Functional films and glass laminates with adhesive layers

Abstract

To provide a glass laminate which can suppress occurrence of perspective distortion, occurrence of poor appearance such as cracks, increase in a sheet resistance value of an inorganic laminate film and increase in a haze value, even when being used under severe environment such as high temperature and high humidity environment.SOLUTION: A glass laminate (GL1) has such a structure that a functional film (F) having a base material resin film (10) and an inorganic laminate film (20) is bonded to one surface of a glass base material (G) through an adhesive layer (40), wherein the base material resin film is an amorphous resin film or an amorphous resin film with a hard coat layer, the inorganic laminate film includes a plurality of dielectric layers (21) containing a zinc oxide, and one or more conductor layers (22) which are sandwiched among the plurality of dielectric layers and contain silver and / or a silver alloy, and the adhesive layer has storage elastic modulus (E') at 80°C of 7-40 kPa.SELECTED DRAWING: Figure 7

Description

Technical Field

[0001] The present disclosure relates to a functional film with an adhesive layer and a glass laminate.

Background Art

[0002] In applications such as window glass for vehicles such as automobiles, a functional film with an adhesive layer in which a functional film and an adhesive layer are sequentially laminated on a base resin film may be bonded to the surface of a glass substrate to impart functions. In this specification, unless otherwise specified, "adhesive layer" includes an adhesive layer.

[0003] One example of the functional film is a transparent electrothermal film. For example, on the inner surface of a vehicle front glass, for the prevention of autonomous driving and collision accidents, an optical device including optical devices such as an ADAS (Advanced Driver Assistance systems) camera, LiDAR (Light Detection And Ranging), radar, and optical sensors that acquire information in front of the vehicle, and a housing called a bracket that houses the same may be installed. In such a configuration, in order to improve the sensing accuracy by the optical device, it is preferable to dispose a transparent electrothermal film that prevents fogging and adhesion of rain, frost, ice, snow, etc. on the glass portion in front of the optical device.

[0004] By bonding a functional film with an adhesive layer in which a transparent electrothermal film as a functional film and an adhesive layer are sequentially laminated on a base resin film to the inner surface of the front glass, the transparent electrothermal film can be easily disposed on the inner surface of the front glass. From the viewpoints of resistance heating characteristics, transmittance, etc., a preferable transparent electrothermal film is an inorganic laminated film including a plurality of dielectric layers and a conductor layer containing silver or a silver alloy sandwiched between the plurality of dielectric layers.

[0005] Patent Document 1 discloses a solar radiation adjustment film as a functional film with an adhesive layer, having a hard coat layer on one main surface of a polyester film and a solar radiation reflective laminated film on the other main surface, wherein the solar radiation reflective laminated film has a laminated structure of a first zinc oxide layer, a first silver alloy layer, a second zinc oxide layer, a second silver alloy layer, a third zinc oxide layer, a protective layer and an adhesive layer (Claim 1-3). Patent Document 1 discloses a glass laminate in which the above-mentioned solar reflective laminate is bonded to a glass substrate (Claim 8).

[0006] Patent Document 2 discloses a transparent conductive film for heaters, in which a first metal oxide layer, a metal layer containing silver or a silver alloy, and a second metal oxide layer are sequentially laminated on a transparent resin substrate as a functional film (Claim 1). A glass laminate is disclosed in which a glass substrate and a transparent conductive film are laminated with an adhesive layer in between (paragraphs 0016, 0017). [Prior art documents] [Patent Documents]

[0007] [Patent Document 1] Japanese Patent Publication No. 2012-37634 [Patent Document 2] International Publication No. 2020 / 022270 [Overview of the project] [Problems that the invention aims to solve]

[0008] In windshields equipped with optical devices, achieving high sensing accuracy requires high optical properties in the glass laminate, which consists of a functional film with an adhesive layer bonded to a glass substrate. Specifically, high transmittance, low haze value, and low transparency distortion are preferable. However, when the above-mentioned glass laminate is used in a high-temperature environment, a high-humidity environment, or a high-temperature, high-humidity environment, its properties may deteriorate, such as an increase in haze value, the occurrence of transparency distortion, cracking in the transparent heating film (inorganic laminate), and an increase in the resistance value of the transparent heating film (inorganic laminate).

[0009] As described in the [Examples] section of Patent Documents 1 and 2, polyethylene terephthalate (PET) has conventionally been used as the base resin film for functional films. Since PET is a crystalline resin, when PET film is used in high temperature and high humidity environments, the film may whiten due to the generation and aggregation of low molecular weight oligomers, and the haze value may increase.

[0010] The coefficients of linear expansion of the substrate resin film and adhesive layer, which are made of organic materials, are significantly larger than those of the glass substrate and transparent electro-heating film (inorganic laminated film), which are made of inorganic materials. Under high-temperature (high-humidity) conditions, the base resin film and adhesive layer expand significantly, while the glass substrate and transparent heating film (inorganic laminate) hardly expand at all. In this case, strain may occur in the adhesive layer, potentially causing distortion in the glass laminate. Furthermore, significant stress may be applied to the transparent heating film (inorganic laminate) sandwiched between organic materials, potentially causing cracks in the transparent heating film (inorganic laminate). Cracks in the transparent heating film (inorganic laminate) may lead to an increase in haze value and / or resistance value.

[0011] This disclosure is made in view of the above circumstances and aims to provide a glass laminate having an inorganic laminate film including a conductive layer and a dielectric layer, which can suppress the occurrence of transparency distortion, appearance defects such as cracks, an increase in the sheet resistance value and haze value of the inorganic laminate film, even when used in harsh environments such as high temperature and high humidity environments, as well as a functional film with an adhesive layer suitable for use in the manufacture of the same. [Means for solving the problem]

[0012] This disclosure provides functional films and glass laminates with adhesive layers as described below. [1] A functional film having a base resin film, an inorganic laminated film laminated on one surface of the base resin film, and an adhesive layer provided on the inorganic laminated film of the functional film, The base resin film is an amorphous resin film, or an amorphous resin film with a hard coat layer, wherein a hard coat layer made of a cured product of a curable composition is formed on at least one surface of the amorphous resin film. The inorganic multilayer film comprises a plurality of dielectric layers containing zinc oxide, and one or more conductive layers sandwiched between the plurality of dielectric layers, each containing at least one metal selected from the group consisting of silver and silver alloys. The adhesive layer is an optically transparent adhesive layer comprising an adhesive containing one or more adhesive resins, and having a storage modulus (E') of 7 to 40 kPa at 80°C, wherein the functional film has an adhesive layer.

[0013] [2] The functional film with adhesive layer of [1] further comprising a lower metal compound layer between the base resin film and the inorganic laminate film, which contains one or more metal compounds including at least one metal element selected from the group consisting of Si and Al, and substantially does not contain zinc oxide. [3] A functional film with an adhesive layer according to [1] or [2], further comprising an upper metal compound layer on the surface of the inorganic laminated film on the adhesive layer side, which contains one or more metal compounds including at least one metal element selected from the group consisting of Al, Si, Ti, Ga, In, Sn, Ta, and W, and substantially free of zinc oxide.

[0014] [4] The constituent resin of the amorphous resin film is at least one amorphous resin selected from the group consisting of polycarbonate resins, cycloolefin polymers, and polyimides, a functional film with an adhesive layer according to any of [1] to [3].

[0015] [5] A functional film with an adhesive layer according to any of [1] to [4], wherein the adhesive is an acrylic adhesive, a silicone adhesive, a urethane adhesive, or a butadiene adhesive. [6] The functional film with an adhesive layer according to any one of [1] to [5], wherein the thickness of the adhesive layer is 25 to 110 μm. [7] The total thickness of the inorganic laminated film is 45~380 nm and is the functional film with an adhesive layer according to any one of [1] to [6].

