refer to paragraph

[0039] of Japanese Patent Publication No. 2017-57370).

[0231] The organic-inorganic composite anti-fog layer has a water-absorbent resin as a main component. In the present invention, the "main component" refers to the component with the highest content rate based on mass. From the viewpoint of film hardness, water absorption and anti-fog properties, the content rate of the water-absorbent resin based on the weight of the organic-inorganic composite anti-fog layer is preferably 50% by mass or more, more preferably 60% by mass or more, particularly preferably 65% ​​by mass or more, and is 95% by mass or less, more preferably 90% by mass or less.

[0232] (Water repellent base)

[0233] In order to fully obtain the above-mentioned effect brought about by the hydrophobic group, it is preferred to use a hydrophobic group with high hydrophobicity. The preferred hydrophobic group is at least one selected from (1) a chain or cyclic alkyl group having 3 to 30 carbon atoms, and (2) a chain or cyclic alkyl group having 1 to 30 carbon atoms in which at least a part of hydrogen atoms is substituted with fluorine atoms (hereinafter sometimes referred to as "fluorine-substituted alkyl group").

[0234] Regarding (1) and (2), the chain or cyclic alkyl group is preferably a chain alkyl group. The chain alkyl group may be an alkyl group having a branch, preferably a straight-chain alkyl group. An alkyl group having more than 30 carbon atoms may sometimes make the antifogging layer cloudy. From the viewpoint of the balance between the antifogging property, strength and appearance of the film, the carbon number of the alkyl group is preferably 20 or less, more preferably 6 to 14. Particularly preferred alkyl groups are straight-chain alkyl groups having 6 to 14 carbon atoms, especially 6 to 12 carbon atoms, such as n-hexyl (6 carbon atoms), n-decyl (10 carbon atoms), and n-dodecyl (12 carbon atoms). Regarding (2), the fluorine-substituted alkyl group may be a group in which only part of the hydrogen atoms of the chain or cyclic alkyl group are substituted with fluorine atoms, or a group in which all the hydrogen atoms of the chain or cyclic alkyl group are substituted with fluorine atoms, such as a straight-chain perfluoroalkyl group. Since the fluorine-substituted alkyl group has high water repellency, a sufficient effect can be achieved by adding a small amount. However, when the content of the fluorine-substituted alkyl group is too high, it is difficult to separate it from other components in the coating liquid used to form the film.

[0235] (Hydrolyzable metal compound having a hydrophobic group)

[0236] In order to incorporate the hydrophobic group into the anti-fog layer, a metal compound having a hydrophobic group (metal compound containing a hydrophobic group), in particular a metal compound having a hydrophobic group and a hydrolyzable functional group or a halogen atom (hydrolyzable metal compound containing a hydrophobic group) or a hydrolyzate thereof may be added to the coating liquid for forming the film. In other words, the hydrophobic group may be derived from a hydrolyzable metal compound containing a hydrophobic group. As the hydrolyzable metal compound containing a hydrophobic group, a hydrolyzable silicon compound containing a hydrophobic group represented by the following formula (I) is preferred.

[0237] R m S Y 4-m (I)

[0238] Among them, R is a hydrophobic group, that is, a chain or cyclic alkyl group with 1 to 30 carbon atoms in which at least part of the hydrogen atoms may be replaced by fluorine atoms, Y is a hydrolyzable functional group or a halogen atom, and m is an integer of 1 to 3. The hydrolyzable functional group is, for example, at least one selected from alkoxy, acetoxy, alkenyloxy and amino, preferably an alkoxy group, especially an alkoxy group with 1 to 4 carbon atoms. The alkenyloxy group is, for example, isopropenyloxy. The halogen atom is preferably chlorine. In addition, the functional groups exemplified here can also be used as the "hydrolyzable functional group" described below. m is preferably 1 to 2.

[0239] When the hydrolysis and polycondensation are completely carried out, the compound represented by the formula (I) provides a component represented by the following formula (II).

[0240] R m SiO (4-m) / 2 (II)

[0241] wherein R and m are as described above. After hydrolysis and polycondensation, the compound represented by formula (II) actually forms a network structure in which silicon atoms are bonded to each other via oxygen atoms in the antifogging layer.

[0242] In this way, the compound shown in formula (I) is hydrolyzed or partially hydrolyzed, and then at least a part of it undergoes polycondensation to form a network structure of siloxane bonds (Si-O-Si) in which silicon atoms and oxygen atoms are alternately connected and three-dimensionally extended. The hydrophobic group R is connected to the silicon atom contained in the network structure. In other words, the hydrophobic group R is fixed on the network structure of the siloxane bonds by R-Si bonds. This structure is conducive to uniformly dispersing the hydrophobic group R in the film. The network structure can also include silicon dioxide components provided by silicon compounds (such as tetraalkoxysilane, silane coupling agent) other than the hydrolyzable silicon compound containing the hydrophobic group shown in formula (I). If a silicon compound (hydrolyzable silicon compound not containing hydrophobic groups) having a hydrolyzable functional group or a halogen atom without a hydrophobic group is combined with a hydrolyzable silicon compound containing a hydrophobic group in a coating liquid for forming an anti-fog layer, a network structure of siloxane bonds containing silicon atoms bonded to the hydrophobic group and silicon atoms not bonded to the hydrophobic group can be formed. With such a structure, it is easy to adjust the content of the water-repellent group and the content of the metal oxide component in the anti-fog layer independently of each other.

[0243] The water-repellent base has the effect of improving the anti-fog performance by increasing the water vapor permeability of the surface of the anti-fog layer containing the water-absorbent resin. Since the two functions of water absorption and water repellency are contradictory, the water-absorbent material and the water-repellent material are usually distributed in different layers. The water-repellent base extends the time until condensation by eliminating the uneven presence of water near the surface of the anti-fog layer, thereby improving the anti-fog property of the anti-fog layer having a single-layer structure. This effect is explained below.

[0244] The water vapor intruding the anti-fog layer containing the water-absorbent resin forms a hydrogen bond with the hydroxyl of the water-absorbent resin, etc., and is retained in the form of bound water. As the amount increases, the water vapor is retained in the form of free water in the gaps in the anti-fog layer from the form of bound water to the form of semi-bound water. In the anti-fog layer, the hydrophobic group hinders the formation of hydrogen bonds and makes the formed hydrogen bonds easy to dissociate. If the content of the water-absorbent resin is the same, there is no difference in the number of hydroxyl groups that can form hydrogen bonds in the film, but the hydrophobic group reduces the formation rate of hydrogen bonds. Therefore, in the anti-fog layer containing the hydrophobic group, moisture is finally retained in the film in any of the above-mentioned forms, but before being retained, it can diffuse to the bottom of the film in the form of water vapor. In addition, the temporarily retained water is also relatively easy to dissociate, and it is easy to move to the bottom of the film in the form of water vapor. As a result, the distribution of the moisture retention amount in the thickness direction of the film is relatively uniform from near the surface to the bottom of the film. In other words, the anti-fog layer can effectively utilize the entire thickness direction to absorb water supplied to the film surface, so it is difficult for water droplets to condense on the surface, thereby improving the anti-fog property. Moreover, since it is difficult for water droplets to condense on the surface, the anti-fog layer that absorbs water has the characteristic of not being easy to freeze even at low temperatures.

[0245] On the other hand, in the anti-fog layer without a hydrophobic group, the water vapor intruding into the film is very easy to be retained in the form of bound water, semi-bound water or free water. Therefore, the intruded water vapor has a tendency to be retained near the surface of the film. As a result, the water content in the film is very large near the surface, and decreases sharply as it goes to the bottom of the film. In other words, although the bottom of the film can still absorb water, the water near the surface of the film is saturated and condensed into water droplets, so the anti-fog property is limited.

[0246] If a hydrolyzable silicon compound containing a hydrophobic group (see formula (I)) is used to introduce a hydrophobic group into the anti-fog layer, a strong network structure of siloxane bonds (Si-O-Si) is formed. The formation of this network structure is beneficial not only from the perspective of improving abrasion resistance, but also from the perspective of improving hardness, water resistance, etc.

[0247] Preferably, the water repellent group is added to the anti-fog layer surface to a degree that the contact angle of water reaches 70 degrees or more, preferably 80 degrees or more, and more preferably 90 degrees or more. The contact angle of water is measured by adding 4 mg of water drops to the film surface. In particular, when a methyl or ethyl group with slightly weak water repellency is used as the water repellent group, it is preferred to coordinate the water repellent group in an amount that makes the contact angle of water reach the above range to the anti-fog layer. The upper limit of the contact angle of the water droplet is not particularly limited, for example, less than 150 degrees, or for example, less than 120 degrees, and further less than 100 degrees. Preferably, the water repellent group is uniformly contained in the anti-fog layer in a manner that the contact angle of the water droplet reaches the above range in all regions of the anti-fog layer surface.

[0248] In addition, the surface of the anti-fog layer can also be made water-repellent. This can suppress the intrusion of alkali components into the anti-fog layer, and can protect the surface of the glass plate 1 from alkali components.

[0249] The antifogging layer preferably contains a hydrophobic group in an amount of 0.05 parts by mass or more, preferably 0.1 parts by mass or more, more preferably 0.3 parts by mass or more, and 10 parts by mass or less, preferably 5 parts by mass or less, based on 100 parts by mass of the water-absorbing resin.

[0250] (Inorganic Oxides)

[0251] Inorganic oxide is an oxide of at least one element selected from, for example, Si, Ti, Zr, Ta, Nb, Nd, La, Ce and Sn, and contains at least Si oxide (silicon dioxide). The organic-inorganic composite anti-fog layer preferably contains 0.01 parts by weight or more, more preferably 0.1 parts by weight or more, further preferably 0.2 parts by weight or more, particularly preferably 1 part by weight or more, most preferably 5 parts by weight or more, 10 parts by weight or more, 20 parts by weight or more as needed, and preferably 50 parts by weight or less, more preferably 45 parts by weight or less, further preferably 40 parts by weight or less, particularly preferably 35 parts by weight or less, most preferably 33 parts by weight or less, and 30 parts by weight or less inorganic oxide according to the circumstances. Inorganic oxide is a component necessary to ensure the strength of the organic-inorganic composite anti-fog layer, especially the wear resistance, but when its content increases, the anti-fog property of the organic-inorganic composite anti-fog layer decreases.

[0252] (Inorganic oxide particles)

[0253] The organic-inorganic composite anti-fog layer may further contain inorganic oxide particles as at least a portion of the inorganic oxide. The inorganic oxide constituting the inorganic oxide particles is an oxide of at least one element selected from, for example, Si, Ti, Zr, Ta, Nb, Nd, La, Ce and Sn, preferably silica particles. Silica particles, for example, can be introduced into the organic-inorganic composite anti-fog layer by adding colloidal silica. The inorganic oxide particles have excellent effects on transmitting the stress applied to the organic-inorganic composite anti-fog layer to the articles supporting the organic-inorganic composite anti-fog layer, and the hardness is also high. Therefore, from the viewpoint of improving the wear resistance of the organic-inorganic composite anti-fog layer, the addition of inorganic oxide particles is advantageous. In addition, if inorganic oxide particles are added to the organic-inorganic composite anti-fog layer, fine gaps are formed at the position where the particles are in contact or close, and water vapor easily enters the film from these gaps. Therefore, the addition of inorganic oxide particles sometimes also plays a beneficial role in improving anti-fog properties. The inorganic oxide fine particles can be provided to the organic-inorganic composite antifogging layer by adding the inorganic oxide fine particles formed in advance to the coating liquid for forming the organic-inorganic composite antifogging layer.

[0254] When the average particle size of the inorganic oxide particles is too large, the organic-inorganic composite anti-fog layer is sometimes turbid, and when the average particle size is too small, agglomeration occurs and it is difficult to disperse evenly. From this point of view, the average particle size of the inorganic oxide particles is preferably 1 to 20 nm, more preferably 5 to 20 nm. In addition, the average particle size of the inorganic oxide particles is described as a primary particle. In addition, the average particle size of the inorganic oxide particles is determined by measuring the particle size of 50 randomly selected particles by observation using a scanning electron microscope, and the average value is used. When the content of the inorganic oxide particles is too much, the water absorption of the organic-inorganic composite anti-fog layer as a whole is reduced, and the organic-inorganic composite anti-fog layer is likely to become turbid. The inorganic oxide particles can be preferably added to 0 to 50 parts by weight, more preferably 2 to 30 parts by weight, further preferably 5 to 25 parts by weight, and particularly preferably 10 to 20 parts by weight relative to 100 parts by weight of the water-absorbent resin.

[0255] (Hydrolyzable metal compound without a hydrophobic group)

[0256] The anti-fog layer may also contain a metal oxide component from a hydrolyzable metal compound without a hydrophobic group (a hydrolyzable compound without a hydrophobic group). A preferred hydrolyzable metal compound without a hydrophobic group is a hydrolyzable silicon compound without a hydrophobic group. The hydrolyzable silicon compound without a hydrophobic group is at least one silicon compound (without a hydrophobic group) selected from, for example, alkoxysilicon, chlorosilane, acyloxysilane, alkenyloxysilane and aminosilane, preferably an alkoxysilicon without a hydrophobic group. In addition, as alkenyloxysilane, isopropenyloxysilane can be exemplified.

