Method for manufacturing glass plate structure

Abstract

The present invention relates to a method for producing a glass plate structure which comprises two or more plates and an intermediate layer that is disposed between at least one pair of plates out of the two or more plates, and in which at least one plate among the pair of plates is a glass plate, said method comprising: applying a sealing agent and a liquid agent for an intermediate layer to at least a part of a main surface of one plate (1A); obtaining a laminate by laminating the other plate (1B) on the main surface of the plate (1A) to which the liquid agent and the sealing agent are applied; and subjecting the laminate to reduced pressure.

Description

[Technical Field]

[0001] The present invention relates to a method for producing a glass sheet structure in which an intermediate layer such as a liquid layer is provided between at least a pair of sheets. [Background technology]

[0002] Glass, a material with a high sound propagation speed, has been attracting attention as a diaphragm for speakers or microphones. Here, high-frequency bands of 20 kHz or more are difficult for the human ear to hear, but they give a strong sense of presence, and therefore faithful reproduction is required. Patent Document 1 describes a glass plate structure having a liquid layer provided between at least a pair of plates as a glass plate structure that has good acoustic performance even in this band. [Prior art documents] [Patent documents]

[0003] [Patent Document 1] International Publication No. 2017 / 175682 Summary of the Invention [Problem to be solved by the invention]

[0004] There are concerns that if the liquid layer of the glass plate structure described in Patent Document 1 contains bubbles, it will significantly impair the appearance, the bubbles will act as a damping effect so that the amplitude of the two plates will not be the same, making it difficult to achieve good acoustic performance, and the internal pressure and size of the bubbles will tend to change depending on the ambient temperature, making it difficult to achieve reproducible acoustic performance, etc. For these reasons, it is preferable that intermediate layers such as liquid layers do not contain bubbles. Because intermediate layers such as liquid layers do not contain air bubbles, the inventors considered a method (vacuum lamination method) in which an intermediate layer liquid and a sealant are applied to one plate, then the pressure is reduced and another plate is laminated on top; however, it was difficult to completely remove the air bubbles.

[0005] Therefore, an object of the present invention is to provide a method for producing a glass plate structure in which an intermediate layer such as a liquid layer is provided between at least a pair of plates, by which the intermediate layer can be produced without containing air bubbles. [Means for solving the problem]

[0006] As a result of extensive research, the present inventors have found that the above problems can be solved by the following manufacturing method. [1] A method for producing a glass plate structure including two or more plates, including an intermediate layer between at least one pair of the plates, and at least one plate of the pair of plates being a glass plate, Applying a liquid agent for an intermediate layer and a sealing agent to at least a part of the main surface of one plate 1A; obtaining a laminate by laminating another plate 1B to the main surface of the plate 1A to which the intermediate layer liquid agent and the sealing agent have been applied; and A method for producing a glass plate structure, comprising subjecting the laminate to a reduced pressure. [2] When subjecting the laminate to a reduced pressure, a reduced pressure chamber is used, The method for producing a glass plate structure according to [1], wherein the spatial volume (L) in the reduced pressure chamber / exhaust capacity (L / min) in the reduced pressure chamber is 1.8 or less. [3] The method for producing a glass plate structure according to [1] or [2], wherein when the laminate is subjected to reduced pressure, the time required for the pressure to reach 100 Pa or less is 1 minute to 180 minutes. [4] The method for producing a glass plate structure according to any one of [1] to [3], wherein the viscosity coefficient of the sealing agent is higher than the viscosity coefficient of the liquid agent for forming an intermediate layer. [5] The viscosity coefficient of the sealing agent is 1×10 -1 Pa·s or more, and the viscosity coefficient of the liquid agent for the intermediate layer is 1×10 3 The method for producing a glass plate structure according to any one of [1] to [4], wherein the viscosity is Pa·s or less. [6] The method for producing a glass plate structure according to any one of [1] to [5], wherein the liquid agent for forming an intermediate layer contains silicone. [7] The method for producing a glass plate structure according to any one of [1] to [6], wherein the coating pattern of the liquid agent for intermediate layer is a layer, a dot, a lattice, or a stripe. [8] The method for producing a glass plate structure according to any one of [1] to [7], wherein the coating thickness of the sealing agent is greater than the coating thickness of the liquid agent for intermediate layer. [9] The method for producing a glass plate structure according to any one of [1] to [8], wherein the coating thickness of the liquid agent for intermediate layer is 5 μm to 500 μm.

[10] The method for producing a glass plate structure according to [8] or [9], wherein the sealing agent has a coating thickness of 10 μm to 1000 μm.

[11] The method for producing a glass plate structure according to any one of [1] to

[10] , further comprising subjecting the laminate to a reduced pressure and then pressurizing the laminate.

[12] The method for producing a glass plate structure according to

[11] , wherein the laminate is pressed by being pressed at a pressure of 0.1 MPa to 10 MPa for a pressing time of 1 minute to 30 minutes.

[13] The method for producing a glass plate structure according to any one of [1] to

[12] , wherein the sealant contains a curable resin, and the method further comprises curing the sealant after subjecting the laminate to reduced pressure.

[14] The method for producing a glass plate structure according to any one of [1] to

[13] , wherein the liquid agent for an intermediate layer contains a curable resin, and the method further comprises curing the liquid agent for an intermediate layer after subjecting the laminate to a reduced pressure.

[15] The method for producing a glass plate structure according to any one of [1] to

[14] , wherein the plate has a curved surface.