[0016] [8] A glass laminate in which a functional film is bonded via an adhesive layer on one surface of a glass substrate, where the functional film has a base resin film and an inorganic laminated film laminated on the surface of the base resin film on the adhesive layer side, the base resin film is an amorphous resin film or an amorphous resin film with a hard coat layer formed of a cured product of a curable composition on at least one surface thereof, the inorganic laminated film includes a plurality of dielectric layers containing zinc oxide and one or more conductor layers containing at least one metal selected from the group consisting of silver and silver alloys, sandwiched between the plurality of dielectric layers, the adhesive layer is an optically transparent adhesive layer composed of an adhesive containing one or more adhesive resins and having a storage elastic modulus (E’) of 7 to 40 kPa at 80°C.

[0017] [9] The glass laminate according to [8], wherein the functional film further has a lower metal compound layer containing one or more metal compounds containing at least one metal element selected from the group consisting of Si and Al and substantially free of zinc oxide, between the base resin film and the inorganic laminated film.

[10] The glass laminate according to [8] or [9], wherein the functional film further has an upper metal compound layer containing one or more metal compounds containing at least one metal element selected from the group consisting of Al, Si, Ti, Ga, In, Sn, Ta, and W and substantially free of zinc oxide, on the surface of the inorganic laminated film on the adhesive layer side.

[0018]

[11] The constituent resin of the amorphous resin film is at least one amorphous resin selected from the group consisting of polycarbonate resins, cycloolefin polymers, and polyimides, and the glass laminate according to any one of [8] to

[10] .

[0019]

[12] The adhesive is an acrylic adhesive, a silicone adhesive, a urethane adhesive, or a butadiene adhesive, and the glass laminate according to any one of [8] to

[11] .

[13] The glass laminate according to any one of [8] to

[12] , wherein the thickness of the adhesive layer is 20 to 105 μm.

[14] The glass laminate according to any one of [8] to

[13] , wherein the total thickness of the inorganic laminate film is 90 to 200 nm. [Effect of the Invention]

[0020] In the functional film with an adhesive layer and the glass laminate of the present disclosure, the base resin film is an amorphous resin film or an amorphous resin film with a hard coat layer, and the adhesive layer is an optically transparent adhesive layer having a storage elastic modulus (E') at 80°C of 7 to 40 kPa. According to the present disclosure, by optimizing the storage elastic modulus (E') of the base resin film and the adhesive layer at 80°C, an inorganic laminate film including a conductor layer and a dielectric layer is provided, and even when used in a harsh environment such as a high-temperature and high-humidity environment, the occurrence of perspective distortion, the occurrence of appearance defects such as cracks, the increase in the sheet resistance value of the inorganic laminate film, and the increase in the haze value can be suppressed. A functional film with an adhesive layer suitable for use in the production thereof can also be provided. [Brief Description of the Drawings]

[0021] [Figure 1] It is a schematic cross-sectional view of the functional film with an adhesive layer according to the first embodiment of the present invention. [Figure 2] It is a schematic cross-sectional view of the functional film with an adhesive layer according to the second embodiment of the present invention. [Figure 3] It is a schematic cross-sectional view of the functional film with an adhesive layer according to the third embodiment of the present invention. [Figure 4]This is a schematic cross-sectional view of a functional film with an adhesive layer according to a fourth embodiment of the present invention. [Figure 5] This is a schematic cross-sectional view of a functional film with an adhesive layer according to a fifth embodiment of the present invention. [Figure 6] This is an overall plan view of a glass laminate according to one embodiment of the present invention. [Figure 7] This is a partially enlarged schematic cross-sectional view (section along line VII-VII) of Figure 6. [Modes for carrying out the invention]

[0022] In this specification, unless otherwise specified, the "surface" of a plate-like member such as a glass plate refers to the main surface with a large area, excluding the end face (also called the side face) of the plate-like member. Generally, thin film structures are referred to as "films" and "sheets," etc., depending on their thickness. In this specification, these are not clearly distinguished. Therefore, the term "film" as used herein may include "sheets." In this specification, unless otherwise specified, "a layer substantially free of a certain component" refers to a layer in which the content of that component is 5 mol% or less. In this specification, unless otherwise specified, "main component" refers to a component present in an amount of 80 mol% or more. In this specification, unless otherwise specified, the "~" symbol indicating a numerical range is used to mean that the numbers before and after it are included as the lower and upper limits, respectively. Embodiments of the present invention will be described below.

[0023] [Functional films with adhesive layers, glass laminates] Referring to Figures 1 to 5, the structures of the functional films with adhesive layers according to the first to fifth embodiments of the present invention will be described. Referring to Figures 6 and 7, the structure of a glass laminate according to one embodiment of the present invention will be described. Figures 1 to 5 and Figure 7 are schematic cross-sectional views of the functional films with adhesive layers or the glass laminates. Figure 6 is a schematic plan view of the glass laminate. Figure 7 is a partially enlarged cross-sectional view of Figure 6 (cross-sectional view along line VII-VII). For ease of viewing, the scale of each component has been appropriately changed from the actual scale. The same reference numerals are used for the same components, and their descriptions are omitted as appropriate.

[0024] As shown in Figures 1 to 5, the functional films AF (AF1 to AF5) with adhesive layers of the first to fifth embodiments each have a functional film F (F1 to F5) having a base resin film 10 and an inorganic laminated film 20 laminated on one surface of the base resin film 10, and an adhesive layer 40 provided on the inorganic laminated film 20 of the functional film F.

[0025] In the functional films AF (AF1 to AF5) with adhesive layers, the base resin film 10 is an amorphous resin film 11, or an amorphous resin film with a hard coat layer, wherein a hard coat layer 12 made of a cured product of a curable composition is formed on at least one surface of the amorphous resin film 11. In the examples shown in Figures 1 to 4, the base resin film 10A is an amorphous resin film 11. In the example shown in Figure 5, the base resin film 10B is an amorphous resin film with a hard coat layer, in which a hard coat layer 12 is formed on both sides of the amorphous resin film 11.

[0026] In the functional films AF (AF1 to AF5) with adhesive layers, the inorganic laminated film 20 includes a plurality of dielectric layers 21 containing zinc oxide, and one or more conductive layers 22 sandwiched between the plurality of dielectric layers 21, each containing at least one metal selected from the group consisting of silver and silver alloys. The inorganic laminated film 20 can be a functional film that imparts a specific function to a desired region of a substrate such as a glass substrate. The inorganic laminated film 20 with the above configuration has good resistance heating characteristics and transmittance, and is suitable as a transparent electric heating film, etc. In the illustrated example, the inorganic laminated film 20 of the adhesive-coated functional film AF (AF1~AF5) consists of two dielectric layers 21 containing zinc oxide and one conductive layer 22 sandwiched between the two dielectric layers 21, which contains at least one metal selected from the group consisting of silver and silver alloys.

[0027] The adhesive-coated functional films AF2 and AF4 further have a lower metal compound layer 31 between the base resin film 10 and the inorganic laminated film 20, which contains one or more metal compounds including at least one metal element selected from the group consisting of Si and Al, and substantially does not contain zinc oxide. The functional films AF3 and AF4 with adhesive layers further have an upper metal compound layer 32 on the surface of the inorganic laminated film 20 on the side of the adhesive layer 40, which contains one or more metal compounds including at least one metal element selected from the group consisting of Al, Si, Ti, Ga, In, Sn, Ta, and W, and substantially does not contain zinc oxide.