[0257] The hydrolyzable silicon compound having no hydrophobic group may be a compound represented by the following formula (III).

[0258] SiY4(III)

[0259] As described above, Y is a hydrolyzable functional group, and is preferably at least one selected from an alkoxy group, an acyloxy group, an alkenyloxy group, an amino group and a halogen atom.

[0260] The hydrolyzable metal compound without a hydrophobic group is hydrolyzed or partially hydrolyzed, and at least a part of it is polycondensed to provide a metal oxide component in which a metal atom is bonded to an oxygen atom. This component firmly bonds the metal oxide particles and the water-absorbing resin, and helps to improve the wear resistance, hardness, water resistance, etc. of the anti-fog layer. The metal oxide component from the hydrolyzable metal compound without a hydrophobic group is 0 to 40 parts by mass, preferably 0.1 to 30 parts by mass, more preferably 1 to 20 parts by mass, particularly preferably 3 to 10 parts by mass, and can be in the range of 4 to 12 parts by mass depending on the situation.

[0261] A preferred example of a hydrolyzable silicon compound having no hydrophobic group is tetraalkoxysilane, more specifically tetraalkoxysilane having an alkoxy group having 1 to 4 carbon atoms. The tetraalkoxysilane is at least one selected from, for example, tetramethoxysilane, tetraethoxysilane, tetra-n-propoxysilane, tetraisopropoxysilane, tetra-n-butoxysilane, tetraisobutoxysilane, tetra-sec-butoxysilane and tetra-tert-butoxysilane.

[0262] When the content of the metal oxide (silicon dioxide) component derived from tetraalkoxysilane is too large, the anti-fogging property of the anti-fogging layer may be reduced. One of the reasons is that the flexibility of the anti-fogging layer is reduced, and the swelling and shrinkage of the film accompanying the absorption and release of water are limited. The metal oxide component derived from tetraalkylsilane can be added in the range of 0 to 30 parts by mass, preferably 1 to 20 parts by mass, and more preferably 3 to 10 parts by mass relative to 100 parts by mass of the water-absorbent resin.

[0263] Another preferred example of a hydrolyzable silicon compound without a hydrophobic group is a silane coupling agent. A silane coupling agent is a silicon compound having reactive functional groups different from each other. Preferably, a part of the reactive functional groups is a hydrolyzable functional group. A silane coupling agent is, for example, a silicon compound having an epoxy group and / or an amino group and a hydrolyzable functional group. As preferred silane coupling agents, glycidoxyalkyltrialkoxysilane and aminoalkyltrialkoxysilane can be exemplified. In these silane coupling agents, the number of carbon atoms of the alkylene group directly bonded to the silicon atom is preferably 1 to 3. Glycidoxyalkyl and aminoalkyl groups contain functional groups (epoxy groups, amino groups) that show hydrophilicity, and therefore, although they contain alkylene groups, they are not hydrophobic as a whole.

[0264] The silane coupling agent firmly combines the water-absorbing resin as an organic component and the metal oxide particles as an inorganic component, etc., and helps to improve the wear resistance, hardness, water resistance, etc. of the anti-fog layer. However, when the content of the metal oxide (silicon dioxide) component derived from the silane coupling agent is too large, the anti-fog property of the anti-fog layer is reduced, and in some cases, the anti-fog layer becomes cloudy. The metal oxide component derived from the silane coupling agent can be added in the range of 0 to 10 parts by mass, preferably 0.05 to 5 parts by mass, and more preferably 0.1 to 2 parts by mass relative to 100 parts by mass of the water-absorbing resin.

[0265] (Cross-linked structure)

[0266] The anti-fog layer may contain a cross-linked structure from a cross-linking agent, preferably from at least one cross-linking agent selected from an organic boron compound, an organic titanium compound, and an organic zirconium compound. The introduction of the cross-linked structure improves the wear resistance, scratch resistance, and water resistance of the anti-fog layer. From another point of view, the introduction of the cross-linked structure makes it easy to improve the durability of the anti-fog layer without reducing the anti-fog performance of the anti-fog layer.

[0267] When a cross-linked structure derived from a cross-linking agent is introduced into an anti-fogging layer whose metal oxide component is a silicon dioxide component, the anti-fogging layer may contain metal atoms other than silicon as metal atoms together with silicon, preferably boron, titanium or zirconium.

[0268] The type of the crosslinking agent is not particularly limited as long as it can crosslink the water-absorbing resin used. Here, only examples of organic titanium compounds are listed. The organic titanium compound is at least one selected from, for example, alkoxy titanium, chelated titanium compounds and acylated titanium. Alkoxy titanium is, for example, tetraisopropoxy titanium, tetra-n-butoxy titanium, tetraoctoxy titanium. Chelated titanium compounds are, for example, titanium acetylacetonate, ethyl titanium acetoacetate, titanium octanediol, triethanolamine titanium, and titanium lactate. Titanium lactate can also be an ammonium salt (ammonium titanium lactate). Acylated titanium is, for example, stearoyl titanium. Preferred organic titanium compounds are chelated titanium compounds, especially titanium lactate.

[0269] When the water-absorbent resin is polyvinyl acetal, the preferred crosslinking agent is an organic titanium compound, particularly titanium lactate.

[0270] (Other optional ingredients)

[0271] Other additives may also be added to the anti-fog layer. As additives, polyols such as glycerol and ethylene glycol that have the function of improving anti-fog properties may be cited. The additives may be surfactants, leveling agents, ultraviolet absorbers, colorants, defoamers, preservatives, etc.

[0272] (basal layer)

[0273] The anti-fog layer can be directly laminated on each functional layer 3, 4, or a base layer can be formed on each functional layer 3, 4, and the anti-fog layer can be laminated on the base layer. In this way, the anti-fog layer is laminated on each functional layer 3, 4 via the base layer, so that the anti-fog layer is not easy to peel off. The base layer can be made of, for example, a silane coupling agent.

[0274] (thickness)

[0275] The thickness of the organic-inorganic composite anti-fog layer can be appropriately adjusted according to the desired anti-fog properties and other properties. The thickness of the organic-inorganic composite anti-fog layer is preferably 1 to 20 μm, more preferably 2 to 15 μm, further preferably 2 to 12 μm, and particularly preferably 3 to 10 μm. If the thickness of the anti-fog layer is 1 μm or more, a sufficient anti-fog effect can be achieved. On the other hand, when the anti-fog layer is too thick, the reflected image may be deformed due to uneven film thickness. In addition, the anti-fog layer is formed by the resin material as described above and has a birefringence, so when it is too thick, the image may be blurred.

[0276] <3-2. Method for forming anti-fog layer>

[0277] The method for forming the antifogging layer having the above composition is not particularly limited, and the antifogging layer can be formed, for example, by the following method.

[0278] First, the organic-inorganic composite antifogging layer coating liquid (antifogging layer solution) is prepared, and then the coating liquid is applied to the substrate 1 using a coater and then dried in a first heating furnace.

[0279] When applying the coating liquid, it is preferred to keep the relative humidity of the atmosphere less than 60%, and further less than 40%. When the relative humidity is kept low, it is possible to prevent the organic-inorganic composite anti-fog layer from excessively absorbing moisture from the atmosphere. If a large amount of moisture is absorbed from the atmosphere, the water that enters the matrix of the organic-inorganic composite anti-fog layer and remains therein may reduce the strength of the film.

[0280] In the first heating furnace, heating is preferably performed at 200°C or less, for example, 50 to 150°C. The heating time is preferably 1 to 20 minutes, more preferably 2 to 10 minutes. In addition, the heating can be performed multiple times. For example, heating can be performed twice or more for 3 to 5 minutes. In this way, the coating liquid is baked, and a cross-linked structure is formed by the water-absorbent resin and Si. However, this is not a strong cross-linked structure of the coating liquid that is completely baked, but a temporary anti-fog layer.

[0281] Then, the substrate dried as described above is immersed in a water tank. As a result, the anti-fog layer swells on the substrate 1, and some crosslinking points are cut. In addition, impurities such as Na and Cl contained in the water-absorbent resin are removed. In addition, the uncrosslinked water-absorbent resin composition is also removed. The water stored in the water tank can be set to, for example, 10 to 80°C, more preferably 20 to 60°C, and particularly preferably 25 to 50°C. The temperature of the water can also be less than 10°C, but when it is lower than 10°C, the effect of removing the alkali component may be reduced. On the other hand, when it is higher than 80°C, the amount of water vapor evaporated from the water tank increases, and the load on the equipment and the working environment may increase. From the above viewpoints, in order to maintain a high effect of removing alkali components and reduce the load on the equipment and the environment, the water temperature is particularly preferably 25 to 50°C. In addition, the time of immersion in the water tank can be, for example, 1 to 30 minutes, more preferably 3 to 20 minutes, and particularly preferably 3 to 10 minutes. Even when the water temperature is low and the alkali component removal efficiency is low as described above, the alkali component can be removed to a sufficient degree by extending the immersion time. However, when the immersion time is long, the production efficiency decreases, so the immersion time is particularly preferably 3 to 10 minutes. According to the above, it can be immersed in water at 25 to 50° C. for about 3 to 10 minutes. In addition, the water treatment can also be performed multiple times. In this way, by performing multiple water treatments, there is no need to enlarge the water tank, and even a small water tank can achieve the effect described later.

[0282] Next, the substrate 1 is heated in a second heating furnace. In the second heating furnace, the swollen anti-fog layer is baked, and the cross-linked structure formed by the water-absorbing resin and Si remaining in the anti-fog layer is strengthened. The heating temperature of the heating furnace is the same as that of the first heating furnace, preferably set to 200°C or less, for example, 50 to 150°C. In addition, the heating time is preferably longer than that of the first heating furnace, for example, 3 to 60 minutes, more preferably 5 to 30 minutes. In this way, the anti-fog layer is fully burned and the anti-fog layer is completed.

[0283] <3-3. Anti-fog layer having a hydrophilic layer>

[0284] The above-mentioned anti-fog layer mainly has a hygroscopic function, but a hydrophilic layer may be further formed on the anti-fog layer (hygroscopic layer).

[0285] The hydrophilic layer may have various structures, and may contain, for example, a polyether-modified dimethylsiloxane represented by the following formula (A).

[0286]

[0287] wherein m, n, x and y are independently integers greater than 1, R 1 is a hydrogen atom or a methyl group, R 2 It is an alkyl group having 1 to 3 carbon atoms.

[0288] Furthermore, in the above formula (A), the following structure is also possible.

[0289] (1) The average molecular weight of the polyether-modified dimethylsiloxane may be 3,000 to 300,000.

[0290] (2) m may be an integer of 2 or 3. In other words, the connecting part between the silicone main chain and its side chain and the polyether side chain is an ethylene group or a propylene group. Such a polyether-modified dimethylsiloxane can be obtained by allowing a dimethylpolysiloxane in which a part of the methyl groups of the dimethylpolysiloxane main chain are substituted with hydrogen atoms to undergo an addition reaction with a polyether having a vinyl group at the end.

[0291] (3) The degree of polymerization n of the polyether side chain may be an integer of 3 to 600. In other words, as polyethylene glycol, the molecular weight is about 200 to 20,000 (the degree of polymerization is about 4 to 400).

[0292] (4) The modification ratio y / (x+y) may be 0.01 or more and less than 1. In other words, one or more of 100 siloxane units may be modified, or all of them (except both ends) may be modified.

[0293] The method for forming the hydrophilic layer as described above can be appropriately adopted by a conventionally known method. For example, polyether-modified dimethylsiloxane is directly or diluted with a solvent that can dissolve it, immersed in cotton cloth, and then the cotton cloth is used to wipe the anti-fog layer to apply it on the anti-fog layer. In addition, the diluent can be applied to the anti-fog layer by spraying, flow coating, etc., and the solvent is evaporated and dried.

[0294] By forming such a hydrophilic layer, the following effects can be achieved. For example, when the moisture absorption of the hygroscopic anti-fog layer progresses and reaches a saturated state, water vapor adheres to the hydrophilic layer and forms a water film on the surface of the hydrophilic layer due to its hydrophilic property. Therefore, after the anti-fog layer reaches a saturated state, although a water film is formed, fogging caused by water droplets can be suppressed.

[0295] <3-4. Anti-fog layer with hydrophilic function>

[0296] Next, the anti-fog layer having a hydrophilic function is described. The anti-fog layer described in the above Item 3-3 is a separate hydrophilic layer, but the anti-fog layer in this item has a hydrophilic function and is formed as a single layer.

[0297] The anti-fog layer is dispersed with a hydrophilic agent inside the above-mentioned anti-fog layer with a hygroscopic function. As a result, the hydrophilicity of the anti-fog layer surface becomes good. That is, even if the above-mentioned water-absorbing resin is saturated with water, a water film can be formed on the surface of the anti-fog layer to maintain the anti-fog property. In addition, in the case where a hydrophilic layer is formed separately on the anti-fog layer as described above, since the apparent refractive index of the hydrophilic layer is higher than that of the anti-fog layer, a glare phenomenon (ギラツキ) may occur. On the other hand, if the hydrophilic agent is dispersed inside the anti-fog layer, the glare phenomenon can be suppressed. Moreover, when the hydrophilic agent is dispersed in the anti-fog layer, even if the hydrophilic agent on the surface is removed due to reasons such as wiping, the hydrophilic agent inside appears on the surface, and the hydrophilic property can be maintained. In addition, as a hydrophilic agent, there is no particular limitation, for example, any one of anionic surfactants, cationic surfactants, nonionic surfactants, and amphoteric surfactants can be used. As an anionic surfactant, for example, sodium dialkyl sulfosuccinate can be used.

