JP2013082602A - Laminated glass and fire prevention equipment provided with laminated glass - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide fire prevention safety glass improved in an appearance of a heat resistant crystallized glass and provided with sufficient safety, in order to widen the range of utilizing the heat resistant crystallized glass that is most excellent in fire prevention performance.SOLUTION: The laminated glass 100 is formed by laminating a plurality of glass plates 10 containing at least one heat resistant glass sheet composed of crystallized glass by an adhesive (adhesive layer 12) through a resin film 11. An adjusting agent adjusting a tone of the glass plates 10 is contained in at least any one of the resin film 11 and the adhesive.

Description

  The present invention relates to a laminated glass obtained by bonding a plurality of glass plates including at least one heat-resistant plate glass made of crystallized glass with an adhesive via a resin film, and a fire prevention equipment including the laminated glass.

  Glass used for windows and doors in commercial facilities such as department stores, supermarkets, public facilities such as city halls, hospitals, and station buildings, and large-scale office buildings, blocks flames and smoke in the event of a fire. Thus, a fire prevention function that suppresses the spread of fire to a minimum and a safety function that does not cause glass fragments to scatter even when broken and does not cause a through hole are required. For this reason, the number of cases in which fireproof safety glass having both functions is adopted in recent buildings is increasing.

  Fireproof safety glass is manufactured using a heat-resistant plate glass excellent in fire resistance. Heat-resistant plate glass is mainly classified into heat-resistant tempered glass and low-expansion fireproof glass, which are also tempered glass, and heat-resistant crystallized glass. The heat-resistant tempered glass is obtained by cutting a soda-lime glass that is usually used as a plate glass for construction to a full size, specially polishing the edge, and then performing a special heat treatment to improve heat resistance and impact resistance. Low-expansion fire-proof glass is a glass that has been heat-treated after reducing the soda and lime content of soda-lime glass that is normally used as building glass, adding a boric acid component, cutting the molded glass to its original size It is.

  On the other hand, the heat-resistant crystallized glass is a glass having a lithium-alumina-silicate system composition in which fine crystals are precipitated on the entire glass by subjecting the formed plate glass to a predetermined heat treatment, and the heat resistance is greatly improved. Since the heat-resistant crystallized glass has a very small average linear expansion coefficient, it does not break even if it is quenched by watering due to fire extinguishing activities when a fire occurs. For this reason, at present, it can be said that the heat-resistant crystallized glass is the most excellent glass in terms of fire prevention performance. However, unlike other heat-resistant plate glass, heat-resistant crystallized glass is not tempered glass, and therefore has a problem that it is easily damaged by impact. In addition, when the heat-resistant crystallized glass is broken, the fragments become sharp and dangerous.

In order to improve the safety of the heat-resistant crystallized glass in the fireproof safety glass of Patent Documents 1 and 2 for these problems, a fluororesin film is bonded to one side or both sides of a plurality of heat-resistant crystallized glass. A fireproof safety glass that improves the shock absorption and penetration resistance of heat-resistant crystallized glass, which is easily damaged, and can prevent glass fragments from being scattered even if the glass is broken.
Patent Document 3 discloses a method for producing fire safety glass. According to this document, after disposing a fluororesin film in the gap between two fireproof glass plates, it is crimped by applying heat to complete a fireproof safety glass excellent in shock absorption and penetration resistance. .
Thus, in heat-resistant crystallized glass, various devices for improving safety have been conventionally made, and as a result, it has been adopted as fire-proof safety glass for buildings.

JP-A-4-224938 JP-A-8-132560 JP-A-9-002847

  However, heat-resistant crystallized glass used for fireproof safety glass has a problem that it lacks transparency compared to normal glass. For example, depending on the type of heat-resistant crystallized glass, the whole glass has a light brown color. There are various possible causes for this, but it is thought to be derived from impurities contained in the heat-resistant crystallized glass and the crystal structure of the heat-resistant crystallized glass. Also in the fire safety glass described in Patent Documents 1 to 3, the heat-resistant crystallized glass is colored due to impurities and the like, and can have an appearance with poor transparency.