[16] The method for producing a glass plate structure according to any one of [1] to

[15] , wherein the plate 1A and the plate 1B are bonded together under normal pressure. [Effects of the Invention]

[0007] According to the manufacturing method of the present invention, a glass plate structure can be manufactured without the intermediate layer such as the liquid layer containing bubbles. Furthermore, the resulting glass plate structure has an excellent appearance because the intermediate layer (hereinafter simply referred to as the "intermediate layer"), such as a liquid layer, does not contain any bubbles, and has good acoustic performance because the two plates do not have the same amplitude, and exhibits well-reproducible acoustic performance even when the ambient temperature changes. [Brief explanation of the drawings]

[0008] [Figure 1] Figures 1(a) to 1(d) are process diagrams showing an example of a method for manufacturing a glass plate structure of the present invention, where Figure 1(a) shows a process of preparing plate 1A, Figure 1(b) shows a process of applying an intermediate layer liquid agent 2 and a sealant 3 to at least a portion of the main surface (first main surface) of plate 1A, Figure 1(c) shows a process of laminating another plate 1B to the applied surface of plate 1A to obtain a laminate 11, and Figure 1(d) shows a process of subjecting laminate 11 to reduced pressure to obtain a glass plate structure 10 including an intermediate layer 21 between plates 1A and 1B. DETAILED DESCRIPTION OF THE INVENTION

[0009] <Method of manufacturing glass plate structure> The present invention relates to a method for producing a glass plate structure including two or more plates, an intermediate layer such as a liquid layer between at least one pair of the plates, and at least one of the pair of plates being a glass plate. 1(a) to 1(d) are process diagrams illustrating an example of a method for producing a glass plate structure of the present invention. As shown in FIG. 1(b), an intermediate layer liquid agent 2 and a sealant 3 are applied to at least a portion of the main surface (first main surface) of one plate 1A of a pair of plates. As shown in FIG. 1(c), the other plate 1B is bonded to the coated surface of plate 1A to obtain a laminate 11. As shown in FIG. 1(d), the laminate 11 is subjected to reduced pressure to obtain a glass plate structure 10 including an intermediate layer 21 between plates 1A and 1B. Note that the intermediate layer 21 may be a layer made of a liquid or a layer made of a solid obtained by hardening the liquid. The method for producing a glass plate structure of the present invention can produce a glass plate structure in which the intermediate layer 21 does not contain bubbles.

[0010] (Plates and glass plates) In the glass plate structure of the present invention, the pair of plates are not fixed to each other due to the presence of an intermediate layer such as a liquid layer, unlike when the pair of plates are provided via an adhesive layer, and each plate can maintain its vibration characteristics. That is, when one plate 1A resonates, the presence of the intermediate layer such as a liquid layer prevents the other plate 1B from resonating or can attenuate the vibration of the resonance of plate 1B, so that the glass plate structure has a higher loss factor than when the plates are provided alone.

[0011] Of the two plates that make up the pair, it is preferable that the peak top values ​​of the resonance frequencies of one plate 1A and the other plate 1B are different, and it is even more preferable that the resonance frequency ranges do not overlap. However, even if the resonance frequency ranges of plates 1A and 1B overlap or the peak top values ​​are the same, if one plate resonates due to the presence of an intermediate layer such as a liquid layer, the vibration of the other plate will not be synchronized, and the resonance will be canceled out to a certain extent, resulting in a higher loss factor than when the plate is alone. That is, when the resonance frequency (peak top) of plate 1A is Qa, the half-width of the resonance amplitude is wa, and the resonance frequency (peak top) of the other plate 1B is Qb, and the half-width of the resonance amplitude is wb, it is preferable to satisfy the relationship in the following [Equation 1]. (wa+wb) / 4<|Qa-Qb| [Equation 1] The larger the value of the left side of the above formula 1, the larger the difference in resonance frequency (|Qa-Qb|) between plates 1A and 1B, and the higher the loss factor, which is preferable.

[0012] Therefore, it is more preferable to satisfy the following [Formula 1'], and it is even more preferable to satisfy the following [Formula 1"]. (wa+wb) / 2<|Qa-Qb|...[Formula 1'] (wa+wb) / 1<|Qa-Qb|...[Formula 1”] The resonance frequency (peak top) and half width of the resonance amplitude of the plate can be measured in the same manner as the loss factor of the glass plate structure.

[0013] The smaller the difference in mass between plates 1A and 1B, the better, and even better if there is no difference in mass at all. If there is a difference in mass between the plates, the resonance of the lighter plate can be suppressed by the heavier plate, but it is difficult to suppress the resonance of the heavier plate with the lighter plate. In other words, if there is an imbalance in the mass ratio, the difference in inertial force will make it impossible in principle for the resonant vibrations to cancel each other out.

[0014] The mass ratio of Plate 1A to Plate 1B represented by (Plate 1A / Plate 1B) is preferably 0.8 to 1.25 (8 / 10 to 10 / 8), more preferably 0.9 to 1.1 (9 / 10 to 10 / 9), and even more preferably 1.0 (10 / 10).

[0015] The thinner the thickness of both plates 1A and 1B, the easier it is for the plates to adhere to each other via a liquid layer, and the plates can vibrate with less energy. Therefore, when used as diaphragms for speakers and the like, the thinner the plates are, the better. Specifically, the thickness of plates 1A and 1B is preferably 15 mm or less, more preferably 10 mm or less, even more preferably 5 mm or less, even more preferably 3 mm or less, particularly preferably 1.5 mm or less, and particularly more preferably 0.8 mm or less. On the other hand, if the thickness is too thin, the effect of surface defects on the plate becomes more pronounced, making it more susceptible to cracking and making it difficult to perform a tempering treatment, so the thickness is preferably 0.01 mm or more, more preferably 0.05 mm or more.

[0016] Furthermore, when used as opening materials for buildings and vehicles to suppress the generation of abnormal noise caused by resonance phenomena, the thickness of plates 1A and 1B is preferably 0.5 mm to 15 mm, more preferably 0.8 mm to 10 mm, and even more preferably 1.0 mm to 8 mm. When used as a glass substrate for a magnetic recording medium with improved vibration isolation, the thickness of each of Plates 1A and 1B is preferably 0.3 mm to 1.2 mm, more preferably 0.4 mm to 1.0 mm, and even more preferably 0.5 mm to 0.8 mm.