[0298] The anti-fog layer may contain a solvent with a high boiling point, for example, a solvent with a boiling point of more than 100°C and less than 300°C. Thus, when the anti-fog layer is formed, for example, the solvent can be dispersed in the anti-fog layer even if it is baked at more than 100°C. Moreover, since the hydrophilic agent is dissolved in the solvent, the hydrophilic agent can be dispersed in the anti-fog layer. In addition, since the resin containing organic materials will yellow and thermally decompose, the heat-resistant temperature is usually below 300°C. Therefore, when a solvent with a boiling point higher than 300°C is used, when baking is performed below 300°C, the solvent may remain in the anti-fog layer excessively. Therefore, the boiling point of the solvent used here is preferably below 300°C. Such a solvent preferably has an alcohol group, thereby making it easy to disperse the hydrophilic agent in the solvent. Specifically, for example, propylene glycol, polyethylene glycol, triethylene glycol or glycerol can be used.

[0299] The anti-fog layer as described above can be formed, for example, as follows. First, the coating liquid for the organic-inorganic composite anti-fog layer is made to contain the above-mentioned solvent and the hydrophilic agent to generate an anti-fog layer solution. Then, the anti-fog layer solution is applied to the substrate 1 by spin coating, roller coating, spraying or the like. Next, after air-cooling and drying, it is baked in a heating furnace. Then, after air cooling at room temperature, an anti-fog layer is made. The anti-fog layer contains a hydrophilic agent inside, so an anti-fog layer can be formed by performing the coating process and the baking process once respectively. Therefore, the manufacturing time can be greatly shortened. In addition, the addition ratio of the high boiling point solvent in the above-mentioned coating liquid is preferably, for example, 0.1 to 40% by mass, and the addition ratio of the hydrophilic agent is preferably, for example, 0.01 to 1.0% by mass.

[0300] <3-5. Anti-fog layer with inorganic compounds as the main component>

[0301] <3-5-1. Composition of anti-fog layer>

[0302] Next, the anti-fog layer with inorganic compounds as the main component is described. Since the anti-fog layer has concavo-convex on the surface, it can exert anti-fog performance by forming a water film on the surface under high humidity conditions. That is, it functions as a so-called hydrophilic anti-fog layer. In addition, by forming such concavo-convex, the refractive index can be reduced in appearance, and the reflection of the surface can be suppressed.

[0303] Such an anti-fog layer may contain, for example, inorganic particles and inorganic adhesives. In addition, it may also contain photocatalyst particles. By containing photocatalyst particles, hydrocarbons or organic dirt accumulated on the surface of the anti-fog layer are decomposed, and a water film is easily formed. For example, once hydrocarbons or organic dirt accumulate on the surface of the anti-fog layer, the contact angle becomes high, and when water droplets adhere, optical deformation may occur. In contrast, if photocatalyst particles are added, since the dirt on the surface is decomposed, the optical deformation caused by water adhesion can be suppressed.

[0304] The inorganic fine particles may be formed of, for example, SiO2, ZrO2, CeO2, ZnO, Al2O3, Nb2O5, Y2O3, or MgO. The particle size of the inorganic fine particles is preferably, for example, 1 to 500 nm, more preferably 5 to 200 nm, or 10 to 150 nm. When the particle size of the inorganic fine particles increases, the haze rate increases, which is not preferred.

[0305] The inorganic binder may contain a metal oxide component derived from a hydrolyzable metal compound. A preferred hydrolyzable metal compound is a hydrolyzable silicon compound having no hydrophobic group. The hydrolyzable silicon compound having no hydrophobic group is at least one silicon compound (which has no hydrophobic group) selected from, for example, alkoxysilicon, chlorosilane, acyloxysilane, alkenyloxysilane and aminosilane, preferably an alkoxysilicon having no hydrophobic group. In addition, as alkenyloxysilane, isopropenyloxysilane can be exemplified.

[0306] The hydrolyzable silicon compound having no hydrophobic group may be a compound represented by the following formula (III).

[0307] SiY4(III)

[0308] As described above, Y is a hydrolyzable functional group, and is preferably at least one selected from an alkoxy group, an acyloxy group, an alkenyloxy group, an amino group, and a halogen atom.

[0309] The hydrolyzable metal compound without a hydrophobic group undergoes hydrolysis or partial hydrolysis, and then at least a part of it is polycondensed to provide a metal oxide component in which metal atoms and oxygen atoms are bonded. This component allows the inorganic particles or photocatalyst particles to be firmly bonded to the substrate or substrate film, which helps to improve the wear resistance, hardness, water resistance, etc. of the anti-fog layer.

[0310] A preferred example of a hydrolyzable silicon compound having no hydrophobic group is tetraalkoxysilane, more specifically tetraalkoxysilane having an alkoxy group having 1 to 4 carbon atoms. Tetraalkoxysilane is at least one selected from, for example, tetramethoxysilane, tetraethoxysilane, tetra-n-propoxysilane, tetraisopropoxysilane, tetra-n-butoxysilane, tetraisobutoxysilane, tetra-sec-butoxysilane and tetra-tert-butoxysilane.

[0311] Another preferred example of a hydrolyzable silicon compound without a hydrophobic group is a silane coupling agent. A silane coupling agent is a silicon compound having reactive functional groups different from each other. Preferably, a part of the reactive functional groups is a hydrolyzable functional group. A silane coupling agent is a silicon compound having, for example, an epoxy group and / or an amino group and a hydrolyzable functional group. As preferred silane coupling agents, glycidoxyalkyltrialkoxysilane and aminoalkyltrialkoxysilane can be exemplified. In these silane coupling agents, the number of carbon atoms of the alkylene group directly bonded to the silicon atom is preferably 1 to 3. Glycidoxyalkyl and aminoalkyl groups contain functional groups (epoxy groups, amino groups) showing hydrophilicity, and therefore, although they contain alkylene groups, they are not hydrophobic as a whole.

[0312] The photocatalyst particles may be formed of, for example, an oxide or oxynitride containing any element of titanium, tungsten, or iron as a main component. The particle size of the photocatalyst particles is preferably, for example, 1 to 50 nm, more preferably 2 to 20 nm, and even more preferably 5 to 10 nm.

[0313] The content of inorganic particles is preferably, for example, 0% by mass or more and 60% by mass or less, more preferably 10% by mass or more and 50% by mass or less, further preferably 20% by mass or more and 40% by mass or less, and particularly preferably 20% by mass or more and 28% by mass or less. In addition, the content of inorganic binder is preferably, for example, 20% by mass to 70% by mass or less, more preferably 30% by mass or more and 50% by mass or less. Moreover, the content of photocatalyst particles is preferably, for example, 10% by mass or more and 50% by mass or less, more preferably 20% by mass or more and 40% by mass or less. In addition, it may also be an anti-fogging layer that does not contain inorganic particles and contains inorganic binder and photocatalyst particles.

[0314] The thickness of the anti-fog layer is preferably, for example, 10 to 500 nm, more preferably 20 to 250 nm, and further preferably 50 to 200 nm. In particular, the film thickness of the anti-fog layer is preferably less than 2 times the particle size of the inorganic particles. When the thickness of the anti-fog layer is more than 2 times the particle size of the inorganic particles, the inorganic particles overlap each other in the film thickness direction, and the bonding between the inorganic particles becomes weak, so the scratch resistance is likely to become weak.

[0315] <3-5-2. Optical properties of transparent laminate>

[0316] The visible light transmittance of the cover component having the anti-fog layer as described above is preferably 85% or more, more preferably 88% or more. In particular, the minimum value of the transmittance in the visible light wavelength region is preferably within ±5% of the transmittance of the substrate, and more preferably within ±2%. On the other hand, the visible light reflectance of the cover component is preferably less than 10%, and more preferably less than 7%. In particular, the maximum value of the reflectance in the visible light wavelength region is preferably within ±5% of the reflectance of the substrate, and more preferably within ±2%. Moreover, it is preferred that the reflectance in the visible light wavelength region of the cover component satisfies: 1≤maximum reflectance / minimum reflectance≤1.5. The reflection curve acts on the hue of the transparent laminate. That is, when the reflectance at a certain specific wavelength is large, a colored cover component is formed, which may not be acceptable depending on the application, but when the above formula is satisfied, the hue can be suppressed. In addition, the maximum reflectance / minimum reflectance can be adjusted by changing the film thickness and composition of the anti-fog layer.

[0317] The haze ratio of the transparent laminate is preferably 1.0 or less, more preferably 0.5 or less, and particularly preferably 0.3 or less. Thus, the transparent laminate can be suitably used for a cover member of a camera or the like.

[0318] <3-6. Other forms of anti-fog layer>

[0319] Although the anti-fog layer is directly laminated on the substrate 1 in the above example, an anti-fog sheet may also be attached. The anti-fog sheet comprises a sheet-shaped transparent substrate film, the anti-fog layer laminated on one surface of the substrate film, and a transparent adhesive layer laminated on the other surface of the substrate film. Then, the anti-fog sheet can be fixed by fixing the adhesive layer on the first main surface 11 of the substrate 1.

[0320] The substrate film may be formed of a transparent resin sheet such as polyethylene or polyethylene terephthalate. The thickness of the substrate film may be, for example, 75 to 100 μm. The adhesive layer may be formed of, for example, an acrylic or silicone adhesive layer.

[0321] In addition, the substrate film may not be used. First, a release film is prepared, and an anti-fog layer and an adhesive layer are laminated in sequence on the release film. Then, after the adhesive layer is pasted on the first main surface 11 of the substrate 1, the release film is removed, thereby laminating the adhesive layer and the anti-fog layer on the substrate 1 in sequence. Therefore, in the case of this mode, the substrate film is not required, and the deformation caused by the substrate film can be eliminated. In addition, a protective film may be pasted on the adhesive layer in advance, and when in use, after the protective film is removed, the adhesive layer is pasted on the substrate.

[0322] <3-7. Surface roughness>

[0323] The surface roughness Ra of the anti-fog layer can be set to, for example, 1 to 1000 nm, more preferably 10 to 1000 nm. By making the surface roughness Ra above 1 nm, an anti-reflection effect can be achieved. In particular, the anti-reflection effect is large in the visible light band with a wavelength of 400 to 800 nm. However, when the surface roughness Ra is greater than 1000 nm, light scattering may occur, so it is not preferred.

[0324] <4. Application>

[0325] The cover member as described above can be used for various purposes. Figure 2 As shown, a cover part 10 can be used as a cover for the lens 51 of the camera device 5. In this case, the cover part 10 can be appropriately mounted on a bracket 6 for mounting to the lens. And, a closed space is formed in front of the lens by the cover part 10 and the bracket 6. In this case, the first main surface 11 of the substrate 1 of the cover part 10 faces the closed space. Therefore, since the first functional layer 2 is laminated on the first main surface 11, fogging of the first main surface 11 caused by the temperature difference or air pressure difference between the closed space and the outside can be suppressed. Therefore, it is possible to prevent the cover part 10 from fogging and causing obstacles to photography.

[0326] Such a camera device can be used, for example, Figure 3 As shown, the monitoring camera of a bullet type or dome type is provided with a camera device 5 in a housing 7 and is isolated from the outside air by the housing 7 and a cover member 10. In this case, the cover member 10 is arranged in front of the lens of the camera device 5. Such a monitoring camera generates a temperature difference across the cover member 10 due to heat release of the camera device 5 and changes in the surrounding environment. Therefore, the cover member 10 is in an environment where condensation and fogging are likely to occur.

[0327] Furthermore, an imaging device mounted on an aircraft whose surrounding air pressure changes significantly is also susceptible to condensation due to changes in air pressure. As described above, the cover member 10 of this embodiment can be suitably used as a cover member for a monitoring camera or an apparatus mounted on an aircraft.

[0328] Furthermore, the present invention is not limited to use in places with large environmental changes as described above, and can also be used as a cover member of an imaging device mounted on a mobile device such as a car, or a cover member of a general imaging device.

[0329] In particular, as described later, a transparent laminate having an anti-fog layer with the above-mentioned inorganic compound as the main component not only has excellent anti-fog performance, but also has excellent peeling, weather resistance and water resistance of the anti-fog layer. Therefore, it can be suitable for use as a cover component of various cameras such as surveillance cameras used outdoors. In addition, if the anti-fog layer contains photocatalyst particles, it can decompose organic dirt attached to the surface of the anti-fog layer when irradiated with ultraviolet rays, and restore the anti-fog performance. As such a cover component, the anti-fog layer can be laminated on any surface of the substrate. That is, it can be any side of the lens side or the external side of the camera. When the anti-fog layer is laminated on the lens side of the camera, it is preferred that an irradiation device for irradiating ultraviolet rays toward the anti-fog layer is provided in the surveillance camera. Thereby, organic dirt attached to the anti-fog layer can be forcibly decomposed when necessary.