  When heat-resistant crystallized glass is employed as fire safety glass, there may be situations where it is not preferred as a building material depending on its color state. For example, in a commercial show window, colorless glass that is as transparent as possible is preferred to show the interior exhibits vividly. For this reason, products that use heat-resistant crystallized glass are often limited in use, such as places where the appearance is not considered much. Such a problem in appearance in the heat-resistant crystallized glass does not affect the fireproof performance, but is not commercially preferable and also leads to a decrease in commercial value.

  In order to improve the color tone of the heat-resistant crystallized glass, it is also conceivable to change the coloration state by changing the production conditions such as the glass composition and the crystal precipitation conditions. However, even if the manufacturing conditions of the heat-resistant crystallized glass are changed, the coloration state cannot be accurately predicted. In addition, for manufacturing equipment such as a glass melting furnace for manufacturing many glass products, it is not easy to change the entire manufacturing conditions for manufacturing a small amount of products, and it is not realistic from the viewpoint of cost.

  The present invention has been made in view of the above problems, and in order to widen the range of use of the heat-resistant crystallized glass, which is the most excellent glass, in terms of fire prevention performance, the appearance of the heat-resistant crystallized glass is improved and sufficient It aims at providing the fire safety safety glass provided with safety. It is another object of the present invention to provide a fire prevention equipment having such a fire safety safety glass and having an excellent appearance.

The characteristic configuration of the laminated glass according to the present invention for solving the above problems is as follows.
A laminated glass in which a plurality of glass plates including at least one heat-resistant plate glass composed of crystallized glass are bonded with an adhesive via a resin film,
In at least one of the resin film and the adhesive, an adjusting agent for adjusting the color tone of the glass plate is included.

As explained in the above problem, heat-resistant plate glass (heat-resistant crystallized glass) composed of crystallized glass has a problem that it is easy to color and lacks transparency, and this is a factor that limits the use of heat-resistant plate glass. It was. In particular, the coloration state of the glass can change due to various factors, and it has been difficult to adjust to a desired color tone by changing the manufacturing conditions of the heat-resistant plate glass.
In this respect, the laminated glass of the present configuration has a color tone of the glass plate on at least one of the resin film and the adhesive when bonding a plurality of glass plates including at least one heat-resistant plate glass made of crystallized glass. The adjustment agent to adjust is included. That is, since the adjusting agent is not included on the side of the heat-resistant plate glass, the color performance of the glass plate can be easily and reliably adjusted without affecting the original performance of the heat-resistant plate glass. Therefore, the laminated glass of this configuration can be a low-cost fire safety glass while having a good appearance.
In the case where the adjusting agent is included in both the resin film and the adhesive, the adjusting agent can be selected individually in the resin film and the adhesive, so that the adjustment range of the color tone is widened. Moreover, when an adjusting agent is contained in an adhesive agent, adjustment of adjusting agent content becomes easy and it becomes easy to adjust a laminated glass to a desired color tone.

In the laminated glass according to the present invention,
The average linear expansion coefficient of the crystallized glass is preferably −10 to 10 × 10 ⁻⁷ / K in the temperature range of 30 to 750 ° C.

  Since the laminated glass of this configuration has the above-mentioned average linear expansion coefficient, it maintains a sufficiently low average linear thermal expansion coefficient not only in normal times but also in the event of a fire, and is quenched by watering from fire extinguishing activities. It will not be damaged.

In the laminated glass according to the present invention,
The resin film is selected from the group consisting of tetrafluoroethylene (TFE) -hexafluoropropylene (HFP) -vinylidene fluoride (VDF) copolymer (THV), polycarbonate (PC), and polyethylene terephthalate (PET). It is preferable that it is at least one.

The resin film used for fireproof safety glass needs to adopt a material that does not emit smoke or fire.
In this respect, the resin film used for the laminated glass of this configuration is selected from the group consisting of THV, PC, and PET, which are resins having excellent heat resistance, and therefore hardly emits smoke even in a high temperature environment. It is difficult to ignite.
When the resin film is sandwiched and bonded between the glass plates, the resin film adheres to the glass plate, and the supply of oxygen to the adhesive (adhesive layer) existing between the resin film and the glass plate is substantially blocked. The For this reason, it is difficult for the adhesive to emit smoke or ignite in a high temperature environment. Therefore, the laminated glass of this configuration can be a fire safety glass having high fire safety and safety performance.