[0017] At least one of plates 1A and 1B has a larger loss factor, which is preferable for use as a vibration plate, since vibration attenuation of the glass plate assembly increases. Specifically, the loss factor of the plate at 25°C is 1 × 10 -4 More than 3×10 is preferable. -4 More than 5×10 is preferable. -4 Although the upper limit is not particularly limited, the loss factor is preferably 5×10 -3 It is preferable that both the plate 1A and the plate 1B have the above loss coefficients.

[0018] At least one of the plates 1A and 1B is preferably used as a diaphragm because a higher longitudinal wave velocity in the plate thickness direction improves the reproducibility of high-frequency sounds. Specifically, the plate has a longitudinal wave velocity of 5.5×10 3 m / s or more is preferable, 5.7×10 3 m / s or more is more preferable, and 6.0×10 3 The upper limit is not particularly limited, but is preferably 7.0 × 10 m / s or more from the viewpoint of productivity of the plate and raw material costs. 3 It is more preferable that both the plate 1A and the plate 1B satisfy the above sound velocity value.

[0019] In the glass plate structure according to the present invention, at least one of the first plate and the second plate is a glass plate. Here, the glass plate refers to inorganic glass and organic glass. Examples of organic glass include PMMA-based resin, PC-based resin, PS-based resin, PET-based resin, and cellulose-based resin, which are generally well known as transparent resins.

[0020] The material of the other plate is arbitrary, and various materials can be used, such as a resin plate made of a resin other than organic glass, a metal plate such as aluminum, a ceramic plate made of ceramic, etc. From the viewpoints of design, processability, and weight, it is preferable to use organic glass, resin materials, composite materials, fiber materials, metal materials, etc., and from the viewpoint of vibration characteristics, it is preferable to use inorganic glass, highly rigid composite materials, fiber materials, metal materials, or ceramic materials.

[0021] The resin material is preferably a resin material that can be molded into a flat or curved plate shape. The composite material or fiber material is preferably a resin material compounded with a high-hardness filler, carbon fiber, Kevlar fiber, or the like. The metal material is preferably aluminum, magnesium, copper, silver, gold, iron, titanium, or SUS, and other alloy materials may also be used as needed. As the ceramic material, ceramics and single crystal materials such as Al2O3, SiC, Si3N4, AlN, mullite, zirconia, yttria, YAG, etc. are more preferable. Furthermore, as for the ceramic material, a material having translucency is particularly preferable.

[0022] When inorganic glass is used in the glass plate constituting at least one plate, the composition is not particularly limited, but it is preferable that the composition is, for example, in the following range in mass % based on oxides. SiO2: 40-80 mass%, Al2O3: 0-35 mass%, B2O3: 0-15 mass%, MgO: 0-20 mass%, CaO: 0-20 mass%, SrO: 0-20 mass%, BaO: 0-20 mass%, Li2O: 0-20 mass%, Na2O: 0-25 mass%, K2O: 0-20 mass%, TiO2: 0-10 mass%, and ZrO2: 0-10 mass%, with the above composition accounting for 95 mass% or more of the entire glass.

[0023] The composition of the inorganic glass plate is more preferably in the following range. SiO2: 55 to 75 mass%, Al2O3: 0 to 25 mass%, B2O3: 0 to 12 mass%, MgO: 0 to 20 mass%, CaO: 0 to 20 mass%, SrO: 0 to 20 mass%, BaO: 0 to 20 mass%, Li2O: 0 to 20 mass%, Na2O: 0 to 25 mass%, K2O: 0 to 15 mass%, TiO2: 0 to 5 mass%, and ZrO2: 0 to 5 mass%, with the above composition accounting for 95 mass% or more of the entire glass.

[0024] The smaller the specific gravity of each of plates 1A and 1B, the less energy is required to vibrate the plates. Specifically, the specific gravity of each of plates 1A and 1B is preferably 2.8 or less, more preferably 2.6 or less, and even more preferably 2.5 or less. There is no particular lower limit to the specific gravity, but 2.2 or more is preferred. The larger the specific elastic modulus, which is the value obtained by dividing the Young's modulus of Plate 1A and Plate 1B by the density, the higher the rigidity of the plate can be. Specifically, the specific elastic modulus of Plate 1A and Plate 1B is 2.5 × 10 7 m 2 / s 2 More than 2.8 × 10 is preferable. 7 m 2 / s 2 More preferably, 3.0 x 10 7 m 2 / s 2 The upper limit of the specific elastic modulus is not particularly limited, but is preferably 4.0×10 7 m 2 / s 2 The following is preferred:

[0025] The shape of the plate is not particularly limited, and may be flat or have a curved surface.

[0026] (Application of intermediate layer liquid and sealant) In the manufacturing method of the present invention, a liquid agent for an intermediate layer and a sealing agent are applied to at least a part of the main surface (first main surface) of one plate 1A of the pair of plates. The intermediate layer liquid (hereinafter also simply referred to as liquid) is a material that forms an intermediate layer of a glass plate structure. In order to achieve a high loss factor for the glass plate structure, the viscosity coefficient of the liquid at 25°C is 1×10 3 Pa·s or less is preferable, and 1×10 -4 A viscosity of Pa·s or higher is preferable. If the viscosity is too low, it becomes difficult to transmit vibrations, and if it is too high, the pair of plates located on either side of the liquid layer will stick together and exhibit vibration behavior as a single plate, making it difficult to attenuate resonant vibrations. The viscosity coefficient is 1×10 -3 Pa·s or more is preferable, 1×10 -2 Pa·s or more is more preferable. 2The viscosity coefficient is more preferably 1×10 Pa·s or less, and even more preferably 1×10 Pa·s or less. The viscosity coefficient can be measured using a rotational viscometer or the like.