[0028] Functional film F1, included in the adhesive-layered functional films AF1 and AF5, has a laminated structure of an inorganic laminated film 20 / base resin film 10. The functional film F2 contained in the adhesive layer functional film AF2 has a laminated structure of inorganic laminated film 20 / lower metal compound layer 31 / base resin film 10. The functional film F3 included in the adhesive-coated functional film AF3 has a laminated structure consisting of an upper metal compound layer 32, an inorganic laminated film 20, and a base resin film 10. The functional film F4 included in the adhesive-coated functional film AF4 has a laminated structure consisting of an upper metal compound layer 32, an inorganic laminated film 20, a lower metal compound layer 31, and a base resin film 10.

[0029] The glass laminate GL1 of one embodiment shown in Figure 7 has a structure in which a glass substrate G and a functional film F are bonded to one surface of the glass substrate G via an adhesive layer 40. The functional film F can be laminated to at least a portion of one surface of the glass substrate G. The functional film F comprises a base resin film 10 and an inorganic laminated film 20 laminated on the surface of the base resin film 10 on the side with the adhesive layer 40. The functional film F can be any of the functional films F1 to F5 shown in Figures 1 to 5. In the illustrated example, the functional film F is the functional film F1 shown in Figure 1.

[0030] The method for manufacturing a functional film AF (any of AF1 to AF5) with an adhesive layer is: The process of preparing the base resin film 10 (S11), Step (S12) is to form a plurality of inorganic layers, including an inorganic laminated film 20, on one surface of a base resin film 10 to obtain a functional film F (any of F1 to F5), The process includes a step (S13) of laminating an adhesive layer 40 onto a functional film F.

[0031] The configuration of the multiple inorganic layers formed in step (S12) is an inorganic multilayer film 20, an inorganic multilayer film 20 / lower metal compound layer 31, an upper metal compound layer 32 / inorganic multilayer film 20, or an upper metal compound layer 32 / inorganic multilayer film 20 / lower metal compound layer 31. As a method for depositing multiple inorganic layers, vapor phase deposition methods such as sputtering and CVD (Chemical Vapor Deposition) are preferred.

[0032] The first method for manufacturing the glass laminate GL1 is: The process of preparing the glass substrate G (S21), The process (S22) involves preparing a functional film AF with an adhesive layer (one of AF1 to AF5), The process includes a step (S23) of laminating the functional film with the adhesive layer onto a glass substrate G. In step (S23), lamination is performed such that the glass substrate G and the functional film F (one of F1 to F5) are bonded together via the adhesive layer 40.

[0033] The second method for manufacturing the glass laminate GL1 is: The process of preparing the glass substrate G (S31), The process of preparing a functional film F (one of F1 to F5) (S32), The process includes a step (S33) of bonding the functional film F to the glass substrate G via an adhesive layer 40.

[0034] (Base resin film) As explained in the [Background Technology] section, polyethylene terephthalate (PET) has conventionally been used as the base resin film for functional films. Since PET is a crystalline resin, when PET films are used in high-temperature and high-humidity environments, the formation and aggregation of low-molecular-weight oligomers can cause the film to whiten and increase the haze value. The base resin film included in the functional film with adhesive layer and glass laminate of this disclosure is an amorphous resin film or an amorphous resin film with a hard coat layer. When the base resin film has such a configuration, even when used in high temperature and high humidity environments, the generation and aggregation of low molecular weight oligomers are suppressed, and the whitening of the film and the increase in haze value are suppressed.

[0035] In this specification, unless otherwise specified, an "amorphous resin film" is a film in which no significant crystal peaks are observed in the X-ray diffraction (XRD) pattern of the resin film alone within the diffraction angle 2θ range of 20 to 30°. XRD measurements are performed on the resin film alone using an XRD instrument. After removing the background and Kα2 peaks, the integral value in the diffraction angle 2θ range of 20 to 30° is determined from the resulting XRD pattern. If this integral value is 100 times or less the integral value similarly measured for soda-lime glass, a typical amorphous material, then there are no prominent crystalline peaks in the diffraction angle 2θ range of 20 to 30°, and the resin film can be said to be amorphous.

[0036] As the constituent resin of the amorphous resin film, at least one amorphous resin selected from the group consisting of polycarbonate resins (PC), cycloolefin polymers (COP), and polyimides (PI) is preferred from the viewpoint of transparency and heat resistance.

[0037] The hard coat layer consists of a cured product of a curable composition and is also called a cured film. The hard coat layer can be an organic cured film made of resins such as acrylic resins and urethane resins. The curable composition contains one or more curable compounds, such as thermosetting or active energy ray curable resins; monomers, oligomers, or prepolymers that become resins upon heating or irradiation with active energy rays. Preferred curable compounds include thermosetting or active energy ray curable acrylic resins and thermosetting or active energy ray curable urethane resins. Examples of active energy rays include ultraviolet rays and electron beams. The hard coat layer can be formed by coating a curable composition onto at least one surface of an amorphous resin film and curing it.

[0038] (Adhesive layer) In the functional film with adhesive layer and glass laminate of this disclosure, the adhesive layer is an optically transparent adhesive layer comprising an adhesive containing one or more adhesive resins. A commercially available optical clear adhesive (OCA) can be used as the material for the adhesive layer. OCA has a structure in which an adhesive resin film containing one or more adhesive resins is sandwiched between a pair of release-type protective films. The adhesive resin film can be removed by peeling off the protective films on both sides. This adhesive resin film can be used as the adhesive layer. When using this adhesive resin film, bonding at room temperature and atmospheric pressure is possible.

[0039] In this specification, unless otherwise specified, "optically transparent" means that visible light (light in the wavelength range of 380 to 780 nm) can be transmitted through it. The optically transparent adhesive layer preferably has low light scattering and high total light transmittance. The optically transparent adhesive layer preferably has a haze value of 1% or less, as measured using a general haze meter in accordance with JIS K 7136. The optically transparent adhesive layer preferably has a total light transmittance of 80% or more, as measured using a general haze meter.

[0040] There are no particular restrictions on when to peel off the protective film on both sides of the OCA. In the manufacture of functional films with an adhesive layer, it is preferable to peel off only one of the protective films on both sides of the OCA and then laminate the OCA to the functional film. The remaining protective film can protect the adhesive layer contained in the functional film with an adhesive layer.

[0041] In the first method for manufacturing a glass laminate, it is preferable to peel off the remaining protective film from the functional film with adhesive layer during the manufacturing of the glass laminate to expose the adhesive layer, and then bond the functional film with adhesive layer to the glass substrate.

[0042] In the second method for manufacturing the glass laminate, it is preferable to peel off only one of the protective films on both sides of the OCA, bond the OCA to the functional film, then peel off the remaining protective film to expose the adhesive layer, and bond the functional film to the glass substrate via the adhesive layer.

[0043] In the second method for manufacturing the glass laminate, one of the protective films on both sides of the OCA may be peeled off, the OCA may be bonded to the glass substrate, the remaining protective film may be peeled off to expose the adhesive layer, and the functional film may be bonded to the glass substrate via the adhesive layer.

[0044] When using OCA for bonding, good adhesion can be achieved by using a dedicated bonding device. Furthermore, since air may remain inside, degassing treatment by vacuum or pressurization may be performed after bonding.

[0045] The adhesive constituting the adhesive layer is not particularly limited and includes acrylic adhesives, silicone adhesives, urethane adhesives, and butadiene adhesives. The technology of this disclosure is preferred when the adhesive layer consists of an acrylic adhesive or the like.