[0330] <5. Others>

[0331] In the above example, since the first main surface 11 of the substrate 1 faces the lens side of the camera of the imaging device, the second main surface 12 is exposed to the outside air. Therefore, in order to prevent water droplets from adhering to the second main surface 12, for example, a water-repellent layer or a hydrophilic layer (third functional layer) may be formed on the second main surface 12. The water-repellent layer and the hydrophilic layer may be formed by applying a known water-repellent film or a hydrophilic film. This is also true in the second embodiment described later.

[0332] [Example]

[0333] (1. Anti-fog layer composed of organic and inorganic composite film)

[0334] The following is an example of the first embodiment, which describes an example having an anti-fogging layer composed of an organic-inorganic composite film as the first functional layer. However, the present invention is not limited to the following examples.

[0335] As Example 1, the following cover member was produced.

[0336] (1) Substrate: Float glass with a thickness of 1.1 mm was used.

[0337] (2) First functional layer: An antifogging layer described below is formed on the first main surface of the substrate.

[0338] (i) Preparation of anti-fog layer coating liquid

[0339] A solution containing a polyvinyl acetal resin ("S-LEC KX-5" manufactured by Sekisui Chemical Co., Ltd., solid content 8 mass%, degree of acetalization 9 mol%, containing an acetal structure derived from benzaldehyde) 62.5 mass% of n-hexyltrimethoxysilane (HTMS, "KBM-3063" manufactured by Shin-Etsu Chemical Co., Ltd.), 0.37 mass% of tetraethoxysilane (TEOS, "KBE-04" manufactured by Shin-Etsu Chemical Co., Ltd.), 1.04 mass% of alcohol solvent ("SOLMIX AP-7" manufactured by Nippon Alcohol Industries), 15.63 mass% of purified water, 0.01 mass% of hydrochloric acid as an acid catalyst, and 0.01 mass% of a leveling agent ("KP-341" manufactured by Shin-Etsu Chemical Co., Ltd.) were placed in a glass container and stirred at room temperature (25°C) for 3 hours to prepare a coating liquid for forming an antifogging layer.

[0340] (ii) Anti-fog layer film forming process

[0341] First, the antifogging coating liquid prepared as described above was applied to the substrate and heated in a heating furnace at 90°C for 5 minutes. Then, the substrate was immersed in water at 50°C for 10 minutes and heated in a heating furnace at 110°C for 10 minutes. In this way, the moisture absorption layer of the antifogging layer was formed.

[0342] Then, polyether-modified dimethylsiloxane (BYK-333 manufactured by BYK-Chemie Japan KK) was diluted to 1 wt% with an alcohol mixed solvent (SOLMIX AP-7 manufactured by Japan Alcohol Trading CO., LTD) to prepare a coating solution, which was applied by flow coating so that the entire water supply film of the inclined substrate was wetted, and then dried as it was. In this way, a hydrophilic layer was formed. In addition, the film thickness of the hydrophilic layer was 10 nm.

[0343] (2. Anti-fog layer with inorganic compounds as the main component)

[0344] Next, an example of a cover member having an anti-fogging layer having an inorganic compound as a main component as the first functional layer will be described.

[0345] As a substrate, a float glass having a thickness of 1.1 mm was prepared, and an antifogging layer having the following composition was formed on one surface thereof: The antifogging layer was coated with an antifogging layer coating liquid by spin coating (rotation speed 3000 rpm), and then baked under the following conditions.

[0346] [Table 1]

[0347]

[0348] The cover members of Examples 1 to 11 formed as described above were subjected to the following tests.

[0349] (2-1. Anti-fog performance test)

[0350] Hot water at 80 to 100° C. was placed in a container, and a cover member was placed 5 cm from the surface of the hot water with the anti-fog layer facing the water surface. Then, evaluation was performed as follows.

[0351] A: A uniform water film is formed on the anti-fog layer within 3 to 5 seconds.

[0352] B: A water film is formed on the anti-fog layer within 3 to 5 seconds, but deformation is visible.

[0353] C: The anti-fog layer fogs up within 3 seconds.

[0354] In addition, irradiation of 60 mW / cm 2 After 10 minutes of ultraviolet light, the anti-fog performance test was carried out again. The results are as follows.

[0355] [Table 2]

[0356] Anti-fog performance Anti-fog performance after UV exposure Example 1 A - Example 2 A - Example 3 A - Example 4 C A Example 5 C A Example 6 C A Example 7 A - Example 8 A - Example 9 A - Example 10 A - Embodiment 11 A -

[0357] The content of SiO2 particles in Examples 4 to 6 is small, so the anti-fogging performance is low. However, after irradiation with ultraviolet rays, the dirt on the surface is decomposed, so the same anti-fogging performance as Examples 1 to 3 and 7 to 11 can be achieved, so it is considered that it is sufficient to withstand practical use. In addition, 60mW / cm 2 The intensity of ultraviolet rays is higher than that of sunlight, but this is an accelerated test. Therefore, it is believed that even if the intensity is 1mW / cm 2 As long as the ultraviolet rays are irradiated for a long time, Examples 4 to 6 can also achieve anti-fogging performance. This is also the case in the tests described below.

[0358] (2-2. Wear test)

[0359] As a cloth, Toraysee manufactured by Toray Industries, Ltd. impregnated with alcohol (A-10 manufactured by Futaba Chemicals Co., Ltd.) was prepared, and the cloth was pressed against the anti-fog layer of each example with a load of 300 g, and was moved back and forth 10 times at a distance of 5 cm. In addition, while performing the above anti-fog performance test, it was visually confirmed whether the anti-fog layer peeled off. In addition, after irradiation for 20 minutes at 60 mW / cm 2 After the UV rays were applied, the anti-fog performance test was conducted again. The results are as follows.

[0360] [Table 3]

[0361] Anti-fog performance Anti-fog performance after UV exposure Stripping Example 1 C A (remaining part of anti-fog layer) have Example 2 C A (remaining part of anti-fog layer) have Example 3 C A (remaining part of anti-fog layer) have Example 4 C A none Example 5 C A none Example 6 C A none Example 7 A - none Example 8 A - none Example 9 A - none Example 10 A - none Embodiment 11 A - none

[0362] In Examples 1 to 3, the anti-fog layer was confirmed to peel off by the wear test. This is believed to be due to the high content of SiO2 particles. However, as in Examples 7 to 9, even if the content of SiO2 particles is high, it is believed that a strong anti-fog layer in which the SiO2 particles are fully cross-linked is formed under high-temperature calcination, and no peeling is observed. Therefore, it can be seen that, for example, even if the anti-fog layer is wiped to remove dirt, the anti-fog layer is prevented from peeling off in Examples 4 to 11 in particular.

[0363] Regarding the anti-fog performance, it can be considered that since the baking temperature of Examples 1 to 6 is low, the organic matter contained in the SiO2 binder remains on the surface of the anti-fog layer, so the surface contact angle becomes high and the anti-fog performance cannot be exerted. On the other hand, since the baking temperature of Examples 7 to 11 is high, the organic matter contained in the SiO2 binder is removed from the surface by thermal decomposition, and the anti-fog performance is exerted. It can also be considered that in such a durability test, hydrocarbons adhere to the surface of the anti-fog layer, organic residues from the SiO2 binder appear on the surface of the anti-fog layer, and the anti-fog layer is contaminated, thereby deteriorating the anti-fog performance.

[0364] (2-3. Weather resistance test)

[0365] The cover parts of each example were placed in a thermostatic chamber at a temperature of 80°C and a humidity of 80% for 48 hours. Then, the above-mentioned anti-fog performance test was performed. Furthermore, 1 mW / cm 2 The time until the anti-fogging performance of the above-mentioned evaluation A is exhibited is measured. The evaluation of this time is as follows.

[0366] P: Less than 10 hours

[0367] Q: 10 to 30 hours

[0368] R: More than 30 hours

[0369] The result is shown below.

[0370] [Table 4]

[0371] Anti-fog performance Anti-fog performance after UV exposure Example 1 C Q Example 2 C Q Example 3 C Q Example 4 C R Example 5 C R Example 6 C R Example 7 C Q Example 8 C Q Example 9 C Q Example 10 C Q Embodiment 11 C P

[0372] In the anti-fog performance test after taking out the cover component from the constant temperature chamber, the anti-fog performance of Examples 1 to 11 was low (evaluation C). On the other hand, after irradiation with ultraviolet rays, although the anti-fog performance in Examples 1 to 3 and 7 to 11 was improved, the anti-fog performance of Examples 4 to 6 was still low. This can be considered to be due to the high content of inorganic binder. In addition, the inventors found that in Examples 1 to 3, although not described in detail in Table 4, the higher the content of TiO2 particles, the shorter the time until the anti-fog performance is exhibited. That is, compared with Example 1, the time until the anti-fog performance is exhibited in Examples 2 and 3 after ultraviolet irradiation is shorter. Therefore, it can be seen that, for example, when the present invention is used as a cover component of a surveillance camera, even in an outdoor high temperature and high humidity environment, as long as ultraviolet rays are irradiated, high anti-fog performance is generally exhibited.

[0373] (2-4. Immersion test)

[0374] The cover member of each example was immersed in water (20°C ± 5°C) for 180 hours. Then, the above-mentioned anti-fog performance test was performed. The results are shown below.

[0375] [Table 5]

[0376] Anti-fog performance Example 1 A,B Example 2 A,B Example 3 A,B Example 4 A,B Example 5 A,B Example 6 A,B Example 7 A Example 8 A Example 9 A Example 10 A Embodiment 11 A

[0377] The evaluation "A, B" of Examples 1 to 5 indicates that a region with the evaluation of B exists in part of the antifogging layer, but all of them are known to have high antifogging performance. Therefore, it is considered that the cover member of the present invention is suitable for outdoor use such as being exposed to rain.

[0378] According to the above test results, Examples 1 to 11 are suitable for outdoor use. In particular, Examples 8 to 11 have high anti-fog performance even in harsh environments.

[0379] (2-5. Transmittance)

[0380] The transmittance of the cover parts and the substrate of Examples 1 to 3 was measured based on JIS R3106. Figure 4 As shown. Figure 4 As shown, in the wavelength region of visible light (about 380 to 780 nm), Examples 1 to 3 show a transmittance of about 89% or more. In particular, considering that the transmittance of the substrate as the glass plate is about 91%, the transmittance of Examples 1 to 3 is within ±2% of the substrate transmittance, indicating that they show high transmittance.

[0381] (2-6. Reflectivity)

[0382] The reflectance of the cover parts and substrates of Examples 1 to 3 was measured based on JIS R3106. Figure 5 As shown. Figure 5As shown, in the wavelength region of visible light (about 380 to 780 nm), Examples 1 to 3 show a reflectivity of about 6 to 8%. In particular, considering that the reflectivity of the substrate as the glass plate is about 8 to 9%, Examples 1 to 3 are about 2% lower than the reflectivity of the substrate, and thus show low reflectivity.

[0383] (3. Anti-fog layer with hydrophilic function)

[0384] Next, Examples 12 to 20 of the cover member having the anti-fogging layer having the hydrophilic function as the first functional layer are described.

[0385] As a substrate, a float glass with a thickness of 1.1 mm was prepared, and an antifog layer was formed on one surface thereof. The antifog layer was coated with the antifog layer coating liquid described below by spin coating, and after air cooling for 10 minutes, it was baked in a heating furnace. In the heating furnace, it was baked at 100°C for 30 minutes. Then, the antifog layer was formed by air cooling at room temperature. The thickness of the antifog layer was about 10 μm.

[0386] The coating liquid for the anti-fog layer was prepared as follows. A solution containing a polyvinyl acetal resin (60.24 mass % (solid content concentration 5.0 mass %), a high boiling point solvent (shown in Table 6) 20.0 mass %, 3-glycidoxypropyltrimethoxysilane (GPTMS, Shin-Etsu Chemical Co., Ltd. "KBM-403") 0.28 mass % (solid content concentration 0.2 mass %), tetraethoxysilane (TEOS, Shin-Etsu Chemical Co., Ltd. "KBE-04") 1.04 mass % (solid content concentration 0.30 mass %), an alcohol solvent (Nippon Alcohol Co., Ltd. "SOLMIX In a glass container, 6.32 mass% of ALP-7”), 11.87 mass% of purified water, 0.10-0.40 mass% of a surfactant (“RAPISOL” manufactured by NOF Corporation) (solid content concentration 0.10-0.40 mass%, refer to Table 6), 0.01 mass% of hydrochloric acid as an acid catalyst, 0.01 mass% of a leveling agent (“KP-341” manufactured by Shin-Etsu Chemical Co., Ltd.), 0.01 mass% of a leveling agent (“KP-112” manufactured by Shin-Etsu Chemical Co., Ltd.), 0.01 mass% of a leveling agent (“DOWSIL 8526 Additive” manufactured by Dow Chemical Japan Co., Ltd.), and 0.01 mass% of a leveling agent (“BKY-349” manufactured by BYK-Chemie Japan) were placed and stirred at room temperature (25°C) for 3 hours to prepare a coating liquid for an anti-fogging layer.

[0387] As the high boiling point solvent, propylene glycol (PG), polyethylene glycol (PEG) and triethylene glycol (TEG) were used. The anti-fogging layer coating liquids of Examples 12 to 20 contained the following high boiling point solvents (unit: mass %).