[0027] Furthermore, from the viewpoint of realizing a high loss factor of the glass plate structure, the liquid preferably has a surface tension of 15 mN / m to 80 mN / m at 25°C. If the surface tension is too low, the adhesion between the plates decreases, making it difficult to transmit vibration. If the surface tension is too high, the pair of plates located on both sides of the liquid layer tend to adhere to each other, and they begin to vibrate as a single plate, making it difficult to attenuate resonant vibration. The surface tension is more preferably 20 mN / m or more, and even more preferably 30 mN / m or more. The surface tension can be measured by the ring method or the like.

[0028] If the vapor pressure of the liquid layer is too high, the liquid layer may evaporate and no longer function as a glass plate component. Therefore, the liquid agent for the intermediate layer should have a vapor pressure of 1×10 at 25°C and 1 atm. 4 Pa or less is preferable, and 5×10 3 Pa or less is more preferable, and 1×10 3 Pa or less is more preferable.

[0029] When the intermediate layer is a liquid layer, it is preferable that the liquid layer is chemically stable and does not react with the plate. Chemical stability means, for example, that it is less susceptible to deterioration (deterioration) due to light irradiation, and that it does not solidify, vaporize, decompose, discolor, or chemically react with glass at least in the temperature range of -20°C to 70°C. On the other hand, when the intermediate layer is a solid layer obtained by hardening a liquid layer, this can be achieved through a predetermined hardening process, such as ultraviolet hardening or heat hardening.

[0030] Specific examples of the liquid for the intermediate layer include water, oil, organic solvent, liquid polymer, ionic liquid, curable resin, and mixtures thereof. More specifically, examples of suitable intermediate layers include propylene glycol, dipropylene glycol, tripropylene glycol, straight silicone oil (dimethyl silicone oil, methylphenyl silicone oil, methylhydrogen silicone oil), modified silicone oil, acrylic acid polymer, acrylic polymer, urethane polymer, silicone polymer, liquid polybutadiene, glycerin paste, fluorine-based solvent, fluorine-based resin, acetone, ethanol, xylene, toluene, water, mineral oil, and mixtures thereof. When the intermediate layer is a liquid layer, it preferably contains at least one selected from the group consisting of propylene glycol, dimethyl silicone oil, methylphenyl silicone oil, methylhydrogen silicone oil, and modified silicone oil, and more preferably contains propylene glycol or silicone oil as the primary component. Furthermore, when silicone oil is the primary component, it is preferable that the intermediate layer, such as a liquid layer, easily dissolves air, thereby suppressing the formation of air bubbles. When the intermediate layer is a solid layer, it preferably contains a curable resin such as an acrylic polymer, urethane polymer, or silicone polymer.

[0031] From the viewpoint of imparting design properties and functionality such as coloring and fluorescence to the glass plate structure, the liquid agent for the intermediate layer may be a slurry in which powder is dispersed, or the liquid agent for the intermediate layer may contain a fluorescent material. The powder content in the intermediate layer liquid is preferably 0% to 10% by volume, more preferably 0% to 5% by volume. The particle size of the powder is preferably 10 nm to 1 μm, more preferably 10 nm to 0.5 μm, from the viewpoint of preventing sedimentation.

[0032] The sealant is applied to prevent leakage of the liquid agent and to prevent peeling at the interface between the plate and the intermediate layer (liquid layer) of the glass plate assembly.

[0033] The sealant must not flow out when applied and must be strong enough to withstand the weight of the plates when they are bonded together. From this perspective, the viscosity coefficient at 25°C is preferably 1 × 10 -1The viscosity coefficient at 25°C is preferably 1 x 10 Pa·s or more, more preferably 1 Pa·s or more. From the viewpoint of good handling properties during application, a certain level of leveling ability, and application with a narrow seal width, the viscosity coefficient at 25°C is preferably 1 x 10 3 Pa·s or less, preferably 1×10 2 It is less than Pa·s.

[0034] Furthermore, from the viewpoint of efficiently removing air bubbles from the intermediate layer, it is preferable that the viscosity coefficient of the sealant is greater than that of the liquid. When air bubbles remaining in the intermediate layer (liquid layer) are removed in the decompression step described below, a flow path for the air bubbles to move is more easily secured if the viscosity coefficient of the sealant is greater than that of the liquid.

[0035] As the sealing agent, highly elastic rubber, resin, gel, etc. can be used. The resin for the sealant can be a material containing a curable resin such as an acrylic, cyanoacrylate, epoxy, silicone, urethane, or phenolic resin. The curing method for the sealant can be one-component, two-component mixture, heat curing, ultraviolet curing, visible light curing, or the like. Thermoplastic resins (hot melt bonds) can also be used as sealing agents, and examples include ethylene vinyl acetate, polyolefin, polyamide, synthetic rubber, acrylic, and polyurethane. Regarding rubber, for example, natural rubber, synthetic natural rubber, butadiene rubber, styrene-butadiene rubber, butyl rubber, nitrile rubber, ethylene-propylene rubber, chloroprene rubber, acrylic rubber, chlorosulfonated polyethylene rubber (Hypalon), urethane rubber, silicone rubber, fluororubber, ethylene-vinyl acetate rubber, epichlorohydrin rubber, polysulfide rubber (Thiokol), and hydrogenated nitrile rubber can be used.

[0036] The order of application of the intermediate layer liquid agent and the sealing agent does not matter: the intermediate layer liquid agent may be applied to the main surface of the plate at a location where a liquid layer is to be formed, and then the sealing agent may be applied to surround the outer periphery thereof, or the sealing agent may be applied to the main surface of the plate first, and then the intermediate layer liquid agent may be applied to the inner periphery thereof.

[0037] The application pattern of the liquid agent for the intermediate layer is not particularly limited, and may be a layer, or may be a dot, grid, or stripe pattern. Among these, a dot pattern is preferred from the viewpoint of easily securing a flow path for air bubbles to escape.