[0046] As explained in the [Background Technology] section, generally, the coefficient of thermal expansion of the substrate resin film and adhesive layer, which are made of organic materials, is much larger than that of the glass substrate and inorganic laminate film, which are made of inorganic materials. Under high temperature (high humidity) conditions, the substrate resin film and adhesive layer expand significantly, while the glass substrate and inorganic laminate film hardly expand at all. In this case, strain occurs in the adhesive layer, which may cause distortion in the glass laminate. In addition, large stresses may be applied to the inorganic laminate film sandwiched between organic materials, which may cause cracks in the inorganic laminate film. Cracks in the inorganic laminate film may lead to an increase in haze value and / or resistance value.

[0047] In the functional film with adhesive layer and glass laminate of this disclosure, the adhesive layer has a storage modulus (E') of 7 to 40 kPa at 80°C. Generally, the following regions exist in the storage modulus curve of a polymer. Note that the storage modulus curve is a curve (DMTA curve) that shows the relationship between temperature and storage modulus, obtained by dynamic thermomechanical analysis (DMTA method). The temperature range up to the glass transition temperature (Tg) is called the glass region. In this region, the storage modulus decreases gradually with increasing temperature. Beyond the glass transition temperature (Tg), there is a temperature range where the storage modulus decreases significantly with increasing temperature. This temperature range is called the glass-rubber transition region. Subsequently, there is a temperature range where the storage modulus does not change significantly even when the temperature is increased. This temperature range is called the rubbery flat region. In the rubbery flat region, the molecular chains of the polymer move, but they do not completely melt. Subsequently, there is a temperature range where the storage modulus decreases significantly as the temperature rises. This temperature range is called the flow region.

[0048] Generally, optically transparent adhesive layers are used within a temperature range that falls within the rubbery flat region of the storage modulus curve. 80°C is a typical temperature within the rubbery flat region of the storage modulus curve for optically transparent adhesive layers. Optically transparent adhesive layers tend to have higher adhesive strength when their storage modulus (E') is high. If the storage modulus (E') of the optically transparent adhesive layer at 80°C is lower than the suitable range, the adhesion of the optically transparent adhesive layer to the glass substrate will be weak at 80°C, and strain may occur in the expanded optically transparent adhesive layer. If the storage modulus (E') at 80°C is 7kPa or higher, strain in the adhesive layer and the resulting transparency distortion of the glass laminate can be effectively suppressed in high-temperature (high-humidity) environments. The storage modulus (E') of the adhesive layer at 80°C is 7 kPa or higher, preferably 10 kPa or higher, more preferably 12 kPa or higher, and particularly preferably 14 kPa or higher.

[0049] If the storage modulus (E') of the optically transparent adhesive layer at 80°C is higher than the suitable range, at 80°C, the inorganic laminated film may be subjected to large stresses from the expanded optically transparent adhesive layer while strongly adhered to it, potentially causing cracks in the inorganic laminated film. If the storage modulus (E') at 80°C is 40kPa or less, cracking of the inorganic laminated film under high-temperature (high-humidity) environments, and the resulting increase in haze value and / or resistance value, can be effectively suppressed. The storage modulus (E') of the adhesive layer at 80°C is 40 kPa or less, preferably 36 kPa or less, more preferably 30 kPa or less, and particularly preferably 20 kPa or less.

[0050] As mentioned above, optically transparent adhesive layers are generally used within the temperature range of the rubbery flat region of the storage modulus curve. Within the rubbery flat region, the storage modulus (E') does not change significantly even if the temperature changes. Furthermore, in applications such as window glass for automobiles, 80°C is a harsher condition than the normal operating environment. Therefore, if the storage modulus (E') of the adhesive layer is 7 to 40 kPa at 80°C, the storage modulus (E') is suitable even at the normal operating environment temperature, and strain in the adhesive layer and cracking of the inorganic laminate can be effectively suppressed.

[0051] The storage modulus (E') of an adhesive layer at 80°C can be measured by dynamic viscoelasticity measurement using a rheometer. Under the condition of a frequency of 1 Hz, the storage modulus (E') of the adhesive layer or its material (for example, an adhesive resin film extracted from an OCA structure in which an adhesive resin film is sandwiched between a pair of peelable protective films, by peeling off the protective films on both sides) can be measured at different temperatures, and the storage modulus (E') at 80°C can be determined from the resulting storage modulus curve.

[0052] The thickness of the adhesive layer is not particularly limited. The thickness of the adhesive layer in the functional film with adhesive layer of this disclosure is preferably 25 to 110 μm, more preferably 30 to 110 μm, particularly preferably 40 to 99 μm, and most preferably 40 to 80 μm. The thickness of the adhesive layer included in the glass laminate of this disclosure is preferably 20 to 105 μm, more preferably 25 to 105 μm, particularly preferably 35 to 95 μm, and most preferably 35 to 75 μm. Furthermore, the thickness of the adhesive layer contained in the glass laminate tends to be about 5 to 10 μm thinner than the thickness of the adhesive layer contained in the functional film with an adhesive layer, due to the pressure applied during lamination. Designing the thickness of the adhesive layer included in the glass laminate to be relatively small is preferable because it can suppress the transparency distortion of the glass laminate.

[0053] (Inorganic multilayer film) The inorganic laminated film included in the functional film with adhesive layer and glass laminate of this disclosure includes a plurality of dielectric layers containing zinc oxide and one or more conductive layers sandwiched between the plurality of dielectric layers, each containing at least one metal selected from the group consisting of silver and silver alloys.

[0054] <Dielectric layer> The number of dielectric layers containing zinc oxide in the inorganic multilayer film is two or more, preferably 2 to 4, and more preferably 2 to 3. The dielectric layer contains zinc oxide, preferably with zinc oxide as the main component. The dielectric layer may optionally contain one or more metallic elements other than Zn, such as Al, Ti, Ga, In, Sn, Ta, and W. From the viewpoint of electrical properties and transmittance, the zinc oxide content in the dielectric layer is 70 mol% or more, preferably 75 mol% or more, and particularly preferably 80 mol% or more. The upper limit of the zinc oxide content in the dielectric layer is not particularly limited, but is preferably 95 mol%, more preferably 92 mol%. From the viewpoint of electrical properties and durability, Ti-doped ZnO (TZO) is preferred as the constituent material of the dielectric layer. The dielectric layer may contain any other optional components and unavoidable impurities not mentioned above. The thickness of the dielectric layer is not particularly limited, but is preferably 20 to 90 nm, more preferably 25 to 70 nm, and most preferably 25 to 50 nm, from the viewpoint of resistance heating characteristics and transmittance. The compositions of the multiple dielectric layers may be the same or different. The thicknesses of the multiple dielectric layers may be the same or different.

[0055] <Conductive layer> The conductive layer contains at least one metal selected from the group consisting of silver and silver alloys. The conductive layer may contain at least one metallic element other than silver, such as Al, Ti, V, Cr, Ni, Cu, Zr, Rh, Pd, W, Ir, Pt, and Au. From the viewpoint of electrical properties and transmittance, the silver content in the conductive layer is preferably 97 mol% or more, and more preferably 98 mol% or more. The thickness of the conductive layer is not particularly limited, but is preferably 5 to 20 nm, more preferably 5 to 15 nm, and most preferably 5 to 10 nm, from the viewpoint of electrical properties and transmittance. The conductive layer may contain any other optional components and unavoidable impurities not mentioned above.

[0056] The total thickness of the inorganic multilayer film is not particularly limited, and from the viewpoint of electrical properties and transmittance, Preferably 45-380nm, more Preferably 45 ~200nm, comfortable 45 ~150nm, particularly preferably 45 It is approximately 120 nm.