  In the laminated glass according to the present invention, the adhesive is preferably a photocurable adhesive mainly composed of an ultraviolet curable resin.

  If it is a laminated glass of this configuration, the adhesive can be cured without applying heat to the glass plate or the resin film.For example, one that is not heat-resistant plate glass is used as one of the plurality of glass plates, Even when a resin film having relatively low heat resistance is used as a resin film sandwiched between a plurality of glass plates, the performance of the glass plate and the resin film is not deteriorated by heat. Moreover, since the crimping | compression-bonding operation | work while applying heat becomes unnecessary, adhesion | attachment with a glass plate and a resin film can be performed, without touching the glass surface after grinding | polishing directly. Therefore, the transparency of the laminated glass is not lowered.

The characteristic configuration of the laminated glass according to the present invention for solving the above problems is as follows.
Between a plurality of glass plates containing at least one heat-resistant plate glass composed of crystallized glass, a laminated glass that is heat-sealed by sandwiching a resin film,
The resin film includes an adjusting agent for adjusting the color tone of the glass plate.

  The laminated glass of this configuration uses a resin film that can be heat-sealed when a plurality of glass plates including at least one heat-resistant plate glass made of crystallized glass are bonded together. It contains an adjusting agent that adjusts the color tone. That is, since the adjusting agent is not included on the side of the heat-resistant plate glass, the color performance of the glass plate can be easily and reliably adjusted without affecting the original performance of the heat-resistant plate glass. Therefore, the laminated glass of this configuration can be a low-cost fire safety glass while having a good appearance.

In the laminated glass according to the present invention,
The resin film is preferably tetrafluoroethylene (TFE) -hexafluoropropylene (HFP) -vinylidene fluoride (VDF) copolymer (THV).

The resin film used for fireproof safety glass needs to adopt a material that does not emit smoke or fire.
In this respect, since the resin film used for the laminated glass of this configuration is composed of THV, which is a resin having excellent heat resistance, it hardly emits smoke or ignites even in a high temperature environment. Moreover, since THV is excellent in strength, when THV is bonded to glass, the impact resistance and penetration resistance of the glass are greatly improved. Furthermore, THV exhibits high flame retardancy due to a barrier effect due to a strong interatomic bond between carbon and fluorine. Therefore, the laminated glass of this configuration can be a fire safety glass having high fire safety and safety performance.

In the laminated glass according to the present invention,
The regulator is at least one blue pigment selected from the group consisting of aluminum-cobalt oxide, aluminum-zinc-cobalt oxide, silicon-cobalt oxide, silicon-zinc-cobalt oxide, and phthalocyanine compounds. Preferably there is.

  The laminated glass having this configuration is selected from the group consisting of aluminum-cobalt oxide, aluminum-zinc-cobalt oxide, silicon-cobalt oxide, silicon-zinc-cobalt oxide, and phthalocyanine compounds as a regulator. Since at least one blue pigment is used, it has a colorless transparent or light blue transparent color tone and has a high commercial value and an excellent appearance.

The characteristic configuration of the fire prevention equipment according to the present invention for solving the above problems is as follows:
Laminated glass according to the present invention;
A frame for fitting the laminated glass;
With
The frame body is provided with a groove portion for receiving the peripheral edge portion of the laminated glass, and in a state where the laminated glass is fitted into the frame body, a gap generated between the peripheral edge portion of the laminated glass and the groove portion is heat-resistant. It is in sealing with a conductive material.

The fire prevention equipment of this structure has sealed the clearance gap which generate | occur | produced between the glass peripheral part of the laminated glass which concerns on this invention, and the groove part of a frame with a heat resistant material. As a result, in the unlikely event of a fire, flames and smoke can be blocked to prevent the spread of fire.
Moreover, since the fire prevention equipment of this structure uses the above-mentioned laminated glass, it has high commercial value as a low-cost fire prevention equipment while having a good appearance.