[0038] The coating thickness of the liquid agent for the intermediate layer may be appropriately set so that the thickness of the intermediate layer falls within a desired range, and is preferably 5 μm to 500 μm.

[0039] In a plan view of the plate 1A, the sealant is preferably applied so as to surround the outer periphery of the intermediate layer liquid agent. In this case, the area of ​​the sealant-applied portion in a plan view of the plate 1A is preferably 20% or less, more preferably 10% or less, and particularly preferably 5% or less of the area of ​​the intermediate layer liquid agent-applied portion so as not to interfere with vibration.

[0040] The thickness of the sealant applied is preferably thicker than the thickness of the intermediate layer liquid agent, from the viewpoint of easily ensuring a flow path for releasing air bubbles, and is preferably 10 μm to 1000 μm.

[0041] The liquid agent for the intermediate layer and the sealing agent can be applied by known methods such as screen printing and using a dispenser.

[0042] (Board lamination) Next, plate 1B is attached to the main surface of plate 1A on which the intermediate layer liquid agent and sealant have been applied, to obtain a laminate (FIG. 1(c)). It is preferable to perform lamination under normal pressure (atmospheric pressure). In the reduced pressure lamination method investigated by the inventors, it was difficult to hold the two plates in position with good accuracy under reduced pressure, and it was difficult to laminate them without misalignment. However, by laminating them under normal pressure, it is possible to laminate the two plates with good positional accuracy. The laminate is preferably not heated, as the plates are prone to deformation due to heating and the sealant is softened by heat, making it difficult to ensure a flow path for air bubbles to escape, making degassing difficult.

[0043] (vacuum degassing) The obtained laminate is subjected to reduced pressure, so that even if air bubbles are present in the intermediate layer (in this case, the liquid layer) during application of the liquid agent or lamination of the plates, they gradually move to the periphery of the plates and are released from the laminate. Specifically, the reduced pressure of the laminate is preferably 100 Pa or less, more preferably 50 Pa or less. The time for which the decompression is performed depends on the degassing speed, but is preferably 1 minute to 180 minutes. Furthermore, from the viewpoint of efficiently releasing bubbles by rapidly depressurizing the laminate, the pressure is reduced to 100 Pa or less, and the time required for the depressurization is preferably within 30 minutes, more preferably within 15 minutes, and particularly preferably within 10 minutes.

[0044] Examples of methods for subjecting the laminate to reduced pressure include a method using a reduced pressure chamber and a method in which the laminate is placed in a bag made of rubber or the like and the inside of the bag is degassed. In this case, from the viewpoint of rapid decompression, the spatial volume (L) in the decompression chamber / exhaust capacity (L / min) in the decompression chamber is preferably 1.8 or less, more preferably 1.5 or less, and even more preferably 0.9 or less.

[0045] (pressurized) After being subjected to reduced pressure, the laminate is preferably pressurized from the outside. This allows for the removal of air bubbles that were not completely removed by the reduced pressure alone. As a pressurization method, the laminate is temporarily pressure-bonded using a roll, and then pressure-bonded using an autoclave. The pressure inside the autoclave is preferably 0.1 MPa to 10 MPa, and the pressure-bonding time is preferably 1 minute to 30 minutes. The temperature of the autoclave is preferably 120°C to 150°C.

[0046] (sealant hardening) Next, the sealant is cured as needed, which prevents leakage of the intermediate layer (in this case, the liquid layer). The curing means can be appropriately selected depending on the material of the sealant. If the sealant is a photocurable resin, it is cured by light irradiation, and if it is a thermosetting resin, it is cured by heating.

[0047] (Liquid layer (liquid for intermediate layer) hardening) The liquid layer from which air bubbles have been removed by the above-mentioned decompression may be used as an intermediate layer (i.e., an intermediate layer made of a liquid layer) as is, or may be cured as necessary to form an intermediate layer (i.e., a solid layer). Furthermore, even if the intermediate layer is a solid layer, it is preferable because it does not contain air bubbles according to the manufacturing method of the present invention. The curing means can be appropriately selected depending on the material of the liquid layer (liquid agent for intermediate layer). If the liquid layer (liquid agent for intermediate layer) is a photocurable resin, it is cured by light irradiation, and if it is a thermosetting resin, it is cured by heating. Furthermore, examples of methods for curing the liquid layer include one-component, two-component mixture, heat curing, ultraviolet curing, and visible light curing. Note that when the intermediate layer is a solid layer formed by curing a liquid layer, the same material as the sealant can be used as the liquid agent for intermediate layer. Furthermore, the curing of the liquid layer (liquid agent for intermediate layer) may be performed after the above-mentioned degassing under reduced pressure or after the above-mentioned pressurization. Furthermore, the curing of the liquid layer (liquid agent for intermediate layer) may be performed simultaneously with the curing of the sealant, or may be performed separately. When the liquid layer (liquid agent for intermediate layer) and the sealant are cured separately, the order of curing can be determined arbitrarily.

[0048] In this way, a glass plate structure is obtained.

[0049] <Glass plate structure> The thinner the thickness of the intermediate layer, the better in terms of maintaining high rigidity and transmitting vibration. From this viewpoint, when the total thickness of the pair of plates is 1 mm or less, the thickness of the intermediate layer is preferably 1 / 10 or less, more preferably 1 / 20 or less, even more preferably 1 / 30 or less, still more preferably 1 / 50 or less, especially preferably 1 / 70 or less, and particularly preferably 1 / 100 or less of the total thickness of the pair of plates. Furthermore, when the total thickness of the pair of plates exceeds 1 mm, the thickness of the intermediate layer is preferably 100 μm or less, more preferably 50 μm or less, even more preferably 30 μm or less, even more preferably 20 μm or less, especially preferably 15 μm or less, and particularly preferably 10 μm or less. The lower limit of the thickness of the intermediate layer is preferably 0.01 μm or more from the viewpoint of film-forming properties and durability. [Example]

[0050] The following examples will explain the present invention in more detail, but the present invention is not limited to these examples. Examples 1 and 2 are working examples, and Example 3 is a comparative example. Furthermore, Examples 4, 5, 6, and 7 are working examples.