[0057] (Lower metal compound layer) The functional films and glass laminates with adhesive layers of the present disclosure may have a lower metal compound layer between the base resin film and the inorganic laminate, which contains one or more metal compounds (MU) comprising at least one metal element selected from the group consisting of Si and Al, and which is substantially free of zinc oxide. Examples of metal compounds (MU) include oxides, nitrides, and oxynitrides of Si; oxides, nitrides, and oxynitrides of Al, etc. As the metal compound (MU), silicon compounds such as silicon dioxide and silicon nitride are preferred. Silicon compounds doped with one or more metal elements such as Al are also preferred. The lower metal compound layer preferably consists mainly of one or more metal compounds (MU). The content of one or more metal compounds (MU) in the lower metal compound layer (total amount if there are multiple types) is preferably 85 mol% or more, more preferably 90 mol% or more, and particularly preferably 95 mol% or more. The lower metal compound layer may contain optional components other than those mentioned above, as well as unavoidable impurities.

[0058] Generally, conductive layers containing silver or silver alloys tend to undergo alteration in the presence of moisture and / or oxygen, such as aggregation of silver or silver alloys or ion migration, which increases their resistance. Therefore, when using glass laminates in a (high temperature) and high humidity environment, moisture and / or oxygen may penetrate the conductive layer from the outside through the base resin film, potentially increasing the resistance of the conductive layer.

[0059] Generally, amorphous resin films do not experience a significant increase in haze values ​​even when used in high-temperature, high-humidity environments, but they tend to have a higher coefficient of thermal expansion and water vapor permeability than PET films. Therefore, when using amorphous resin films as the base resin film, problems arising from the difference in the coefficient of thermal expansion between inorganic and organic materials, and the water vapor permeability of the base resin film, tend to occur more frequently.

[0060] The lower metal compound layer, which contains the above-mentioned metal compound (MU) and substantially does not contain zinc oxide, tends to have lower permeability to water vapor and / or oxygen than the dielectric layer containing zinc oxide. The lower metal compound layer can act as a barrier layer against water vapor and / or oxygen. In (high temperature) and high humidity environments, the lower metal compound layer can effectively suppress the intrusion of moisture and / or oxygen from the outside through the substrate resin film into the conductive layer, and can effectively suppress the deterioration and increase in resistance of the conductive layer containing silver or a silver alloy.

[0061] The lower metal compound layer, which contains the above-mentioned metal compound (MU) and substantially does not contain zinc oxide, can act as a stress-relieving layer that alleviates stress on the inorganic laminated film in high-temperature (high-humidity) environments, etc., due to the difference between the coefficient of thermal expansion of the glass substrate and inorganic laminated film made of inorganic materials and the coefficient of thermal expansion of the substrate resin film and adhesive layer made of organic materials. The lower metal compound layer can alleviate stress on the inorganic laminated film in (high-temperature) high-humidity environments, etc., and effectively suppress cracks in the inorganic laminated film and the resulting increase in haze value and / or resistance value.

[0062] (Top metal compound layer) The functional films and glass laminates with adhesive layers of the present disclosure may have an upper metal compound layer on the adhesive layer side surface of the inorganic laminate that contains one or more metal compounds (MT) comprising at least one metal element selected from the group consisting of Al, Si, Ti, Ga, In, Sn, Ta, and W, and substantially free of zinc oxide. Examples of metal compounds (MTs) include SnO2 (tin oxide), ITO (indium tin oxide), TTO (tantalum tin oxide), GIT (gallium indium tin oxide), WO3, Al2O3, Ga2O5, TiO2, Ta2O5, and combinations thereof. As the metal compound (MT), a metal compound containing at least one metal element selected from the group consisting of Ga, In, Sn, and Ta is preferred. For example, SnO2, ITO, TTO, and GIT are preferred. The upper metal compound layer preferably consists mainly of one or more metal compounds (MT). The content of one or more metal compounds (MT) (or the total amount if there are multiple types) in the upper metal compound layer is preferably 85 mol% or more, more preferably 90 mol% or more, and particularly preferably 95 mol% or more. The upper metal compound layer may contain any other optional components and unavoidable impurities not mentioned above.

[0063] If the acid value of the adhesive resin contained in the adhesive layer is relatively high, under (high temperature) and high humidity conditions, the adhesive resin may hydrolyze and generate acid, which may affect the dielectric layer containing zinc oxide, which has poor chemical resistance to acid. An upper metal compound layer containing the above-mentioned metal compound (MT) and substantially free of zinc oxide tends to have higher acid resistance than a dielectric layer containing zinc oxide. The upper metal compound layer can act as an acid barrier layer. Even when acid is generated in an adhesive layer containing a highly acidic adhesive resin under (high temperature) and high humidity environments, the upper metal compound layer can effectively suppress the penetration of that acid into the dielectric layer and effectively suppress the deterioration of the dielectric layer. Examples of adhesives containing high acid value tack resins include acrylic adhesives. Acrylic tack resins contain carboxyl groups, which may generate carboxylic acids in (high temperature) and high humidity environments. Therefore, the upper metal compound layer is particularly effective when the adhesive layer consists of an acrylic adhesive.

[0064] (Glass substrate) In applications such as windows for automobiles and other vehicles, the glass substrate preferably includes laminated glass or tempered glass, in which multiple glass plates are bonded together with an interlayer film in between. There are no particular limitations on the type of glass sheet used as the material for laminated glass and tempered glass, and examples include soda-lime glass, borosilicate glass, aluminosilicate glass, lithium silicate glass, quartz glass, sapphire glass, and alkali-free glass. Tempered glass is obtained by strengthening a glass plate as described above using known methods such as ion exchange and air-cooled strengthening. Air-cooled tempered glass is preferred as the tempered glass.

[0065] The thickness of the laminated glass is not particularly limited, but for applications such as vehicle windows (windshields, side windows, and rear windows), it is preferably 1 to 6 mm, more preferably 1 to 3 mm. The thickness of tempered glass is not particularly limited, but for applications such as vehicle windows (windshields, side windows, and rear windows), it is preferably 1 to 6 mm, more preferably 1 to 3 mm. The multiple glass plates that make up laminated glass are usually a combination of multiple untempered glass panes, but they may also be a combination of tempered glass and untempered glass.

[0066] Vehicle window glass may have a curved shape such that the outer side is convex when installed in a vehicle. If the vehicle window glass is laminated glass, both the inner and outer glass panes may have a curved shape such that the outer side is convex. Vehicle window glass may have a single-bend shape curved in only one direction, either left-right or up-down, or a double-bend shape curved in both the left-right and up-down directions. The radius of curvature of vehicle window glass may be between 2000 and 11000 mm. The radii of curvature in the left-right and up-down directions may be the same or different. Gravity forming, press forming, and roller forming are used for bending vehicle window glass.

[0067] The interlayer of laminated glass consists of a resin film. The constituent resin is not particularly limited as long as it is a resin that can bond multiple glass plates well. Preferably, the interlayer contains one or more resins selected from the group consisting of polyvinyl butyral (PVB), ethylene vinyl acetate copolymer (EVA), cycloolefin polymer (COP), polyurethane (PU), and ionomer resins. The interlayer may contain one or more additives other than resin, as needed. As the material for the interlayer, a resin film containing the resin exemplified above is preferred. The interlayer in laminated glass can be either a single layer or a multilayer film.

[0068] Laminated glass and tempered glass may have a coating on at least a portion of their surface that has functions such as water repellency, low reflectivity, low emissivity, ultraviolet shielding, infrared shielding, and coloring. Laminated glass may have a film in at least a portion of its interior that has functions such as low reflectivity, low emissivity, ultraviolet shielding, infrared shielding, and coloring. At least a portion of the interlayer of the laminated glass may have functions such as ultraviolet shielding, infrared shielding, and coloring.