[0388] [Table 6]

[0389] PG PEG TEG Surfactants Example 12 20 0 0 0.1 Embodiment 13 20 0 0 0.2 Embodiment 14 20 0 0 0.4 Embodiment 15 0 5 0 0.2 Example 16 15 5 0 0.2 Embodiment 17 0 0 5 0.2 Embodiment 18 0 0 10 0.2 Embodiment 19 15 0 5 0.2 Embodiment 20 10 0 10 0.2

[0390] The antifogging layer formed as described above was subjected to the following tests.

[0391] (3-1 Anti-fog performance test)

[0392] Place hot water at 80-100°C in a container, and place a cover component 5 cm away from the water surface with the anti-fog layer facing the water surface. Then, check whether there is no fogging for more than 10 seconds (anti-fog performance), whether a water film is formed within 1 second, and whether there are any problems with the appearance. In the appearance inspection, visually observe whether the surface of the anti-fog layer is smooth and whether there are any deformations or stripes. The results are as follows, and "OK" means there is no problem.

[0393] [Table 7]

[0394] Anti-fog performance Water film Appearance Example 12 OK OK OK Embodiment 13 OK OK OK Embodiment 14 OK OK OK Embodiment 15 OK OK OK Example 16 OK OK OK Embodiment 17 OK OK OK Embodiment 18 OK OK OK Embodiment 19 OK OK OK Embodiment 20 OK OK OK

[0395] From the above results, it can be seen that the anti-fog layers of Examples 12 to 20 exhibit sufficient anti-fog performance.

[0396] (3-2 Wear test)

[0397] As a cloth, Toraysee manufactured by Toray Industries, Ltd. impregnated with alcohol (A-10 manufactured by Futaba Chemicals Co., Ltd.) was prepared, and the anti-fog layer of each example was pressed with a load of 300 g and moved back and forth 10 times within a distance of 5 cm. Then, the same anti-fog performance test as in (3-1) above was performed. The results are shown below.

[0398] [Table 8]

[0399] Anti-fog performance Water film Appearance Example 12 OK OK OK Embodiment 13 OK OK OK Embodiment 14 OK OK OK Embodiment 15 Deformation OK OK Example 16 Deformation OK OK Embodiment 17 OK OK OK Embodiment 18 Deformation OK OK Embodiment 19 OK OK OK Embodiment 20 Deformation OK OK

[0400] As can be seen from the results in Table 8, after wiping, deformation was observed on the surface of the anti-fog layer in Examples 15, 16, 18, and 20, while the anti-fog performance was maintained in the other Examples.

[0401] (3-3. Weather resistance test)

[0402] The cover member of each example was stored in a thermostatic chamber at a temperature of 85° C. and a humidity of 85% for 48 hours. Then, the same anti-fogging performance test as in the above (3-1) was performed. The results are shown below.

[0403] [Table 9]

[0404] Anti-fog performance Water film Appearance Example 12 OK OK OK Embodiment 13 OK OK OK Embodiment 14 OK OK OK Embodiment 15 OK OK OK Example 16 OK OK OK Embodiment 17 OK OK OK Embodiment 18 OK OK OK Embodiment 19 OK OK OK Embodiment 20 OK OK OK

[0405] <B. Second Embodiment>

[0406] A second embodiment in which the transparent laminate of the present invention is applied to a cover member will be described below with reference to the drawings. Figure 6 It is a cross-sectional view of a cover member according to a second embodiment.

[0407] The cover member 20 of this embodiment is different from the first embodiment in that a second functional layer 3 is further laminated on the first functional layer 2, and the other structures are the same as those described in the first embodiment.

[0408] <1. Overview of Cover Parts>

[0409] like Figure 6 As shown, the cover member 20 of this embodiment includes a substrate 1, a first functional layer 2 laminated on a first main surface 11 of the substrate 1, and a second functional layer 3 laminated on the first functional layer 2. The substrate 1 and the first functional layer 2 are the same as those shown in the first embodiment.

[0410] As the second functional layer 3, for example, an antireflection film, an antiglare film, an antistatic film, an antibacterial film, etc., can be used. Hereinafter, an example in which an antifogging layer is used as the first functional layer 2 and an antireflection layer is used as the second functional layer 3 will be described.

[0411] The anti-fog layer of the first functional layer 2 is not the topmost layer having a hydrophilic layer as shown in the first embodiment, but a hygroscopic layer formed by, for example, an organic-inorganic composite anti-fog layer. If the anti-reflection layer is laminated on such a hygroscopic anti-fog layer, the hygroscopic effect may be hindered. Therefore, the anti-reflection layer of this embodiment forms a passage for water vapor to the anti-fog layer 2 by having a gap inside. The following is a detailed description.

[0412] <2. Second functional layer>

[0413] Figure 7 is a cross-sectional view of the second functional layer. Figure 6As shown, the second functional layer 3 has hollow particles 31 and a binder 32. The hollow particles 31 are formed of a material with a refractive index of 1.15 to 2.70. The binder 32 is formed of at least polysilsesquioxane and bonds the hollow particles 31. In the second functional layer 3, the absorbance from the hydrocarbon group not directly bonded to the silicon atom, the absorbance from the bond between the silicon atom and the non-reactive functional group, and the absorbance from the bond between the silicon atom and the hydroxyl group, determined by the total reflection measurement method (ATR method) using a Fourier transform infrared spectrophotometer, are represented as Ia, Ib, and Ic, respectively. The second functional layer 3 satisfies at least one of the conditions Ib / Ia≥0.7 and Ib / Ic≥0.3. In this specification, Ib / Ia is also referred to as an organic-inorganic parameter (D), and Ib / Ic is referred to as a hydrophobic parameter (H). The absorbance Ia, absorbance Ib, and absorbance Ic can be determined, for example, from an absorption spectrum obtained by the ATR method according to the method described in the Examples.

[0414] The smaller the number of hydrocarbon groups not directly bonded to silicon atoms contained in the adhesive 32, the larger the organic-inorganic parameter (D). If the number of hydrocarbon groups not directly bonded to silicon atoms contained in the adhesive 32 is small, the Si-O-Si network in the adhesive 32 is dense, and the density of the inorganic components in the adhesive 32 becomes high. Thus, the hollow particles 31 are firmly fixed by the Si-O-Si network. Therefore, in the second functional layer 3, as long as Ib / Ia≥0.7, the hollow particles 31 are firmly fixed in the second functional layer 3, and the second functional layer 3 has characteristics that are conducive to low refractive index coating. If the hollow particles are not sufficiently fixed in the film, the mechanical strength of the film may be reduced.

[0415] The fewer the hydroxyl groups bonded to the silicon atoms in the binder 32, the greater the hydrophobic parameter (H). For example, in the raw material of the binder 32, if the hydroxyl groups are condensed with each other and the network composed of Si-O-Si is developed, the number of hydroxyl groups bonded to the silicon atoms in the binder 32 becomes less. As long as the hydrophobic parameter (H) is above the specified value, the network composed of Si-O-Si is densely developed in the binder 32, and the hollow particles 31 can be firmly fixed through the network. Therefore, in the second functional layer 3, as long as Ib / Ic≥0.3, the hollow particles 31 are firmly fixed in the second functional layer 3, and the second functional layer 3 has a characteristic that is conducive to low refractive index coating.

[0416] The second functional layer 3 preferably further satisfies the conditions of Ib / Ia≥0.7 and Ib / Ic≥0.3. Thus, the hollow particles 31 are more reliably and firmly fixed in the second functional layer 3, and the second functional layer 3 has characteristics that are conducive to low refractive index coating.

[0417] When there is a silanol group (Si-OH) in the adhesive 32, the silanol group forms a hydrogen bond with the silanol group existing on the surface of the glass plate 1, so the affinity is high. Therefore, the film with a hydrophobic parameter (H) below a specified value is also easy to adhere to the glass plate 1. In order to show good adhesion to both substrates having a hydrophilic surface and substrates having a hydrophobic surface, the second functional layer 3 more preferably satisfies the condition of 0.3≤Ib / Ic≤2.0.

[0418] In the second functional layer 3, the first absorbance, the second absorbance and the third absorbance from the bonding of one oxygen atom to two silicon atoms determined by the ATR method are represented as Id, Ie and If, respectively. The first absorbance Id corresponds to the first wave number. The second absorbance Ie corresponds to the second wave number greater than the first wave number. The third absorbance If corresponds to the third wave number greater than the second wave number. The second functional layer 3 preferably satisfies at least one of the conditions of Id / Ib≤60, Ie / Ib≤20 and If / Ib≤174. In this specification, Id / Ib is also referred to as the first network parameter (N1), Ie / Ib is also referred to as the second network parameter (N2), and If / Ib is also referred to as the third network parameter (N3).

[0419] The first wave number is at, for example, 455 ± 50 cm -1 The second wave number is, for example, 780 ± 50 cm -1 The third wave number is, for example, 1065 ± 50 cm -1 The wave number at which the maximum of the absorption spectrum occurs.

[0420] The more bonds (Si-O-Si) between oxygen atoms and two silicon atoms in the adhesive 32, the larger the first network parameter (N1), the second network parameter (N2) and the third network parameter (N3). In the raw material of the adhesive 32, the more developed the Si-O-Si network generated by the condensation of hydroxyl groups, the larger the first network parameter (N1), the second network parameter (N2) and the third network parameter (N3). On the other hand, in order to ensure good film-making properties, it is important to suppress the aggregation of hollow particles so as to keep the thickness of the coating uniform. In order to suppress the aggregation of hollow particles, it is preferred to prevent the overdevelopment of the Si-O-Si network. From such a viewpoint, in the second functional layer 3, it is preferred to satisfy at least one of N1 being less than 60, N2 being less than 20 and N3 being less than 174. Thus, the second functional layer 3 can be well formed, and an anti-reflection structure with good anti-reflection performance can be provided by the second functional layer 3.

[0421] The second functional layer 3 preferably further satisfies the conditions of Id / Ib≤60, Ie / Ib≤20, and If / Ib≤174.

[0422] Typically, the polysilsesquioxane of the binder 32 has a non-reactive functional group bonded to a silicon atom. In order for the polysilsesquioxane of the binder 32 to exert an appropriate hydrophobic effect, the non-reactive functional group is a hydrophobic functional group such as an alkyl group. Preferably, the polysilsesquioxane of the binder 32 is a polysilsesquioxane in which a hydrocarbon group having 16 or less carbon atoms is bonded to a silicon atom as a non-reactive functional group. In this case, since the non-reactive functional group is not large in size, a Si-O-Si network is easily formed densely.

[0423] The adhesive 32 can be further formed of, for example, silicon dioxide. In this case, the polysilsesquioxane contained in the adhesive 32 is likely to exert a hydrophobic effect, and the silicon dioxide contained in the adhesive 32 is likely to exert a hydrophilic effect. Therefore, in the adhesive 32, by adjusting the ratio (Mp / Ms) of the amount Mp of the polysilsesquioxane to the amount Ms of the silicon dioxide, the hydrophilicity or hydrophobicity of the second functional layer 3 can be adjusted to an appropriate level. Thus, the second functional layer 3 can be appropriately formed on a substrate having a hydrophilic surface such as a glass substrate, and the second functional layer 3 can be appropriately formed on a substrate having a hydrophobic surface such as a resin. From this point of view, the ratio (Mp / Ms) of the amount Mp of the polysilsesquioxane to the amount Ms of the silicon dioxide in the adhesive 32 is, for example, 3 / 7 or more, preferably 1 to 9, and more preferably 3 / 2 to 4.

[0424] The hollow particles 31 are not particularly limited as long as they have a hollow structure, and may have, for example, a spherical, cylindrical, or flaky shape. The hollow particles 31 have, for example, an average particle size (primary particle size) of 10 to 150 nm. Thus, the hollow particles 31 are easily dispersed uniformly in the second functional layer 3. The average particle size of the hollow particles 31 can be determined by taking the arithmetic average of the particle sizes of 50 or more hollow particles 31 observed using, for example, a transmission electron microscope (TEM) or a scanning electron microscope (SEM). In addition, the particle size of each particle refers to the maximum diameter.

[0425] The hollow particles 31 preferably have an average particle size of 20 to 100 nm, more preferably 30 to 70 nm. In addition, the maximum size of the internal space of the hollow particles 31 is, for example, 5 to 100 nm, preferably 10 to 70 nm, more preferably 20 to 50 nm. The hollow particles 31 are preferably monodisperse particles having a coefficient of variation of 0.1 or less.

[0426] The material of the hollow particle 31 can be any material with a refractive index of 1.15 to 2.70, and can be an inorganic material or an organic material. The material of the hollow particle 31 is preferably a material with a refractive index of 1.20 to 2.00, more preferably a material with a refractive index of 1.30 to 1.50, and further preferably a material with a refractive index of 1.38 to 1.46. From the viewpoint of being less likely to be deformed by external forces, the hollow particle 31 is preferably formed of an inorganic material. In this case, the hollow particle 31 can be formed of at least one selected from, for example, silicon dioxide, magnesium fluoride, aluminum oxide, aluminum silicate, titanium oxide, and zirconium oxide.

[0427] The hollow particles 31 are preferably made of silicon dioxide or magnesium fluoride in order to provide an anti-reflection structure having high anti-reflection performance by using a low refractive index coating of the second functional layer 3. The refractive index of silicon dioxide is 1.46, and the refractive index of magnesium fluoride is 1.38.