FIG. 1 is an exploded perspective view of a laminated glass according to the first embodiment of the present invention. FIG. 2 is a perspective view of the laminated glass according to the first embodiment of the present invention. FIG. 3 is a perspective view of a laminated glass according to the second embodiment of the present invention. FIG. 4 is a third embodiment of the present invention, a front view of the fire prevention equipment using the laminated glass according to the first embodiment, and a main part of the fire prevention equipment viewed from the side with a part of the frame removed. It is an expanded sectional view.

  Hereinafter, the laminated glass concerning this invention and embodiment regarding the fire protection equipment using the said laminated glass are described based on FIGS. 1-4. However, the present invention is not intended to be limited to the configurations described in the embodiments and drawings described below.

<First embodiment>
FIG. 1 is an exploded perspective view of a laminated glass 100 according to the first embodiment of the present invention. The laminated glass 100 is composed of two glass plates 10 (10a, 10b), a resin film 11 sandwiched between the two glass plates 10, and two glass plates 10 attached via the resin film 11. And an adhesive layer 12 made of an adhesive to be combined. FIG. 2 is a perspective view of a laminated glass 100 according to the first embodiment of the present invention, and shows a laminated glass 100 in which two glass plates 10 are integrated by an adhesive layer 12 via a resin film 11. . The laminated glass 100 is a heat-resistant plate glass (heat-resistant crystallized glass) in which at least one of the two glass plates 10 (10a, 10b) is made of crystallized glass. Thereby, it can become fire prevention safety glass provided with high fire prevention and safety performance. Note that either of the two glass plates 10 (10a, 10b) may be heat-resistant crystallized glass.

  The colored state of the glass plate (heat-resistant crystallized glass) 10 made of crystallized glass is considered to change depending on impurities contained in the glass, the crystal structure of the glass, and the like. As described in the section of the prior art, the coloration in the heat-resistant crystallized glass does not affect the fireproof performance, but is not commercially preferable. Therefore, in the laminated glass 100, an adjusting agent for adjusting the color tone of the glass plate 10 is included in at least one of the adhesive layer 12 composed of the resin film 11 and the adhesive. In the present invention, since the adjusting agent is not included in the glass plate 10, the original performance of the glass plate 10 is not affected, and the color tone of the glass plate 10, and thus the color tone of the entire laminated glass 100 is easily and reliably adjusted. can do. In addition, a color tone can be evaluated by the transmittance | permeability of measurement light, for example using the Shimadzu Corporation ultraviolet visible spectrophotometer (UV-3100).

  In the laminated glass 100 after adjusting the color tone, in order to realize a transparent appearance with a high commercial value, the color tone is set to 0.300 to 0.317 in the xyY display system of the CIE chromatogram. It is preferable to set it as the range. Thereby, the laminated glass exhibits a color tone of colorless transparent to light blue transparent, and a laminated glass excellent in transparency can be realized.

  In FIG. 1 and FIG. 2, the laminated glass 100 is configured by sandwiching one resin film 11 between two glass plates 10, but the number of glass plates 10 may be more than two. For example, the structure which pinches | interposes the two resin films 11 between each glass plate 10 with the three glass plates 10 is mentioned. When the three glass plates 10 are composed of a glass plate 10a, a glass plate 10b, and a glass plate 10c (not shown), any one of the glass plates 10a, 10b, and 10c is heat resistant crystallized glass. However, two of the glass plates 10a, 10b, and 10c may be heat-resistant crystallized glass, and all of the three glass plates may be heat-resistant crystallized glass. When the number of the glass plates 10 exceeds two, an adhesive is applied to both surfaces of the glass plate 10 existing on the inner side to form an adhesive layer 12, which is bonded to another glass plate 10 via the resin film 11. Details of the adhesive will be described later.

The heat-resistant crystallized glass is a transparent crystallized glass in which crystals of β-quartz solid solution are precipitated, and is characterized in that the average crystal grain size is sufficiently smaller than the visible light wavelength. The preferable characteristic of heat-resistant crystallized glass has an average linear expansion coefficient of −10 to 10 × 10 ⁻⁷ / K in a temperature range of 30 to 750 ° C. As a result, the laminated glass 100 maintains a sufficiently low average linear thermal expansion coefficient not only in normal times but also in the event of a fire, and will not break even if quenched with water sprays (sprinklers, etc.) for fire fighting activities. Absent.