[0051] The materials used in the following examples are as follows: Intermediate layer liquid A: KF96 (viscosity coefficient 3 Pa·s) manufactured by Shin-Etsu Chemical Co., Ltd. Intermediate layer liquid B: Uncured UV-curable modified acrylate (viscosity coefficient 4 Pa·s) Intermediate layer liquid C: Uncured addition polymerization type silicone (viscosity coefficient 1.5 Pa·s) Sealant A: Uncured UV-curable silicone (viscosity coefficient 7.5 Pa·s) Sealant B: Uncured UV-curable modified acrylate (viscosity coefficient 12 Pa·s) Sealant C: Uncured UV-curable silicone (viscosity coefficient 15 Pa·s)

[0052] (Example 1) Preparation of glass plate structure (intermediate layer is liquid layer) Two glass plates (soda-lime glass, 30 cm long x 30 cm wide x 1.1 mm thick) were prepared as glass plate constructing members. 0.9 g of intermediate layer liquid agent A was applied to the first main surface of the first glass plate using a screen printing machine (LS-34GX manufactured by Newlong Precision Industries Co., Ltd., mesh ST250, 3 mm diameter, 10 mm pitch dot pattern). The applied liquid agent had a thickness of approximately 20 μm. Subsequently, sealant A was applied to the periphery of the applied liquid agent area on the first main surface of the first glass plate using a dispenser (DSP SMDS-CV2-400 manufactured by Musashi Engineering Co., Ltd.) so as to surround the applied liquid agent. The applied sealant had a thickness of approximately 150 μm. The area of ​​the sealant in a plan view of the first glass plate was approximately 7% of the area of ​​the applied liquid agent area. The main surface (first main surface) of the first glass plate coated with the liquid agent and sealant was bonded to one main surface of the second glass plate under atmospheric pressure to obtain a laminate. The obtained laminate was placed in a vacuum chamber and degassed for 10 minutes to reduce the pressure to 100 Pa or less. Space volume inside the decompression chamber (L) / exhaust capacity inside the decompression chamber (L / min) = 1.445 The sealant was then cured by UV irradiation. A glass plate structure 1 was obtained by the above method.

[0053] (Example 2) Preparation of glass plate structure (intermediate layer is liquid layer) Two glass plates (soda-lime glass, 100 cm long x 100 cm wide x 1.1 mm thick) were prepared as glass plate components. 0.9 g of intermediate layer liquid A was applied to the first main surface of the first glass plate using a high-speed jet dispenser (Saneitec Corporation, dispense valve SJVH3000, Sanei Tech Corporation, dispense controller SJVC3000) in a dot pattern with 0.9 mg per dot and a 10 mm pitch. The applied thickness of the liquid was approximately 20 μm. Subsequently, sealant A was applied to the periphery of the applied liquid on the first main surface of the first glass plate using a small digital dispenser (Musashi Engineering, Inc., ML-5000XII) so as to surround the applied liquid. The applied thickness of the sealant was approximately 120 μm. The area of ​​the sealant in a plan view of the first glass plate was approximately 10% of the area of ​​the applied liquid. The main surface (first main surface) of the first glass plate to which the liquid agent and sealant had been applied was bonded to one main surface of the second glass plate under atmospheric pressure to obtain a laminate. The obtained laminate was placed in the chamber of a laminator (1834N manufactured by NISSHINBO) and degassed for 12 minutes to reduce the pressure to 100 Pa or less. Space volume inside the decompression chamber (L) / exhaust capacity inside the decompression chamber (L / min) = 1.734 Thereafter, with the laminator still in a decompressed state, the laminate was atmospherically pressed for 30 minutes. After atmospheric pressure pressing, the laminate was removed from the chamber and the sealant was cured by UV irradiation. A glass plate structure 2 was obtained by the above method.

[0054] (Example 3) Preparation of glass plate structure (intermediate layer is liquid layer, vacuum lamination method) Two glass plates (soda lime glass, 30 cm long x 30 cm wide x 1.1 mm thick) were prepared as glass plate components. Intermediate layer liquid agent A was applied to the first main surface of the first glass plate at 0.5 mg per dot, a total of 1,800 evenly spaced dots, using a dispenser (DSP SMDS-CV2-400, manufactured by Musashi Engineering Co., Ltd.). The applied thickness of the liquid agent was approximately 15 μm. Then, sealant A was applied to the periphery of the applied liquid agent area on the first main surface of the first glass plate using a dispenser (DSP SMDS-CV2-400, manufactured by Musashi Engineering Co., Ltd.) so as to surround the applied liquid agent. The applied thickness of the sealant was approximately 120 μm. The area of ​​the sealant in a plan view of the first glass plate was approximately 7% of the area of ​​the applied liquid agent area. Next, the other main surface (second main surface) of the second glass plate was fixed to the upper plate of the vacuum lamination device with double-sided tape so that the main surface (first main surface) of the first glass plate coated with the intermediate layer liquid and sealant was bonded to one of the main surfaces (first main surface) of the second glass plate, and the first glass plate was placed underneath with the main surface coated with the liquid and sealant facing up, and the pressure was reduced to below 100 Pa by degassing for 15 minutes. Space volume inside the decompression chamber (L) / exhaust capacity inside the decompression chamber (L / min) = 2.167 Thereafter, the second glass plate was slowly lowered vertically and bonded to the surface of the first glass plate coated with the liquid agent and the sealant, thereby obtaining a laminate. The sealant was then cured by UV irradiation. A glass plate structure 3 was obtained by the above method.