[0428] The structure and material of the hollow particle 31 are determined in such a way that the hollow particle 31 has a desired refractive index. For example, the material of the hollow particle 31 and the ratio of the internal space to the overall volume of the hollow particle 31 are determined in such a way that the hollow particle 31 has a desired refractive index. The hollow particle 31 has a refractive index of, for example, 1.10 to 1.40, preferably 1.20 to 1.35, and more preferably 1.25 to 1.30. For example, among a plurality of hollow particles formed of materials having different refractive indices, when the ratio of the internal space to the overall volume of the hollow particle is the same, the refractive index of the hollow particle formed of a low refractive index material is lower than the refractive index of the hollow particle formed of a high refractive index material.

[0429] The refractive index of the hollow particle 31 can be measured, for example, by an immersion method (Becke line method). For example, in the case where the hollow particle 31 is formed of silicon dioxide, the refractive index of the hollow particle 31 can be measured according to the following steps. (i) The dispersion medium of the dispersion liquid of the hollow particle 31 is evaporated and dried to obtain a powder. (ii) The powder obtained in (i) is mixed with various standard refractive index liquids having different refractive indices such as series A and series AA manufactured by GARGILL. (iii) The refractive index of the standard refractive index liquid used when the mixed liquid obtained in (ii) becomes transparent is determined as the refractive index of the hollow particle 31.

[0430] The hollow particles 31 can be commercially available or can be made by a prescribed method. For example, the hollow particles 31 can be made by removing the core after forming a shell around the core. For example, a shell formed of silicon or a shell formed of magnesium fluoride is formed around a polymer core having a particle size of several tens of nanometers. Then, the polymer core is removed by dissolving in a solvent or burning to obtain hollow particles 31 as hollow silica particles or hollow magnesium fluoride particles. In addition, by forming a shell formed of magnesium fluoride around a core formed of silica and dissolving the core formed of silica with an alkali, hollow particles 31 as hollow magnesium fluoride particles can also be obtained.

[0431] In the second functional layer 3, the ratio of the mass Wh of the hollow particles 31 to the mass Wb of the binder 32 (Wh / Wb) is, for example, 1 / 5 to 20, preferably 1 / 3 to 10, and more preferably 1 to 5. Thus, by using the low refractive index coating of the second functional layer 3, an anti-reflection structure with high anti-reflection performance can be provided.

[0432] The thickness of the second functional layer 3 is not particularly limited, and can be determined, for example, according to the wavelength of the light whose reflection needs to be prevented. Specifically, when the central wavelength of the wavelength of the light whose reflection needs to be prevented is set to λ (nm), the thickness of the second functional layer 3 is set so that the optical film thickness (refractive index × physical film thickness) satisfies λ / 4. For example, in order to prevent the reflection of light belonging to the visible light region (practical wavelength 380nm~780nm), the central wavelength λ is set to λ=550nm, and when the refractive index of the low refractive index film used is set to 1.20, the optimal physical film thickness is 115nm. The thickness of the second functional layer 3 that is practically effective for preventing the reflection of visible light is 50~300nm, preferably 70~200nm, and more preferably 90~170nm. Thus, the low refractive index coating of the second functional layer 3 can be used to provide an anti-reflection structure with high anti-reflection performance. In addition, in order to prevent the reflection of light close to the visible light region and with λ=850nm as the central wavelength in the near infrared region (e.g., wavelength 800nm~2500nm), when the refractive index of the low refractive index film used is set to 1.20, the optimal physical film thickness is 177nm. The thickness of the practically effective second functional layer 3 for preventing near infrared reflection is 80~350nm, preferably 130~250nm, and more preferably 150~220nm. Thus, the low refractive index coating of the second functional layer 3 can be used to provide an anti-reflection structure with high anti-reflection performance. As an anti-reflection structure, when using a multilayer film, a low refractive index layer with a film thickness of 50nm or less can be used. In addition, the physical film thickness of the low refractive index film is not limited to this, and its cross section can be measured by SEM, TEM or ellipsometer.

[0433] The second functional layer 3 has a refractive index of, for example, 1.45 or less, preferably 1.1 to 1.35. Thus, it is possible to provide an anti-reflection structure with high anti-reflection performance using a low refractive index coating of the second functional layer 3. The second functional layer 3 preferably has a refractive index of 1.30 or less, and more preferably has a refractive index of 1.25 or less. From the viewpoint of reducing the refractive index of the second functional layer 3, the second functional layer 3 may include a space between the hollow particles 31 or an air layer (air space) in the adhesive 32. The refractive index of the second functional layer 3 can be determined, for example, by reflectivity spectroscopy. By increasing the proportion (porosity) of the air layer, the refractive index of the second functional layer 3 can be reduced. The porosity is, for example, 0 to 70% by volume, preferably 10 to 50% by volume, and more preferably 20 to 50% by volume. This is also the case in the second functional layer composed of multiple layers described later.

[0434] The second functional layer 3 is, for example, a solidified product obtained by solidifying a prescribed liquid composition. The liquid composition contains hollow particles, polysilsesquioxane, and a solvent. The hollow particles are formed of a material having a refractive index of 1.15 to 2.70. In the solidified product obtained by applying the liquid composition on a substrate and solidifying the liquid composition, at least one of the conditions of Ib / Ia≥0.7 and Ib / Ic≥0.3 is satisfied. The solvent contained in the liquid composition is, for example, an alcohol such as ethanol, methanol, 1-propanol, 2-propanol, or water.

[0435] The second functional layer solution can be applied to the antifog layer as the first functional layer by various methods such as spin coating, roller coating, and spray coating. However, methods such as roller coating and spray coating require leveling of the solution during, for example, the period from coating to baking, so it takes time from coating to baking. Therefore, the solvent evaporates during this time, and drying may be performed unevenly. As a result, for example, in the adhesive, it is possible that the refractive index of the area where the solvent evaporates before the network is formed in the heating furnace is different from that of the area where the solvent remains when the network is formed, or the film thickness is different.

[0436] Therefore, when coating at such a high temperature, it is preferred to use a high boiling point solvent. As a result, in the solution for the second functional layer, the volatilization of the solvent can be suppressed, so that the refractive index and film thickness of the film can be made uniform. In addition, since the formation of the network in the adhesive occurs due to dehydration polycondensation reaction, etc., the baking temperature is preferably about 100°C. Therefore, the boiling point of the high boiling point solvent is preferably above 100°C. In addition, since the first functional layer contains an organic resin, yellowing may occur above 300°C. Therefore, the baking temperature of the second functional layer is preferably below 300°C. In contrast, when a solvent with a boiling point of more than 300°C is used, a large amount of solvent may remain after baking. As a result, the refractive index of the second functional layer changes, and the desired optical properties may not be obtained. Therefore, the boiling point of the high boiling point solvent is preferably above 100°C and below 300°C.

[0437] The high boiling point solvent is not particularly limited, and can be, for example, 1-methoxy-2-propanol or 3-methoxy-3-methyl-1-butanol as the main component. In addition, the content of such a high boiling point solvent in the solution is preferably, for example, 1 ppb or more, 5 g / cm 3 Below, more preferably 3g / cm 3 Below, more preferably 1g / cm 3 The reason is as follows. In the above-mentioned second functional layer solution, a solvent with a higher temperature than the baking temperature is added, so after baking, more than 1 ppb of the solvent remains in the second functional layer. Here, if the second functional layer contains 5 g / cm 3 If the solvent is more than 5 g / cm, the refractive index may change due to the residual solvent, so the function of the optical film may not be exerted. 3 The following solvents are used. In addition, the volume of the second functional layer 3 is calculated from the average value of the thickness of the second functional layer 3 measured at 10 points and the area of ​​the second functional layer 3. In addition, the amount of the high boiling point solvent is analyzed and calculated by gas chromatography or the like. Then, the concentration (g / cm 3 ).

[0438] In addition, in the liquid composition, an organosilane compound having a fluoroalkyl group is not required, so phase separation is not likely to occur in the liquid composition, and the liquid composition is easy to become uniform. In addition, the liquid composition has high wettability to the substrate and the resin substrate, and it is easy to obtain an anti-reflection layer with a uniform structure through the liquid composition.

[0439] In the above-mentioned cured product, it is preferred that the conditions of Ib / Ia≥0.7 and Ib / Ic≥0.3 are further satisfied.

[0440] In the above-mentioned cured product, it is preferred that at least one of the conditions of Id / Ib≤60, Ie / Ib≤20 and If / Ib≤174 is satisfied.

[0441] In the above-mentioned cured product, it is more preferable that the conditions of Id / Ib≤60, Ie / Ib≤20 and If / Ib≤174 are further satisfied.

[0442] The polysilsesquioxane in the liquid composition is, for example, a polysilsesquioxane in which a hydrocarbon group having 16 or less carbon atoms is bonded to a silicon atom as a non-reactive functional group.

[0443] The characteristics of the hollow particles 31 in the second functional layer 3 are also typically applicable to the hollow particles in the liquid composition. Therefore, the hollow particles in the liquid composition have an average particle size (primary particle size) of, for example, 10 to 150 nm. In addition, the hollow particles in the liquid composition are preferably at least one selected from silicon dioxide, magnesium fluoride, aluminum oxide, aluminum silicate, titanium oxide, and zirconium oxide.

[0444] The liquid composition may contain silicon dioxide in addition to the hollow particles, for example.

[0445] The second functional layer 3 can be formed, for example, by applying a liquid composition to the first functional layer 2 and curing the liquid composition. Thus, a low refractive index layer is formed using the second functional layer 3. By using a liquid composition, an organosilane compound having a fluoroalkyl group is not required, and a low refractive index coating layer can be easily formed.

[0446] The polysilsesquioxane of the liquid composition is formed, for example, by hydrolysis and dehydration condensation of trifunctional alkoxysilane contained in the raw material of the liquid composition. In addition, when the liquid composition contains silicon dioxide in addition to the hollow particles, the silicon dioxide is formed, for example, by hydrolysis and dehydration condensation of tetrafunctional alkoxysilane contained in the raw material of the liquid composition. For example, the tetrafunctional alkoxysilane forms silicon dioxide (SiO2) by the following reaction of (Formula 1) and (Formula 2). a The trifunctional alkoxysilane forms polysilsesquioxane (R b SiO 3 / 2 ). b Represents a non-reactive functional group, R c It represents an alkyl group.

[0447] Si(OR a )4+4H2O→Si(OH)4+4R a OH (Formula 1)

[0448] Si(OH)4→SiO2+2H2O (Formula 2)

[0449] R b Si(OR c )3+3H2O→R b Si(OH)3+3R c OH (Formula 3)

[0450] R b Si(OH)3→R b SiO 3 / 2 +3 / 2H2O (Formula 4)

[0451] The hydrolysis catalyst contained in the raw material of the liquid composition is, for example, a carboxylic acid such as formic acid and acetic acid.

[0452] <3. Adjustment of refractive index>

[0453] In order to make the second functional layer 3 function properly as an anti-reflection layer, the refractive index of the second functional layer 3 needs to be determined in consideration of the refractive index of the anti-fog layer as the first functional layer 2. The refractive index of the anti-fog layer depends on the material, but is generally 1.5 to 1.6. In addition, in order to reduce the refractive index of the first functional layer 2 and the second functional layer 3 as a whole, it is known to make the refractive index of the second functional layer 3 1 / 2 of the refractive index of the first functional layer 1. For example, when the refractive index of the anti-fog layer is 1.55, the refractive index of the second functional layer 3 is preferably 1.24.

[0454] As described above, the second functional layer 3 is composed of hollow particles 31, a binder 32 and an air layer. Since the second functional layer 3 contains hollow particles containing air, the refractive index can be reduced. Moreover, since the second functional layer 3 also contains an air layer, the refractive index can be further reduced when the proportion (porosity) of the air layer is increased. Therefore, by adjusting the proportion or porosity of the hollow particles, the refractive index of the second functional layer 3 can be, for example, about 1 / 2 of the refractive index of the first functional layer 2 ± 0.1.

[0455] <4. Second functional layer composed of multiple layers>

[0456] In the above example, the second functional layer 3 is formed by a single layer, but it can also be formed by two layers. Figure 8 As shown, the second functional layer 3 may be composed of a first layer 301 laminated on the first functional layer 2 and a second layer 302 laminated on the first layer 301. Here, in order to reduce the overall refractive index of the functional layers 2 and 3, the refractive index of the first layer 301 is made smaller than that of the anti-fog layer 2, and the refractive index of the second layer 302 is made smaller than that of the first layer 301. The refractive index of the first layer 301 may be, for example, 1.35 to 1.55, and the refractive index of the second layer 302 may be, for example, 1.10 to 1.25.

[0457] As such an example, the second layer 302 is formed by the above-mentioned single-layer second functional layer 3. Then, the first layer 301 is a layer in which the hollow particles 31 are removed from the second layer 302, and is a layer composed of at least one of polysilsesquioxane and silica constituting the adhesive. The second layer 302 can be set to, for example, 30 to 300 nm. In addition, although the first layer 301 does not contain hollow particles and does not include an air layer, water vapor can pass through because the adhesive 32 is porous. Therefore, even if such a first layer 301 is formed, water vapor can reach the anti-fog layer 2 through the first layer 301 and the second layer 302. However, since water vapor is not easy to pass through compared to the second layer 302, the film thickness of the first layer 301 is preferably thinner than the second layer 302.