Resistant crystallized glass, a _composition, SiO 2 60 to 70 _{wt%, Al} 2 O 3 _{17~27 wt%,} Li 2 O 3 to 6 _wt%, Na 2 O 0.05 to 1 _{wt%, K} 2 O 0.1-1 wt%, _ZrO 2 1 to 3 wt%, _TiO 2 1 to 3 wt%, MgO 0.1 to 0.9 _{wt%, P} 2 O 5 _0.05~2 wt%, _As 2 O _{3 0-2%} by _weight, preferably contains Sb ₂ O 3 0-2% by weight. The color tone of the heat-resistant crystallized glass having such a composition is such that x of reflected light is in the range of 0.318 to 0.330 in the xyY display system of the CIE chromatogram. If it is this range, the color tone of the laminated glass 100 using heat-resistant crystallized glass can be easily adjusted using a regulator. The detail about each composition of heat-resistant crystallized glass is demonstrated below.

SiO ₂ is a component that forms a network structure and constitutes a crystal. When the SiO ₂ content is less than 60% by weight, the average linear expansion coefficient increases and the mechanical strength also decreases. On the other hand, when it exceeds 70% by weight, it becomes difficult to melt the glass, and defects such as bubbles and devitrified substances are generated. The SiO ₂ content is more preferably 64 to 66% by weight. Thereby, while maintaining a predetermined average linear expansion coefficient, transparency of glass can also be maintained.

Al ₂ O ₃ is a component constituting the crystal. When the Al ₂ O ₃ content is less than 17% by weight, the devitrification of the glass becomes strong and the chemical durability is lowered. On the other hand, if the amount is more than 27% by weight, the viscosity of the glass becomes too high to obtain a uniform glass. The Al ₂ O ₃ content is more preferably 21 to 23% by weight. Thereby, while maintaining chemical durability, transparency of glass can also be maintained.

Li ₂ O is a component constituting the crystal. When the Li ₂ O content is less than 3% by weight, it becomes difficult to form a desired crystal and the solubility is deteriorated. On the other hand, if it exceeds 6% by weight, the devitrification of the glass becomes strong. The content of Al ₂ O ₃ is more preferably 3 to 5% by weight. Thereby, while forming desired crystallization and heat resistance can be improved, transparency of glass can also be maintained.

Na ₂ O is a component that improves the solubility of the glass. If the Na ₂ O content is less than 0.05% by weight, the desired solubility cannot be obtained. On the other hand, if it exceeds 1% by weight, the average linear expansion coefficient and dielectric loss of the glass increase. The Na ₂ O content is more preferably 0.4 to 0.6% by weight. Thereby, while maintaining a predetermined average linear expansion coefficient, the uniformity of glass can be maintained.

K ₂ O is a component that improves the solubility of the glass. If the K ₂ O content is less than 0.1% by weight, the desired solubility cannot be obtained. On the other hand, if it exceeds 1% by weight, the average linear expansion coefficient and dielectric loss of the glass increase. The K ₂ O content is more preferably 0.2 to 0.4% by weight. Thereby, while maintaining a predetermined average linear expansion coefficient, the uniformity of glass can be maintained.

In addition, it is preferable that the total content of Na ₂ O and K ₂ O is 0.5 to 2% by weight. When the total content of Na ₂ O and K ₂ O is less than 0.5% by weight, the solubility of the glass is lowered, and when it exceeds 2% by weight, the strength and heat resistance of the glass are lowered.

ZrO ₂ is a component that acts as a nucleating agent. If the ZrO ₂ content is less than 1% by weight, it will not be stably crystallized, and coarse and large crystals will be formed, making it difficult to obtain transparent crystallized glass. On the other hand, when it exceeds 3% by weight, an undecomposed product of zirconia is generated, and devitrified matter is generated in the glass.