[0055] (Example 4) Preparation of a curved glass plate structure (intermediate layer is a liquid layer) Two glass plates (soda-lime glass, 60 cm long x 40 cm wide x 1.1 mm thick) with a curvature radius of approximately 1000 mm in the vertical direction were prepared as glass plate components. 0.9 g of intermediate layer liquid agent A was applied to the first main surface (concave side) of the first glass plate using a dispenser (ACCURA-8 manufactured by Iwashita Engineering Co., Ltd.) in a dot pattern with 0.9 mg dots and a 10 mm pitch. The applied thickness of the liquid agent was approximately 15 μm. Subsequently, sealant A was applied to the periphery of the applied liquid agent on the first main surface (concave side) of the first glass plate using a dispenser (ACCURA-8 manufactured by Iwashita Engineering Co., Ltd.) so as to surround the applied liquid agent. The applied thickness of the sealant was approximately 150 μm. The area of ​​the sealant in a plan view of the first glass plate was approximately 9% of the area of ​​the applied liquid agent. The first glass plate was bonded to the other convex surface of the second glass plate under atmospheric pressure, and the resulting laminate was placed in a vacuum chamber and degassed for 10 minutes to reduce the pressure to 100 Pa or less. Space volume inside the decompression chamber (L) / exhaust capacity inside the decompression chamber (L / min) = 1.445 The sealant was then cured by UV irradiation. A glass plate structure 4 was obtained by the above method.

[0056] Example 5: Preparation of a glass plate assembly having a curved surface subjected to a thermocompression treatment (intermediate layer is a liquid layer). Two glass plates (soda-lime glass, 60 cm long x 40 cm wide x 1.1 mm thick) with a curvature radius of approximately 1000 mm in the vertical direction were prepared as glass plate assembly members. 0.9 g of intermediate layer liquid A was applied to the first main surface, which would be the concave side of the first glass plate, in a dot pattern of 0.9 mg per dot and 10 mm pitch using a dispenser (ACCURA-8, manufactured by Iwashita Engineering Co., Ltd.). The applied thickness of the liquid was approximately 15 μm. Subsequently, sealant A was applied to the periphery of the applied liquid on the first main surface, which would be the concave side of the first glass plate, surrounding the liquid using a dispenser (ACCURA-8, manufactured by Iwashita Engineering Co., Ltd.). The applied thickness of the sealant was approximately 150 μm. In addition, the area of ​​the sealant in a plan view of the first glass plate was approximately 9% of the area of ​​the liquid agent application portion. The main surface (first main surface) of the first glass plate coated with the liquid agent and sealant was bonded to the other main surface (the convex side) of the second glass plate under atmospheric pressure to obtain a laminate. The laminate was placed in the chamber of a laminator (Nisshinbo 1834N) and degassed for 12 minutes to reduce the pressure to 100 Pa or less. Space volume inside the decompression chamber (L) / exhaust capacity inside the decompression chamber (L / min) = 1.734 The laminate was then removed from the vacuum chamber, placed in an aluminum pack, and degassed for 10 minutes under a reduced pressure of 10 kPa absolute. It was then placed in an autoclave and subjected to a thermocompression treatment at a pressure of 1.3 MPa and a temperature of 135°C for approximately 30 minutes. After the thermocompression treatment, the laminate was removed from the aluminum pack, and the sealant was cured by UV irradiation. A glass plate structure 5 was obtained by the above method.

[0057] (Example 6) Preparation of glass plate structure (intermediate layer is a solid layer made of a cured product of UV-curable resin) Two glass plates (soda-lime glass, 100 cm long x 100 cm wide x 1.1 mm thick) were prepared as glass plate components. 0.9 g of intermediate layer liquid B was applied to the first main surface of the first glass plate using a high-speed jet dispenser (Saneitec Corporation, dispense valve SJVH3000, Saneitec Corporation, dispense controller SJVC3000) in a dot pattern with 0.9 mg per dot and a 10 mm pitch. The applied thickness of the liquid was approximately 20 μm. Subsequently, sealant B was applied to the periphery of the applied liquid on the first main surface of the first glass plate using a small digital dispenser (Musashi Engineering, Inc., ML-5000XII) so as to surround the applied liquid. The applied thickness of the sealant was approximately 120 μm. The area of ​​the sealant in a plan view of the first glass plate was approximately 10% of the area of ​​the applied liquid. The main surface (first main surface) of the first glass plate coated with the liquid agent and sealant was bonded to one main surface of the second glass plate under atmospheric pressure to obtain a laminate. The obtained laminate was placed in a vacuum chamber and degassed for 10 minutes to reduce the pressure to 100 Pa or less. Space volume inside the decompression chamber (L) / exhaust capacity inside the decompression chamber (L / min) = 1.445 Thereafter, the liquid agent for the intermediate layer and the sealing agent were cured by UV irradiation to obtain an intermediate layer made of a solid layer. A glass plate structure 6 was obtained by the above method.

[0058] (Example 7) Preparation of glass plate structure (intermediate layer is a solid layer made of a cured thermosetting resin) Two glass plates (soda-lime glass, 100 cm long x 100 cm wide x 1.1 mm thick) were prepared as glass plate components. 0.9 g of intermediate layer liquid C was applied to the first main surface of the first glass plate using a high-speed jet dispenser (Saneitec Corporation, dispense valve SJVH3000, Saneitec Corporation, dispense controller SJVC3000) in a dot pattern with 0.9 mg per dot and 10 mm pitch. The applied thickness of the liquid was approximately 20 μm. Subsequently, sealant C was applied to the periphery of the applied liquid on the first main surface of the first glass plate using a small digital dispenser (Musashi Engineering, Inc., ML-5000XII) so as to surround the applied liquid. The applied thickness of the sealant was approximately 120 μm. The area of ​​the sealant in a plan view of the first glass plate was approximately 10% of the area of ​​the applied liquid. The main surface (first main surface) of the first glass plate coated with the liquid agent and sealant was bonded to one main surface of the second glass plate under atmospheric pressure to obtain a laminate. The obtained laminate was placed in a vacuum chamber and degassed for 10 minutes to reduce the pressure to 100 Pa or less. Space volume inside the decompression chamber (L) / exhaust capacity inside the decompression chamber (L / min) = 1.445 The sealant was then cured by UV irradiation, and the intermediate layer liquid was then cured by heating at 80°C for 1 hour, yielding an intermediate layer made of a solid layer. A glass plate structure 7 was obtained by the above method.