[0458] In this way, when the second functional layer 3 is formed in multiple layers, the refractive index of each layer may be gradually reduced as it goes toward the outermost layer from the first functional layer 2. Therefore, the second functional layer 3 may be formed in three or more layers.

[0459] <5. Physical properties of the second functional layer>

[0460] When the first functional layer 2 is an anti-fog layer, the volume sometimes changes due to moisture absorption. Moreover, since the second functional layer 3 is laminated on the first functional layer 2, the second functional layer 3 preferably follows the volume change of the first functional layer 2. If the follow-up is insufficient, cracks may occur in the second functional layer 3. Therefore, for example, when the bending modulus of the anti-fog layer 2 is 2 to 3 GPa, the bending modulus of the second functional layer 3 is preferably in a range overlapping with the bending modulus of the anti-fog layer 2, for example 1 to 10 GPa, more preferably 1 to 4 GPa. That is, polysilsesquioxane (bending modulus 2 to 3 GPa) that exhibits the same bending modulus as the anti-fog layer 2 can be suitably used as an adhesive for the second functional layer 3.

[0461] In addition, the first functional layer and the second functional layer expand and contract due to temperature changes, so the difference in linear expansion coefficient between the first functional layer 2 and the second functional layer 3 is preferably 30 ppm / °C. For example, the linear thermal expansion coefficient of the anti-fog layer is 60 to 84 ppm / °C, while the linear thermal expansion coefficient of polysilsesquioxane is 40 to 70 ppm / °C, so it can be used as a binder for the second functional layer 3. That is, even if the film volume increases or decreases due to the water absorption of the anti-fog layer, cracks in the first functional layer 2 and the second functional layer 3 can be suppressed.

[0462] <6. Other Implementation Methods>

[0463] The first functional layer 2 and the second functional layer 3 of this embodiment can adopt various forms. For example, when the second functional layer 3 is a single layer, such as Fig. 9 As shown, on the substrate film 81, the anti-fog layer 2 and the anti-reflection layer 3 can be sequentially laminated, and then the substrate film 81 can be attached to the substrate 1 through an adhesive layer (omitted from the figure). Similarly, in the case where the second functional layer 3 is multilayered, such as Fig.10 As shown, the antifog layer 2, the first layer 301 and the second layer 302 of the antireflection layer can be sequentially stacked on the base film 81, and then the base film 81 can be attached to the base material 1 through the adhesive layer 82. In addition, the base film 81 and the adhesive layer 82 are the same as those shown in the first embodiment.

[0464] The transparent laminate of the present invention may contain an ultraviolet absorber and / or an infrared absorber. At least one of the first functional layer, the second functional layer, and the third functional layer may contain an ultraviolet absorber and / or an infrared absorber.

[0465] Alternatively, at least one of the substrate film, adhesive layer and anti-fogging layer may contain an ultraviolet absorber and / or an infrared absorber.

[0466] Examples of the ultraviolet absorber include benzotriazole compounds [2-(2'-hydroxy-5'-methylphenyl)benzotriazole, 2-(2'-hydroxy-3',5'-di-tert-butylphenyl)benzotriazole, etc.], benzophenone compounds [2,2',4,4'-tetrahydroxybenzophenone, 2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-octyloxybenzophenone, 5,5'-methylenebis(2-hydroxy-4-methoxybenzophenone)], hydroxyphenyltriazine compounds, Organic substances such as compounds [2-(2-hydroxy-4-octyloxyphenyl)-4,6-bis(2,4-di-tert-butylphenyl)-s-triazine, 2-(2-hydroxy-4-methoxyphenyl)-4,6-diphenyl-s-triazine, 2-(2-hydroxy-4-propoxy-5-methylphenyl)-4,6-bis(2,4-di-tert-butylphenyl)-s-triazine, etc.] and cyanoacrylate compounds [ethyl-α-cyano-β,β-diphenylacrylate, methyl-2-cyano-3-methyl-3-(p-methoxyphenyl)acrylate, etc.]. The ultraviolet absorber can be used alone or in combination of two or more. In addition, the ultraviolet absorber can also be at least one organic pigment selected from polymethine compounds, imidazoline compounds, coumarin compounds, naphthylimide compounds, perylene compounds, azo compounds, isoindolinone compounds, quinophthalone compounds and quinoline compounds. Among the ultraviolet absorbers, organic ultraviolet absorbers are preferred, and at least one selected from benzotriazole compounds, benzophenone compounds, hydroxyphenyltriazine compounds and cyanoacrylate compounds is more preferred, and benzophenone compounds are further preferred. Benzophenone compounds are preferred because they have good solubility in the alcohol solvent contained in the coating liquid for forming the organic-inorganic composite anti-fog film and are more uniformly dispersed in the polyvinyl acetal resin.

[0467] The ultraviolet absorber preferably has a hydroxyl group, and more preferably has two or more hydroxyl groups bonded to one benzene skeleton of the ultraviolet absorber. The ultraviolet absorber can be added in an amount of preferably 0.1 to 50 parts by weight, more preferably 1.0 to 40 parts by weight, and even more preferably 2 to 35 parts by weight relative to 100 parts by weight of the water-absorbing resin.

[0468] As infrared absorbers, for example, organic infrared absorbers such as polymethine compounds, cyanine compounds, phthalocyanine compounds, naphthalocyanine compounds, naphthoquinone compounds, anthraquinone compounds, dithiol compounds, immonium compounds, diimmonium compounds, ammonium compounds, pyrylium compounds, cerylium compounds, squarylium compounds, counter ion combinations of benzenedithiol metal complex anions and cyanine pigment cations; inorganic infrared absorbers such as tungsten oxide, tin oxide, indium oxide, magnesium oxide, titanium oxide, chromium oxide, zirconium oxide, nickel oxide, aluminum oxide, zinc oxide, iron oxide, antimony oxide, lead oxide, bismuth oxide, lanthanum oxide, tungsten oxide, indium tin oxide, antimony tin oxide, etc. can be listed. Infrared absorbers can be used alone or in combination of two or more. Among infrared absorbers, inorganic infrared absorbers are preferred, and indium tin oxide and / or antimony tin oxide are more preferred.

[0469] Indium tin oxide and / or antimony tin oxide are preferred because they have good stability in the coating liquid for forming the organic-inorganic composite antifogging film and can be more uniformly dispersed in the polyvinyl acetal resin. The infrared absorber can be added in an amount of preferably 0.1 to 50 parts by weight, more preferably 1.0 to 40 parts by weight, and further preferably 2 to 35 parts by weight relative to 100 parts by weight of the water-absorbing resin.

[0470] The first functional layer 2 and the second functional layer 3 may not be adjacent to each other. For example, a primer layer, an absorption layer or a modification layer that absorbs a specific wavelength may be provided between the first functional layer 2 and the second functional layer 3.

[0471] <7. Application>

[0472] The cover component of this embodiment can also be used as a cover component for a camera device provided on an aircraft such as a drone, or a cover component for a surveillance camera, as in the first embodiment described above. In particular, when an anti-reflection layer is formed as the second functional layer 3, it is suitable for use as a cover component for a camera device of an aircraft that is mostly photographed outdoors where the environment changes. In particular, when an aircraft suddenly rises, the pressure changes drastically. It can also be understood from Boyle-Charles' law that when the pressure decreases, the temperature decreases. Therefore, the transparent laminate with anti-fog function of the present invention can be used appropriately.

[0473] Example

[0474] Examples 21 to 27 of the second embodiment will be described below. However, the present invention is not limited to the following examples.

[0475] (Example 21)

[0476] As Example 21, the following cover parts were produced.

[0477] (1) Substrate: float glass with a thickness of 2.8 mm.

[0478] (2) First functional layer: The antifogging layer described in Example 1 of the first embodiment 1 was formed on the first main surface of the substrate. However, no hydrophilic layer was formed in the antifogging layer. The film thickness was 8 μm and the refractive index was 1.55.

[0479] (3) Second functional layer: A single-layer antireflection layer as shown below was formed.

[0480] After the anti-fog layer was formed, the coating liquid for the anti-reflection layer was prepared as follows. First, 0.6 g of tetraethoxysilane (TEOS) (manufactured by Tokyo Chemical Industry Co., Ltd.), 1.18 g of methyltriethoxysilane (MTES) (manufactured by Tokyo Chemical Industry Co., Ltd.), 0.82 g of 0.3 mass % formic acid (manufactured by Kishida Chemical Co., Ltd.), 3 g of a sol of hollow silica particles (manufactured by JGC Catalysts & Chemicals Co., Ltd., product name: THRULYA 4110, silica solid content: about 25 mass %) and 22.4 g of ethanol (manufactured by Kishida Chemical Co., Ltd.) were mixed and reacted at 35° C. for 3 hours. Thus, the coating liquid for the second functional layer of Example 22 was obtained. In the sol of hollow silica particles, the average particle size of the hollow silica particles is about 50 nm, the thickness of the shell formed by silica is 10 to 20 nm, the maximum size of the internal space of the hollow silica particles is about 10 to 30 nm, and the refractive index of the hollow silica particles is 1.25. The solid content in the coating liquid contains 0.6% by mass of silica from TEOS, 1.6% by mass of polymethylsilsesquioxane from MTES, and 2.6% by mass of hollow silica particles. The mass ratio of MTES to the mass ratio of TEOS added when preparing the liquid composition of Example 1 is 7 / 3. The weight ratio of the weight of the hollow silica particles to the total weight of the solid content of silica from TEOS and polymethylsilsesquioxane from MTES is 1.3 / 1.1.

[0481] Next, the anti-fogging layer was coated with the coating liquid by spin coating, and a uniform coating film having a good appearance immediately after coating was obtained. The coating film was then dried in an oven at 200° C. for 10 minutes, thereby obtaining a cover member of Example 22.

[0482] The thickness of the anti-reflection film is 100 nm, and the refractive index is 1.24±0.5. In addition, the volume ratio of the materials constituting the anti-reflection film is as follows: 50 volume % of hollow silica particles, 23 volume % of binder, and 23 volume % of porosity.

[0483] (Example 22)

[0484] As Example 22, the following cover parts were produced.

[0485] (1) Substrate: Float glass with a thickness of 2.8 mm was used.

[0486] (2) First functional layer: The antifogging layer described in Example 1 of the first embodiment was formed on the first main surface of the substrate. However, no hydrophilic layer was formed in the antifogging layer. The film thickness was 8 μm and the refractive index was 1.55.

[0487] (3) Second functional layer: The following two antireflection layers are formed.

[0488] After the anti-fog layer was formed, a coating liquid for an anti-reflection layer was prepared as follows. That is, a coating liquid for the first layer was prepared in the same manner as the coating liquid of Example 21, except that the sol of hollow silica particles was not added. Then, the coating liquid was applied to the anti-fog layer by spin coating. Then, the coating film was dried in an oven at 200° C. for 10 minutes to form a first layer. The refractive index of the first layer was 1.46 and the thickness was 90 nm.

[0489] Then, on the first layer, the same coating liquid as that of Example 21 was applied by spin coating. However, a coating liquid having a higher ratio of hollow silica particles and a higher porosity than that of Example 21 was used. Then, the coating film was dried in an oven at 200° C. for 10 minutes to form a second layer. The refractive index of the second layer was 1.16 and the thickness was 95 nm.

[0490] (Examples 23 to 27)

[0491] As Examples 23-27, the following cover parts were produced.

[0492] (1) Substrate: Glannova (manufactured by Nippon Sheet Glass Co., Ltd.) having a thickness of 1.1 mm was used.

[0493] (2) First functional layer: The antifogging layer described in Example 1 of the first embodiment was formed on the first main surface of the substrate. However, no hydrophilic layer was formed in the antifogging layer. The film thickness was 8 μm and the refractive index was 1.55.

[0494] (3) Second functional layer: A single-layer antireflection layer as shown below was formed.

[0495] After the anti-fog layer was formed, a coating liquid for an anti-reflection layer having a composition (in mass %) shown in Table 10 was prepared. First, tetraethoxysilane (TEOS) (manufactured by Tokyo Chemical Industry Co., Ltd.), methyltriethoxysilane (MTES) (manufactured by Tokyo Chemical Industry Co., Ltd.), 0.3 mass % formic acid (manufactured by KISHIDA CHEMICAL CO., LTD.), a sol of hollow silica particles (manufactured by JGC Catalysts & Chemicals Co., Ltd., product name: THRULYA 4110, silica solid content concentration: about 25 mass %), a solvent, a leveling agent, etc. were mixed and reacted at 35° C. for 3 hours. Thus, the coating liquid for the second functional layer of Examples 23 to 27 was obtained. In the sol of hollow silica particles, the average particle size of the hollow silica particles was about 50 nm, the thickness of the shell formed by silica was 10 to 20 nm, the maximum size of the internal space of the hollow silica particles was about 10 to 30 nm, and the refractive index of the hollow silica particles was 1.25.

[0496] [Table 10]

[0497]

[0498] The solvents, leveling agents, etc. shown in Table 10 are as follows: E to H are high boiling point solvents having a boiling point of 100° C. or higher.

[0499] A: Methanol

[0500] B: Ethanol

[0501] C: 2-Propanol

[0502] D: 1-Propanol

[0503] E: 1-Butanol

[0504] F: 1-methoxy-2-propanol

[0505] G: 3-methoxy-3-methyl-1-butanol

[0506] H: 3-methoxy-3-methyl-1-butyl acetate

[0507] MIBK: Methyl isobutyl ketone

[0508] KP-341: Leveling agent (manufactured by Shin-Etsu Chemical Co., Ltd.)