TiO ₂ is a component that acts as a nucleating agent. If the TiO ₂ content is less than 1% by weight, the effect of promoting crystallization cannot be obtained, and desired crystals cannot be obtained. On the other hand, when the amount is more than 3% by weight, the liquid phase temperature becomes high, and the molding operation becomes difficult. Furthermore, the heat-resistant crystallized glass is colored brown and the transparency is impaired. The TiO ₂ content is more preferably 1.3 to 3% by weight. Thereby, while achieving a desired crystallinity degree and heat resistance can be improved, transparency of glass can also be maintained.

The total content of ZrO ₂ and TiO ₂ is preferably 2.6 to 5% by weight. When the total content of ZrO ₂ and TiO ₂ is less than 2.6% by weight, the effect of promoting crystallization cannot be obtained, and the mechanical strength is lowered. On the other hand, when the total content exceeds 5% by weight, devitrification becomes strong, and it becomes difficult to obtain uniform crystallized glass.

MgO is a component that improves solubility and prevents the occurrence of bubble defects. If the MgO content is less than 0.1% by weight, bubbles tend to be generated. On the other hand, if the MgO content is more than 0.9% by weight, the thermal expansion coefficient increases and the thermal characteristics deteriorate. Furthermore, in the presence of TiO ₂ , the color may develop and the transparency may be impaired. The MgO content is more preferably 0.4 to 0.6% by weight. Thereby, generation | occurrence | production of a bubble defect can be prevented and transparency of glass can also be maintained.

P ₂ O ₅ is a component that improves the poor solubility of ZrO ₂ contained as a nucleating agent. If the P ₂ O ₅ content is less than 0.05% by weight, there is no improvement effect. On the other hand, when the amount is more than 2% by weight, the phase separation is facilitated, the amount of crystal formation increases, and the transparency is lowered. The content of P ₂ O ₅ is more preferably 1 to 2% by weight. Thereby, desired crystallization can be obtained and the transparency of the glass can be maintained.

Further, _As 2 _{O 3} and _Sb 2 _{O 3} content _of added as a refining agent, the total content is preferably 0.2 to 2 wt%. Thereby, the solubility of glass, workability | operativity, and uniformity can be improved. When the total content is less than 0.2%, the clarification effect is lowered, and when it exceeds 2% by weight, it is not environmentally preferable. A more preferable total content of As ₂ O ₃ and Sb ₂ O ₃ is 0.2 to 0.4% by weight.

Furthermore, the heat-resistant crystallized glass used in the present invention may contain 0.5 to 3 wt% of arbitrary components such as CaO, PbO, F ₂ , Cl ₂ or CeO ₂ . Thereby, the laminated glass suitable for a desired use can be comprised.

  Moreover, 1-12 mm is preferable and, as for the thickness of the heat-resistant crystallized glass utilized by this invention, 4-12 mm is more preferable. Thereby, the laminated glass 100 can adjust the color tone of glass to a desired grade easily, providing a desired fire prevention and safety performance as fire prevention equipment. Moreover, since the heat-resistant crystallized glass having the above thickness range is compatible with a normal glass plate, it can be applied to a conventional place of use as it is.

  At least one of the resin film 11 and the adhesive contains an adjusting agent that adjusts the color tone of the heat-resistant plate glass. The heat-resistant crystallized glass has a light brown color. When the laminated glass 100 is produced using this heat-resistant crystallized glass, the transparency is insufficient depending on the coloration state of the laminated glass 100, which causes a problem in appearance. The adjusting agent is used for adjusting the coloration state of the laminated glass 100 to a desired color tone. Here, “adjusting the color tone” means that for a certain color, the complementary color is used to cancel the color, improve the transparency, and actively add a desired color. means.

  The adjusting agent used in the present invention is not particularly limited as long as it is a blue pigment, and can be appropriately selected according to the laminated glass to be produced. For example, aluminum-cobalt oxide, aluminum-zinc-cobalt oxidation Products, silicon-cobalt oxide, silicon-zinc-cobalt oxide, and phthalocyanine compounds can be used. These blue pigments can be used in combination. Preferred blue pigments are phthalocyanine compounds, among which C.I. which is a β crystal of copper phthalocyanine. I. Pigment blue 15: 3 and C.I. I. Pigment Blue 15: 4 is more preferable. Although the quantity of the adjusting agent to add can be suitably adjusted according to the laminated glass to produce, Preferably it is 0.1 to 5 weight% with respect to the resin film 11 or an adhesive agent. If the amount of the adjusting agent is less than 0.1% by weight, the color tone of the laminated glass cannot be sufficiently adjusted, and if it exceeds 5% by weight, the transparency of the laminated glass may be impaired.