[0069] Laminated glass and tempered glass may have a light-shielding layer in a predetermined area of ​​their surface. The light-shielding layer can be formed by a known method, for example, by coating a ceramic paste containing a black pigment and glass frit onto a predetermined area of ​​the surface of a glass plate or tempered glass that is the material for the laminated glass, and then firing it. The thickness of the light-shielding layer is not particularly limited, for example, 5 to 20 μm. The light-shielding layer can be formed in the peripheral area of ​​any surface of the laminated glass and tempered glass, for example, in the peripheral area of ​​the inner surface of the laminated glass and tempered glass.

[0070] The glass laminate of this disclosure can be a vehicle window glass (windshield, side glass, and rear glass, etc.), and the inorganic laminate can be a transparent electric heating film. The glass laminate GL1 shown in Figure 6 is a vehicle windshield and has an optical device mounting area OP on which an optical device is attached, a light-transmitting area TP located within the optical device mounting area OP through which incident light from the outside to the optical device and / or light emitted from the optical device passes, and a light-shielding layer BL. As shown in the figure, the light-transmitting portion TP can be formed in a region relatively close to one end edge (the upper edge in the illustrated example) of the glass substrate G. The region where the light-shielding layer BL is formed may include the region excluding the light-transmitting portion TP from the optical device mounting region OP, the region surrounding the optical device mounting region OP, and the peripheral region of the glass substrate G.

[0071] The optical device may include, for example, optical equipment such as cameras, LiDAR (Light Detection and Ranging), radar, and optical sensors that acquire information in front of the vehicle for purposes such as autonomous driving and collision prevention, as well as a housing called a bracket or the like that houses them. The shapes of the optical device mounting area OP and the light-transmitting section TP can be appropriately designed to match the shape of the optical device, and examples include a roughly trapezoidal shape and a roughly rectangular shape. The shapes of the optical device mounting area OP and the light-transmitting section TP may be similar or asymmetrical. In the illustrated example, the shapes of the optical device mounting area OP and the light-transmitting section TP are roughly trapezoidal. In the illustrated example, the light-shielding layer BL surrounds all four sides of the light-transmitting portion TP, but the light-shielding layer BL only needs to surround at least a portion of the light-transmitting portion TP. For example, it may surround only three sides of a roughly trapezoidal or roughly rectangular light-transmitting portion TP. The wavelength range of light transmitted by the light-transmitting portion TP is not particularly limited, and can include, for example, the visible light range, the infrared light range, and the visible light range to the infrared light range.

[0072] The functional film F can be laminated onto the inner surface of the glass substrate G. The lamination area of ​​the functional film F includes the light-transmitting portion TP. Preferably, the lamination area of ​​the functional film F is within the optical device mounting area OP. As shown in the figure, the glass substrate G or the functional film F may have a pair of power supply electrodes (also called busbars) 50B in the lamination area of ​​the functional film F, excluding the light-transmitting portion TP, for supplying power to the inorganic laminated film 20 which functions as a transparent electric heating film. The pair of power supply electrodes 50B are formed to be electrically conductive with the inorganic laminated film 20. The power supply electrodes 50B can be formed by known methods, and their number and formation positions can be designed as appropriate.

[0073] [Physical properties after environmental testing] The haze value of the glass laminate of this disclosure is preferably 1.0% or less. The glass laminate of this disclosure can have a haze value of 1.0% or less after an environmental test in which the glass laminate is left standing for 670 hours in an environment of 80°C and 95% relative humidity. When the glass laminate of this disclosure is subjected to an environmental test in which the glass laminate is left standing for 670 hours at 80°C and 95% relative humidity, the ratio of the resistance value of the inorganic laminate before the environmental test to the resistance value of the inorganic laminate before the environmental test can be 0.8 to 1.2. Furthermore, for applications such as windows in automobiles and other vehicles, 80°C and 95% relative humidity are more severe conditions than typical real-world usage environments.

[0074] As described above, the present disclosure provides a glass laminate having an inorganic laminate film including a conductive layer and a dielectric layer, which can suppress the occurrence of transparency distortion, appearance defects such as cracks, an increase in the sheet resistance value and haze value of the inorganic laminate film, even when used in harsh environments such as high temperature and high humidity environments, as well as a functional film with an adhesive layer suitable for use in the manufacture of the same.

[0075] [Application] The functional films with adhesive layers and glass laminates of this disclosure are suitable for windows of vehicles such as automobiles and buildings. For example, they are suitable for the portion of a vehicle's window glass where an optical device is installed; and for glass antennas and frequency selectors formed on windows of vehicles such as automobiles, buildings, and houses. [Examples]

[0076] The present invention will be described below based on examples, but the present invention is not limited to these. Examples 1-3, 11, 21, 22, and 31-44 are examples, and Examples 51-56 are comparative examples.

[0077] [Evaluation items and evaluation methods] The evaluation items and methods are as follows: (Thickness of the adhesive layer) The total thickness of the functional film with adhesive layer was measured using a digital caliper. From this total thickness, the thickness of the base resin film and the thickness of the multiple inorganic layers, including the inorganic laminate film laminated on top of it, were subtracted to determine the thickness of the adhesive layer [μm] in the functional film with adhesive layer before lamination to the glass substrate. This thickness is also called the "thickness before lamination." Using a digital caliper, the total thickness of the resulting glass laminate was measured. From this total thickness, the thickness of the base resin film, the thickness of the multiple inorganic layers including the inorganic laminate film laminated on top of it, and the thickness of the glass substrate were subtracted to determine the thickness of the adhesive layer in the glass laminate [μm]. This thickness is also called the "thickness after lamination."

[0078] (Storage modulus (E')) Dynamic viscoelasticity measurements were performed using a rheometer (Anton Paar "Physica MCR301"). One protective film was peeled off from an OCA (Optical Composite Adhesive) consisting of an adhesive resin film sandwiched between a pair of peelable protective films. One end of the OCA was attached to the stage, and the other end was attached to the measuring probe. The other protective film was then peeled off. The storage modulus (E') of the adhesive resin film was measured at a frequency of 1 Hz and varying temperatures. The storage modulus (E') at 80°C was determined from the resulting storage modulus curve.

[0079] (perspective distortion) Transparency distortion was evaluated in accordance with German Industrial Standard 52305. The resulting glass laminate was placed between a zebraboard and a screen, and the zebraboard stripe pattern projected onto the screen through the glass laminate was observed. This stripe pattern was compared with the zebraboard stripe pattern projected directly onto the screen without passing through the glass laminate. As a change in the zebraboard stripe pattern caused by transmission through the glass laminate, the change in the spacing between the stripe lines was measured using a ruler. When the difference in the spacing of the zebraboard stripes projected onto the screen through the glass laminate was 20% or more compared to the difference in the spacing of the zebraboard stripes projected directly onto the screen without passing through the glass laminate, it was judged as "perspective distortion present (poor, ×)". When the difference was less than 20%, it was judged as "perspective distortion absent (good, ○)".

[0080] (exterior) The obtained glass laminates were observed from the surface side of the inorganic laminate using an optical microscope, and the presence or absence of surface defects such as cracks was evaluated. The evaluation was performed according to the following criteria. ○ (Good): Cosmetic defects such as cracks. × (Defective): No cosmetic defects such as cracks.

[0081] (Sheet resistance value) The sheet resistance values ​​of multiple inorganic layers, including an inorganic multilayer film, were measured using a non-contact resistance meter manufactured by DELCOM.