[0509] BYK-378_10%: Leveling agent (manufactured by BYK-Chemie Japan Co., Ltd.)

[0510] Then, the anti-fogging layer was coated with the coating liquid of Example 23 by spin coating, and the coating liquids of Examples 24 to 27 were coated by roll coating. A uniform coating film having a good appearance immediately after coating was obtained. Then, the coating film was dried in a heating furnace at 120° C. for 10 minutes to obtain the cover parts of Examples 24 to 27.

[0511] When air was blown toward the second functional layers of the cover members of Examples 24 to 27 thus formed, and the anti-fogging performance was evaluated, fogging did not occur in any of them.

[0512] Next, the single-side reflectivity of Examples 23 and 26 was measured. The results are as follows Fig.11 As shown. The average visible light reflectance of Examples 23 and 26 is 0.71% and 0.31%, respectively. In addition, although the illustration is omitted, the reflectance of the cover component without the second functional layer and only the anti-fog layer is 4-5%. Therefore, it can be seen that the cover components of Examples 23 and 26 can significantly reduce the reflectance.

[0513] (Examples 28 to 30)

[0514] As Examples 28 to 30, the following cover parts are prepared. First, an anti-fog film (manufactured by FujiFilm, model: MF-600) is prepared. The film is a product in which a TAC film having a modified layer (anti-fog layer) showing anti-fog properties by modifying a TAC (triacetylcellulose) film and a PET film are bonded together via an adhesive layer. Specifically, a film having the following structure is prepared. Protective film (PE: 60μm) / TAC modified layer (5μm) / TAC (120μm) / adhesive layer (15μm) / PET (50μm) / adhesive layer (25μm) / protective film (PET: 38μm).

[0515] Next, peel off the protective film (PE: 60μm) on the TAC modified layer side, and perform corona discharge treatment on the surface of the TAC modified layer (manufactured by Shinko Electric Instruments Co., Ltd., model: corona master-PS-1M, 14.5kW). Apply the coating liquid of Example 21 to the corona discharge treated surface by spin coating (5000rpm, 20 seconds, room temperature) (Example 28). Treat at a baking temperature of 120°C for 10 minutes. Use a reflectivity measuring device (manufactured by Olympus Corporation, model: USPM-RUIII) to measure the single-sided reflectivity of the surface formed with the anti-reflection layer. Using this device, high-precision spectral reflectivity measurement can be performed without being affected by the back reflected light. The refractive index calculated from the reflectivity obtained by the reflectivity meter is 1.2382, and the film thickness is 107nm (Table 11). Moreover, by changing the rotation speed of spin coating, anti-reflection layers with different film thicknesses are formed on the film (Example 29, Example 30).

[0516] After forming an antireflection film on the TAC modified layer (antifogging layer) as described above, the protective film (PET: 38 μm) on the adhesive layer side was peeled off, and the adhesive layer side was attached to a glass substrate (manufactured by Nippon Sheet Glass Co., Ltd., product name: Glanova, thickness: 2.11 mm). In this way, cover parts of Examples 28 to 30 were prepared. Next, evaluation was performed as described below.

[0517] [Table 11]

[0518] Embodiment 28 Embodiment 29 Embodiment 30 Spin coating speed (rpm) 5000 6000 6000 Calcination temperature (℃) 120 120 120 Film thickness(nm) 107 102 109 Refractive Index 1.2382 1.2216 1.2355

[0519] The single-side reflectances at 400 to 700 nm of the films on which the antireflection films of Examples 28 to 30 were formed are shown in FIG. Fig.12 The single-side reflectivity without anti-reflection film is expressed as a film without anti-reflection layer. Fig.12 It is clearly known that when the anti-reflection film of the present invention is not formed, that is, the single-sided reflectivity of the anti-fog layer (TAC modified layer) is more than 4%. On the contrary, when an anti-reflection film is formed on the anti-fog layer (TAC modified layer) as in Examples 28 to 30, the single-sided reflectivity is less than 1% in the range of 400 to 700 nm, confirming a significant anti-reflection effect.

[0520] Furthermore, when air was blown to the anti-fogging layers on which the anti-reflection films were formed in Examples 28 to 30 and the anti-fogging performance was evaluated, fogging did not occur in any of them.

[0521] <C. Modification example>

[0522] Although the embodiments of the present invention have been described above, the present invention is not limited to the above embodiments, and various modifications can be made without departing from the spirit of the present invention. In addition, the following modified examples can be appropriately combined.

[0523] <1> The substrate 1 may be a composite material of a resin material and a glass plate, or may be a laminated glass in which an interlayer film is sandwiched between two glass plates.

[0524] <2> The substrate 1 may be, for example, a mirror having an anti-glare layer (or a surface subjected to an anti-glare treatment).

[0525] The mirror may peel off at the part touched by the user's hand, and the surface film peeling durability is often required for long-term use. Therefore, as mentioned above, when the anti-fog layer is directly applied to the mirror as a substrate, the substrate (glass plate) and the anti-fog layer are firmly bonded through the siloxane bond, so high durability can be expected even during long-term use.

[0526] In addition, when the mirror is used in a bathroom or a washstand, etc., since it is an environment with particularly high humidity, a high anti-fog property is required. On the other hand, if the anti-fog layer only has water absorption performance, when the saturation amount is exceeded, water droplets will be generated on the surface of the anti-fog layer, which will cause fogging. Therefore, if a hydrophilic layer as described above is formed on the surface of the anti-fog layer, when the hygroscopic layer is saturated, a water film will be generated on the surface, and even in a high humidity environment, for example, it is possible to avoid the image being invisible due to fogging. In addition, when a water film is generated, the contact angle of water is less than 20 degrees. In addition, not only a hydrophilic layer but also a water-repellent layer may be provided. The water-repellent layer referred to herein refers to a layer having a water contact angle of less than 90 degrees.

[0527] When a mirror is used as a substrate, it is preferred that the anti-fog layer of the substrate film such as PET mentioned above is not laminated. When there is no substrate film, deformation caused by the substrate film can be prevented. In particular, in the case of a mirror, image clarity and high low deformability are required. In addition, in a mirror, incident light and reflected light pass through the anti-fog layer. That is, light passes through the anti-fog layer twice, so an anti-fog layer without a substrate film is particularly advantageous for deformation. In addition, when the thickness of the anti-fog layer is a certain thickness of 1 to 20 μm, the bending rigidity is 1 to 4 GPa, so it can be handled even without a substrate film such as PET. In addition, an anti-fog layer with high tensile strength is suitable.

[0528] <3> In the above-mentioned second embodiment, an example of a second functional layer laminated on the first functional layer as an anti-reflection layer is shown, but this anti-reflection layer can also be directly laminated on the substrate 1 as the first functional layer. In this case, in addition to laminating the first functional layer directly on the substrate, a sheet laminated with an adhesive layer, a substrate sheet and a first functional layer can also be prepared, and the adhesive layer can be pasted on the substrate. In this case, the substrate sheet can be formed by, for example, polyethylene terephthalate, polyvinyl chloride, polyvinylidene chloride, polycarbonate or acrylic resin. In addition, the adhesive layer can be used as long as the substrate sheet can be fixed to the substrate 1 with sufficient strength. Specifically, an adhesive layer of a resin such as acrylic acid, rubber, and methacrylic acid and acrylic monomer copolymers with viscosity at room temperature and set to the required glass transition temperature can be used. In addition, the anti-reflection layer can contain a second solvent having a boiling point higher than the boiling point of water and below the heat-resistant temperature of the substrate sheet.

[0529] In addition, the first functional layer as the antireflection layer may also be formed of two layers. Figure 8 The second functional layer 3 described above has the same structure.

[0530] <4> The above-mentioned cover components can be used in, for example, wirelessly controlled aircraft, namely, drones. Fig.13 is a schematic side view of the drone. Fig.13As shown in FIG. 1 , the drone has a main body 91 extending in the front-to-back direction, a camera 5 mounted on the front end of a support member 92 extending downward from the front of the main body 91, two legs 93 mounted on each of the left and right sides of the main body, and a propeller 4 provided at the upper end of each leg 93. The main body 91 has built-in drive sources for the propellers 4, flight control devices, communication equipment, etc. In addition, the camera 5 is provided with a lens 51, and a cover member 10 is mounted in front of the lens. The cover member 10 is provided with a bracket 6 for mounting to the lens 51. Moreover, a closed space is formed in front of the lens 51 by the cover member 10 and the bracket 6. In this case, the first main surface 11 of the base material 1 of the cover member 10 faces the closed space. Therefore, since the first functional layer 2 is laminated on the first main surface 11, fogging on the first main surface 11 due to the temperature difference or air pressure difference between the closed space and the outside can be suppressed. In particular, since the drone repeatedly rises and falls during flight, the above-mentioned temperature changes and air pressure changes are sometimes significant. Therefore, the cover member 10 is easily fogged. Therefore, by using the cover member of the present embodiment as a cover member of an imaging device mounted on a drone, it is possible to prevent the obstruction of imaging due to fogging.

[0531] in addition, Fig.13 The drone shown is only an example, and can be used for all known drones equipped with a camera device. For example, as a drone, there is a drone that can move in water, and the cover component of this embodiment can also be used for such a drone. That is, when moving in water, the temperature change and air pressure change will also be significant, so the above-mentioned cover component can be used well. In addition, as the cover component 10, all the cover components shown in this specification can be used.

[0532] In addition to drones, the present invention can also be applied to various mobile devices other than existing automobiles, airplanes, helicopters, ships, and submarines. That is, the camera device and the cover member can be mounted on an unmanned mobile device or a manned mobile device whose control method is selected from wireless control, autonomous control, direct control by a person, or a combination thereof, and the mobile device is at least one of an aircraft, a ground mobile device, a water mobile device, and an underwater mobile device.

Claims

1. A transparent laminate, characterized in that: The transparent laminated body comprises: A transparent substrate having a first main surface and a second main surface; a transparent first functional layer laminated on the first main surface of the substrate; and a second functional layer laminated on the first functional layer and having moisture permeability, The first functional layer has a hygroscopic anti-fog layer, and the anti-fog layer contains a water-absorbent resin, a metal oxide having a hydrophobic group, and inorganic fine particles including an oxide of at least one element selected from Ti, Ta, and Nb. The second functional layer contains hollow particles and a binder for bonding the hollow particles. When the refractive index of the first functional layer is set to X, the refractive index of the second functional layer is √X±0.

1.

2. The transparent laminate according to claim 1, characterized in that: The surface roughness Ra of the first functional layer is 1-1000 nm.

3. The transparent laminate according to claim 1 or 2, characterized in that: The first functional layer comprises: a substrate film having a first main surface and a second main surface; an adhesive layer laminated on the second main surface of the substrate film; and The anti-fog layer laminated on the first main surface of the substrate film, The base film is fixed to the first main surface of the substrate via the adhesive layer.

4. The transparent laminate according to claim 1 or 2, characterized in that: The first functional layer includes an adhesive layer and the anti-fog layer, The anti-fog layer is fixed to the first main surface of the substrate through the adhesive layer.

5. The transparent laminate according to claim 1 or 2, characterized in that: The first functional layer has the anti-fog layer, The anti-fog layer is laminated on the first main surface of the substrate.

6. The transparent laminate according to claim 1, wherein: The refractive index of the hollow particles is 1.15 to 2.

70.

7. The transparent laminate according to claim 1 or 6, characterized in that: The average particle size of the hollow particles is 20 to 100 nm.

8. The transparent laminate according to any one of claims 1, 6 and 7, characterized in that: The hollow particles are selected from the group consisting of silicon dioxide, magnesium fluoride, aluminum oxide, aluminosilicate, titanium oxide and zirconium oxide.

9. The transparent laminate according to any one of claims 1, 6 to 8, characterized in that: The second functional layer contains a solvent having a boiling point of 100° C. to 300° C.

10. The transparent laminate according to claim 9, characterized in that: The solvent contains 3-methoxy-3-methyl-1-butanol as a main component.

11. The transparent laminate according to claim 9 or 10, characterized in that: The second functional layer contains 1 ppb or more and 5 g / cm 3 The solvents described below.

12. The transparent laminate according to any one of claims 1, 6 to 8, characterized in that: The binder contains at least one of polysilsesquioxane and silicon dioxide.

13. The transparent laminate according to any one of claims 1, 6 to 12, characterized in that: The porosity of the second functional layer is 0 to 70 volume %.

14. The transparent laminate according to claim 1, wherein: The second functional layer includes a first layer stacked on the first functional layer and a second layer stacked on the first layer and having a lower refractive index than the first layer.

15. The transparent laminate according to any one of claims 1 to 14, characterized in that: The substrate is a float glass produced by a float process, and a concentration of tin oxide in the first main surface is lower than a concentration of tin oxide in the second main surface.

16. The transparent laminate according to any one of claims 1 to 14, characterized in that: The substrate is a float glass produced by a float process, and a concentration of tin oxide in the first main surface is higher than a concentration of tin oxide in the second main surface.

17. The transparent laminate according to any one of claims 1 to 16, characterized in that: The invention also includes a third functional layer laminated on the second main surface of the substrate.

Images