  The resin film 11 used for fireproof safety glass needs to employ a material that does not emit smoke or fire. Such a resin film 11 includes tetrafluoroethylene (TFE) -hexafluoropropylene (HFP) -vinylidene fluoride (VDF) copolymer (THV), polycarbonate (PC), and polyethylene, which are resins having excellent heat resistance. It is preferably at least one selected from the group consisting of terephthalate (PET). In addition, polyvinyl butyral resin (PVB), ethylene vinyl acetate (EVA), polymethyl methacrylate (PMMA), fluorinated ethylene propylene (FEP), tetrafluoroethylene-perfluoroalkoxyethylene copolymer (PFA), polychloro Trifluoroethylene (PCTFE), tetrafluoroethylene / ethylene copolymer (ETFE), polyvinylidene fluoride (PVDF), and the like can also be used. Further, the thickness of the resin film is preferably 0.2 to 2 mm. Thereby, the laminated glass 100 can be a fire safety glass having high fire safety and safety performance. If the thickness of the resin film 11 is less than 0.2 mm, it is difficult for the laminated glass 100 to obtain desired impact resistance. On the other hand, if the thickness of the resin film 11 exceeds 2 mm, not only is it difficult to ensure the transparency of the laminated glass 100, but smoke is also generated due to melting and decomposition of the resin film 11 in the event of a fire. The amount may increase significantly.

  As an adhesive for bonding a glass plate and a resin film, a liquid adhesive having a relatively low viscosity before curing (for example, a material mainly composed of a thermosetting resin, a material mainly composed of an ultraviolet curable resin, etc.) However, a photo-curing adhesive mainly composed of an ultraviolet curable resin is preferable. When the laminated glass is a combination of a heat-resistant plate glass and a normal glass plate, the average linear expansion coefficients of the two glasses are greatly different, so bonding with a heat-curable adhesive will cause the glass plate to warp or break during heating. May occur. Moreover, a resin film and an adhesive agent deteriorate by heating, and a transparent feeling may fall. On the other hand, when a photocurable adhesive is used, the adhesive layer 12 can be cured without applying heat to the glass plate 10 or the resin film 11. Therefore, even if it is the combination of a heat-resistant plate glass and a normal glass plate, both can be integrated reliably, the glass plate does not warp or break, and a laminated glass with good transparency can be produced. Even when one of the plurality of glass plates 10 is not a heat-resistant plate glass, or when a resin film 11 sandwiched between the plurality of glass plates 10 has a relatively low heat resistance, the glass plate 10 and the resin are used. The performance of the film 11 is not deteriorated by heat. Furthermore, since the crimping operation while applying heat becomes unnecessary, the glass plate 10 and the resin film 11 can be bonded without directly touching the glass surface. Therefore, the transparency of the laminated glass 100 does not decrease.

  Examples of the ultraviolet curable resin include an acrylic resin doped with a functional group such as a methacryloyl group or an anthracene group that reacts with ultraviolet rays. The photocurable adhesive is applied to the unpolished surface of the glass plate 10 with a uniform film thickness using a bar coater, a spin coater or the like, and the adhesive layer 12 is formed. When the resin film 11 is sandwiched between the glass plates 10 on which the adhesive layer 12 is formed and irradiated with ultraviolet rays from the side, the adhesive layer 12 is cured and the integral laminated glass 100 is completed.

  The adjusting agent can be included in at least one of the resin film 11 and the adhesive. However, when the adjusting agent is included in both the resin film 11 and the adhesive, the adjusting agent is individually adjusted in the resin film 11 and the adhesive. Since the agent can be selected, the range of color tone adjustment is expanded. Moreover, when including in an adhesive agent, adjustment of content of a regulator becomes easy and it becomes easy to adjust the laminated glass 100 to a desired color tone.