[0059] No bubbles were visually observed in the liquid layer (intermediate layer) of the glass plate structure 1 obtained in Example 1. Further, no misalignment between the two glass plates was confirmed. In the glass plate structure 2 obtained in Example 2, no bubbles were visually observed in the liquid layer (intermediate layer), and no misalignment between the two glass plates was confirmed. In the glass plate structure 3 obtained in Example 3, bubbles were visually observed in the liquid layer (intermediate layer), and misalignment of the two glass plates was confirmed. In the glass plate structure 4 obtained in Example 4, no bubbles were visually observed in the liquid layer (intermediate layer), and no misalignment between the two glass plates was confirmed. In the glass plate structure 5 obtained in Example 5, no bubbles were visually observed in the liquid layer (intermediate layer), and no misalignment between the two glass plates was confirmed. In the glass plate structure 6 obtained in Example 6, no bubbles were visually observed in the solid layer (intermediate layer), and no misalignment between the two glass plates was confirmed. In the glass plate structure 7 obtained in Example 7, no bubbles were visually observed in the solid layer (intermediate layer), and no misalignment between the two glass plates was confirmed.

[0060] [Table 1]

[0061] Although the present invention has been described in detail and with reference to specific embodiments, it will be apparent to those skilled in the art that various changes and modifications can be made without departing from the spirit and scope of the present invention. This application is based on a Japanese patent application (Patent Application No. 2020-176882) filed on October 21, 2020, the contents of which are incorporated herein by reference. [Industrial Applicability]

[0062] The glass plate structure obtained by the manufacturing method of the present invention has a high longitudinal wave sound velocity value and a high loss factor, and is therefore useful for applications such as diaphragms used in speakers, microphones, earphones, and mobile devices, materials for openings in buildings and vehicles, and glass substrates for magnetic recording media. [Explanation of symbols]

[0063] 1A, 1B... plates, 2... liquid agent for intermediate layer, 3... sealing agent, 10... glass plate structure, 11... laminate, 21... intermediate layer

Claims

1. A method for producing a glass plate structure comprising two or more plates, an intermediate layer between at least one pair of the plates, and at least one plate of the pair of plates being a glass plate, Applying a liquid agent for an intermediate layer and a sealing agent to at least a part of the main surface of one plate 1A; obtaining a laminate by laminating another plate 1B to the main surface of the plate 1A to which the intermediate layer liquid agent and the sealing agent have been applied; subjecting the laminate to a reduced pressure; and and curing the intermediate layer liquid agent after subjecting the laminate to a reduced pressure. The method for producing a glass plate structure, wherein the liquid agent for forming an intermediate layer contains a curable resin.

2. When subjecting the laminate to a reduced pressure, a reduced pressure chamber is used, The method for producing a glass plate structure according to claim 1, wherein the spatial volume (L) in the reduced pressure chamber / exhaust capacity (L / min) in the reduced pressure chamber is 1.8 or less.

3. The method for producing a glass plate structure according to claim 1 or 2, wherein when the laminate is subjected to reduced pressure, the time required for the pressure to reach 100 Pa or less is 1 minute to 180 minutes.

4. 4. The method for manufacturing a glass plate structure according to claim 1, wherein the sealant has a viscosity coefficient higher than that of the liquid agent for forming an intermediate layer.

5. The viscosity coefficient of the sealing agent is 1×10 －１ Pa s or more, and the viscosity coefficient of the liquid agent for the intermediate layer is 1×10 ３ The method for producing a glass plate structure according to any one of claims 1 to 4, wherein the viscosity is Pa·s or less.

6. The method for producing a glass plate structure according to any one of claims 1 to 5, wherein the liquid agent for forming an intermediate layer contains silicone.

7. The method for producing a glass plate structure according to any one of claims 1 to 6, wherein the coating pattern of the liquid agent for intermediate layer is a layer, a dot, a grid, or a stripe.

8. The method for manufacturing a glass plate structure according to any one of claims 1 to 7, wherein the coating thickness of the sealing agent is greater than the coating thickness of the liquid agent for intermediate layer.

9. The method for manufacturing a glass plate structure according to any one of claims 1 to 8, wherein the coating thickness of the liquid agent for intermediate layer is 5 µm to 500 µm.

10. The method for manufacturing a glass plate structure according to claim 8 or 9, wherein the sealing agent has a coating thickness of 10 μm to 1000 μm.

11. The method for producing a glass plate structure according to any one of claims 1 to 10, further comprising applying pressure to the laminate after subjecting it to a reduced pressure.

12. The method for producing a glass plate structure according to claim 11, wherein the laminate is pressed by being pressed at a pressure of 0.1 MPa to 10 MPa for a pressing time of 1 minute to 30 minutes.

13. the sealing agent contains a curable resin, The method for producing a glass plate structure according to any one of claims 1 to 12, further comprising curing the sealant after subjecting the laminate to a reduced pressure.

14. The method for producing a glass plate structure according to any one of claims 1 to 13, wherein the plate has a curved surface.

15. The method for producing a glass plate structure according to any one of claims 1 to 14, wherein the plate 1A and the plate 1B are bonded together under normal pressure.

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