[0082] (Haze value) The haze value of the obtained glass laminate was measured using the HZ-2 haze meter manufactured by Suga Test Instruments Co., Ltd. A carbon-12 (C) light source was used, and the outermost surface of the inorganic laminate side of the glass laminate was used as the incident surface for the measurement light.

[0083] (Heat and moisture resistance) Environmental testing was conducted on the obtained glass laminates using an environmental testing machine manufactured by ESPEC Corporation, by placing them in a high-temperature, high-humidity environment of 80°C and 95% relative humidity. Visual distortion, appearance, sheet resistance, and haze values ​​were evaluated initially (before environmental testing), after 670 hours of environmental testing, and after 1000 hours of environmental testing. For sheet resistance, the resistance change rate expressed by the following formula was determined. [Resistance change rate] = [Sheet resistance value after 670 hours or 1000 hours of environmental testing] / [Initial sheet resistance value] In all cases, the initial evaluation results for both perspective distortion and appearance were all "good (○)".

[0084] [material] The abbreviations for the materials used in each example are as follows: <Glass substrate> (G1) Soda-lime glass plate (10cm x 10cm, 2mm thick).

[0085] <Base resin film> (5cm x 5cm) (PC) 100μm thick polycarbonate resin film, AGC Corporation's "Carboglass (registered trademark) C110C". (PC:HC) A polycarbonate resin film with a hard coat layer, total thickness 100 μm, in which a hard coat layer made of acrylic resin is formed on both sides of the above (PC) using a curable composition containing a polyfunctional acrylic monomer having multiple (meth)acryloyl groups in one molecule. (COP) 100 μm thick cycloolefin polymer film, manufactured by Zeon Corporation of Japan ("Zeonor Film (registered trademark) ZF-16"). (PI) 50 μm thick polyimide film. (PET) Polyethylene terephthalate film with easy-adhesion treatment on both sides, total thickness 100 μm, manufactured by Toray Industries, Inc., "Lumirror (registered trademark) U34".

[0086] <Optical Transparent Adhesive Film (OCA)> (5cm x 5cm) (OCA1) Nitto Denko's "LUCIACS(registered trademark) CS9862" has a structure in which an acrylic adhesive resin film (thickness: 25μm, 50μm, 75μm, 100μm, or 125μm) is sandwiched between a pair of peelable protective films. (OCA2) PANAC's "Panaclean (registered trademark) PD-C3" has a structure in which an acrylic adhesive resin film (thickness: 50 μm or 75 μm) is sandwiched between a pair of peelable protective films. (OCA3) PANAC's "Panaclean (registered trademark) PD-R5" has a structure in which an acrylic adhesive resin film (thickness: 50 μm) is sandwiched between a pair of peelable protective films. (OCA4) Mitsubishi Chemical Corporation's "ClearFit (registered trademark) G6.0" has a structure in which an acrylic adhesive resin film (thickness: 50 μm) is sandwiched between a pair of peelable protective films. (OCA5) Lintec's "NCF-N632" has a structure in which an acrylic adhesive resin film (thickness: 50 μm) is sandwiched between a pair of peelable protective films. (OCA6) A structure in which a 3M acrylic adhesive resin film (thickness: 200 μm) is sandwiched between a pair of peelable protective films. (OCA7) AGC's "AD20" has a structure in which an acrylic adhesive resin film (thickness: 500 μm) is sandwiched between a pair of peelable protective films.

[0087] [Examples 1-3, 11, 21, 22, 31-44, 51-56] As shown in Tables 1-1 and 1-2, in each example, a base resin film was prepared, and multiple inorganic layers, including an inorganic laminated film (transparent electric heating film), were deposited on almost the entire surface of one of its surfaces by sputtering. In Examples 31-44 and 53-56, the laminated structure of multiple inorganic layers consisted of five layers, from the base resin film side: a lower metal compound layer, a first dielectric layer, a conductive layer, a second dielectric layer, and an upper metal compound layer. In other examples, a three-layer or four-layer structure was used, excluding the lower metal compound layer and / or the upper metal compound layer.

[0088] The abbreviations in the table are as follows: UC: lower metal compound layer, OC: upper metal compound layer, Dielectric layer 1: First dielectric layer, Dielectric layer 2: The second dielectric layer. In the examples shown in the table, conditions not listed in the table were considered common conditions.

[0089] A substrate resin film and a sputtering target were set in the deposition chamber of the sputtering apparatus. Sputtering was performed while introducing Ar gas, and N2 gas or O2 gas as needed, into the deposition chamber. The gas composition was adjusted according to the film composition. Multiple inorganic layers were stacked by performing film deposition multiple times while varying the combination of target composition and the type of introduced gas. The thickness of each layer was designed as follows and adjusted by controlling the power density and deposition time.

[0090] Thickness of the lower metal compound layer: 20 nm, Thickness of the first dielectric layer: 45 nm, Thickness of the conductive layer: 8nm, The total thickness of the second dielectric layer and the upper metal compound layer is 45 nm. The thickness of the upper metal compound layer in each example is shown in Tables 1-1 and 1-2.

[0091] <Lower metal compound layer> As the lower metal compound layer, Al:SiN x A film or SiO2 film was deposited. (Al:SiN x film) Using a Si target containing 10% by mass of Al, Al-doped SiN is produced in the presence of an Ar / N2 mixed gas.x Membrane (Al:SiN x A film was formed. (SiO2 film) An SiO2 film was deposited using a Si target in the presence of an Ar / O2 mixed gas.

[0092] <First dielectric layer, second dielectric layer> TZO films were deposited as the first and second dielectric layers. (TZO film) A Ti-doped ZnO film (TZO film) was deposited using a ZnO target containing 10% by mass of TiO2 in the presence of an Ar / O2 mixed gas.

[0093] <Conductive layer> An Ag film was deposited as a conductive layer. (Ag film) An Ag film was deposited using an Ag target in the presence of Ar.

[0094] <Top metal compound layer> An ITO film, TTO film, or GIT film was deposited as the upper metal compound layer. (ITO film) Using an In2O3 target containing 10% by mass of SnO2, a Sn-doped In2O3 film (ITO film) was deposited in the presence of an Ar / O2 mixed gas. (TTO film) A Ta-doped SnO2 film (TTO film) was deposited using a SnO2 target containing 15% by mass of Ta2O5 in the presence of an Ar / O2 mixed gas. (GIT film) A GIT film was deposited using a target consisting of Ga, In, and Sn oxides (GIT) in the presence of an Ar / O2 mixed gas.

[0095] In each example, the OCAs shown in Tables 1-1 and 1-2 were prepared. In each example, one of the protective films on both sides of the OCA was peeled off, and this OCA was laminated onto multiple inorganic layers, including an inorganic laminate film, using a dedicated device at room temperature and atmospheric pressure. In this way, an adhesive-coated functional film having a laminated structure of protective film / adhesive layer / multiple inorganic layers including an inorganic laminate film / base resin film was obtained.

[0096] The protective film was peeled off from the functional film with adhesive layer, and this functional film with adhesive layer was laminated onto a glass substrate. The resulting laminate was placed in a film bag, degassed under vacuum, and then removed from the bag. As described above, a glass laminate having a laminated structure of multiple inorganic layers including a base resin film / inorganic laminated film / adhesive layer / glass substrate was obtained as shown in Figures 1 to 5.

[0097] The main manufacturing conditions and evaluation results are shown in Tables 1-1, 1-2, 2-1, and 2-2. The adhesive layer thickness in Tables 1-1 and 1-2 is the thickness of the adhesive layer in the functional film with the adhesive layer before lamination to the glass substrate (thickness before lamination). The adhesive layer thickness in Tables 2-1 and 2-2 is the thickness of the adhesive layer in the obtained glass laminate (thickness after lamination).

[0098] [Table 1-1]

[0099] [Table 1-2]

[0100] [Table 2-1]

[0101] [Table 2-2]

[0102] [Summary of results] In Examples 1-3, 11, 21, 22, and 31-44, an amorphous resin film or an amorphous resin film with a hard coat layer was used as the base resin film. In these examples, multiple inorganic layers were formed on the above-mentioned base resin film, including an inorganic laminate film consisting of two dielectric layers containing zinc oxide and a conductive layer containing silver sandwiched between these two dielectric layers. In these examples, an adhesive layer consisting of an optically transparent adhesive layer with a storage modulus (E') of 7 to 40 kPa at 80°C was laminated on top of the above-mentioned inorganic layers. In all of these examples, the glass laminates obtained effectively suppressed the occurrence of transparency distortion, appearance defects such as cracks, and increases in the sheet resistance and haze values ​​of multiple inorganic layers, including the inorganic laminate, even after undergoing a 670-hour high-temperature, high-humidity environmental test. The glass laminates obtained in Examples 11, 22, and 31-44 effectively suppressed the occurrence of transparency distortion, appearance defects such as cracks, and increases in the sheet resistance and haze values ​​of multiple inorganic layers, including the inorganic laminate, even after undergoing a 1000-hour high-temperature, high-humidity environmental test. In examples 31-44, where an inorganic multilayer film was sandwiched between a lower metal compound layer and an upper metal compound layer, excellent results were obtained.

[0103] In Examples 52 and 55, the glass laminates obtained in which the storage modulus (E') of the adhesive layer at 80°C was less than 7 kPa developed transparency distortion after a 670-hour high-temperature, high-humidity environment test. The glass laminates obtained in examples 51, 53, 54, and 56, in which the storage modulus (E') of the adhesive layer at 80°C was 40 kPa or higher, developed appearance defects such as cracks after a 670-hour high-temperature, high-humidity environment test. The glass laminate obtained in example 51 showed an increase in sheet resistance after a 670-hour high-temperature, high-humidity environment test. The glass laminate obtained in example 56 showed an increase in haze value after a 670-hour high-temperature, high-humidity environment test.

[0104] The present invention is not limited to the embodiments and examples described above, and the design can be modified as appropriate without departing from the spirit of the invention. [Explanation of symbols]

[0105] 10, 10A, 10B: Base resin film, 11: Amorphous resin film, 12: Hard coat layer, 20: Inorganic laminate, 21: Dielectric layer, 22: Conductive layer, 31: Lower metal compound layer, 32: Upper metal compound layer, 40: Adhesive layer, AF, AF1~AF5: Functional film with adhesive layer, F, F1~F5: Functional film, G: Glass substrate, GL1: Glass laminate.

Claims

1. A functional film having a base resin film, an inorganic laminated film laminated on one surface of the base resin film, and an adhesive layer provided on the inorganic laminated film of the functional film, The base resin film is an amorphous resin film, or an amorphous resin film with a hard coat layer, wherein a hard coat layer made of a cured product of a curable composition is formed on at least one surface of the amorphous resin film. The inorganic multilayer film comprises a plurality of dielectric layers containing zinc oxide and one or more metal elements other than Zn selected from the group consisting of Al, Ti, Ga, In, Sn, Ta, and W, and one or more conductive layers sandwiched between the plurality of dielectric layers, each containing at least one metal selected from the group consisting of silver and silver alloys, wherein the zinc oxide content in the dielectric layers is 70 to 95 mol%, the thickness of the dielectric layers is 20 to 90 nm, the number of dielectric layers is 2 to 4, the silver element content in the conductive layers is 97 mol% or more, and the thickness of the conductive layers is 5 to 20 nm. The adhesive layer is an optically transparent adhesive layer comprising an adhesive containing one or more adhesive resins containing carboxyl groups, and having a storage modulus (E') of 10 to 40 kPa at 80°C, wherein the adhesive layer is an adhesive film with an adhesive layer.

2. Furthermore, the functional film with an adhesive layer according to claim 1, comprising a lower metal compound layer between the base resin film and the inorganic laminate film, the lower metal compound layer containing one or more metal compounds selected from the group consisting of Si and Al, and substantially free of zinc oxide.

3. Furthermore, the functional film with an adhesive layer according to claim 1 or 2, wherein the surface of the inorganic laminated film on the adhesive layer side contains one or more metal compounds comprising at least one metal element selected from the group consisting of Al, Si, Ti, Ga, In, Sn, Ta, and W, and substantially does not contain zinc oxide.

4. The functional film with an adhesive layer according to claim 1 or 2, wherein the constituent resin of the amorphous resin film is at least one amorphous resin selected from the group consisting of polycarbonate resins, cycloolefin polymers, and polyimides.

5. The functional film with an adhesive layer according to claim 1 or 2, wherein the adhesive is an acrylic adhesive.

6. The functional film with an adhesive layer according to claim 1 or 2, wherein the thickness of the adhesive layer is 25 to 110 μm.

7. The functional film with an adhesive layer according to claim 1 or 2, wherein the total thickness of the inorganic laminated film is 45 to 380 nm.

8. A glass laminate comprising a glass substrate and a functional film bonded to one surface of the glass substrate via an adhesive layer, The functional film comprises a base resin film and an inorganic laminated film laminated on the adhesive layer side surface of the base resin film. The base resin film is an amorphous resin film, or an amorphous resin film with a hard coat layer, wherein a hard coat layer made of a cured product of a curable composition is formed on at least one surface of the amorphous resin film. The inorganic multilayer film comprises a plurality of dielectric layers containing zinc oxide and one or more metal elements other than Zn selected from the group consisting of Al, Ti, Ga, In, Sn, Ta, and W, and one or more conductive layers sandwiched between the plurality of dielectric layers, each containing at least one metal selected from the group consisting of silver and silver alloys, wherein the zinc oxide content in the dielectric layers is 70 to 95 mol%, the thickness of the dielectric layers is 20 to 90 nm, the number of dielectric layers is 2 to 4, the silver element content in the conductive layers is 97 mol% or more, and the thickness of the conductive layers is 5 to 20 nm. The aforementioned adhesive layer is an optically transparent adhesive layer comprising an adhesive containing one or more adhesive resins containing carboxyl groups, and having a storage modulus (E') of 10 to 40 kPa at 80°C, in a glass laminate.

9. The glass laminate according to claim 8, wherein the functional film further comprises a lower metal compound layer between the base resin film and the inorganic laminate, the lower metal compound layer containing at least one metal element selected from the group consisting of Si and Al, and substantially free of zinc oxide.

10. The glass laminate according to claim 8 or 9, wherein the functional film further comprises an upper metal compound layer on the adhesive layer side surface of the inorganic laminate, which contains one or more metal compounds comprising at least one metal element selected from the group consisting of Al, Si, Ti, Ga, In, Sn, Ta, and W, and substantially does not contain zinc oxide.

11. The glass laminate according to claim 8 or 9, wherein the constituent resin of the amorphous resin film is at least one amorphous resin selected from the group consisting of polycarbonate resins, cycloolefin polymers, and polyimides.

12. The glass laminate according to claim 8 or 9, wherein the adhesive is an acrylic adhesive.

13. The glass laminate according to claim 8 or 9, wherein the thickness of the adhesive layer is 20 to 105 μm.

14. The glass laminate according to claim 8 or 9, wherein the total thickness of the inorganic laminate is 45 to 380 nm.

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