<Second embodiment>
1 and 2 show the laminated glass 100 including the adhesive layer 12 as the first embodiment. However, in the present invention, at least one piece of heat-resistant crystallized glass does not have such an adhesive layer 12. The laminated glass may be formed by sandwiching the resin film 11 between a plurality of glass plates 10 and including heat sealing. FIG. 3 is a perspective view of a laminated glass 200 according to the second embodiment of the present invention, in which two glass plates 10 are integrated through a resin film 11. In the laminated glass 200, at least one of the two glass plates 10 may be heat-resistant crystallized glass. In the present embodiment, the resin film 11 includes an adjusting agent that adjusts the color tone of the glass plate 10. Thereby, the transparency of the laminated glass 200 improves. In addition, as a regulator, the same thing as the regulator demonstrated in 1st embodiment can be used.

  Examples of heat-sealable resin films include polyvinyl butyral resin (PVB), ethylene vinyl acetate (EVA), tetrafluoroethylene (TFE) -hexafluoropropylene (HFP) -vinylidene fluoride (VDF) copolymer. (THV), fluorinated ethylene propylene (FEP), tetrafluoroethylene-perfluoroalkoxyethylene copolymer (PFA), polychlorotrifluoroethylene (PCTFE), tetrafluoroethylene / ethylene copolymer (ETFE) And polyvinylidene fluoride (PVDF). Of these, tetrafluoroethylene (TFE) -hexafluoropropylene (HFP) -vinylidene fluoride (VDF) copolymer (THV) is preferred. The thickness of the resin film is preferably 0.2 to 2 mm. Thereby, the laminated glass 200 can be a fireproof safety glass having high fireproofing / safety performance. When the thickness of the resin film is less than 0.2 mm, it is difficult for the laminated glass 200 to obtain desired impact resistance. On the other hand, if the thickness of the resin film 11 exceeds 2 mm, not only is it difficult to ensure the transparency of the laminated glass 200, but smoke is also generated due to melting and decomposition of the resin film 11 in the event of a fire. The amount may increase significantly.

Here, the structure of the laminated glasses 100 and 200 which concern on said 1st embodiment and 2nd embodiment is illustrated. However, the laminated glass of this invention is not limited to the following structures.
(1) Heat-resistant crystallized glass + THV resin film + heat-resistant crystallized glass (2) Heat-resistant crystallized glass + photocurable adhesive + polycarbonate (PC) resin film + photocurable adhesive + heat-resistant crystallized glass (3) Heat-resistant crystallized glass Crystallized glass + photo-curable adhesive + polycarbonate (PC) resin film + photo-curable adhesive + other heat-resistant plate glass (for example, alkali-free glass (OA-10 manufactured by Nippon Electric Glass Co., Ltd.), high strain point glass (Japan) Electric Glass PP8) etc.)
(4) Other heat-resistant plate glass + THV resin film + heat-resistant crystallized glass + THV resin film + other heat-resistant plate glass (5) Heat-resistant crystallized glass + polyvinyl butyral resin (PVB) + heat-resistant crystallized glass

<Third embodiment>
FIG. 4 is a third embodiment of the present invention, a front view of a fire prevention equipment 300 using the laminated glass 100 according to the first embodiment, and a fire prevention equipment viewed from the side with a part of the frame body 20 removed. It is a principal part expanded sectional view of 300. FIG. An arrow in the enlarged cross-sectional view of the main part shows the front side of the fire prevention equipment 300. As shown in FIG. 4, the fire prevention equipment 300 is fitted with the laminated glass 100 into the frame body 20, and a gap generated between the peripheral edge portion of the laminated glass 100 and the groove portion 21 of the frame body 20 is formed as a heat resistant material. It is configured with sealing. Specifically, the frame 20 is formed with a groove 21 that receives the peripheral edge of the laminated glass 100, and the width of the groove 21 is configured to be larger than the thickness of the laminated glass 100. A ceramic fiber blanket 22, which is a heat resistant material, is provided outside the peripheral edge of the laminated glass 100. A gap between the peripheral edge portion of the laminated glass 100 and the groove portion 21 is filled with a fireproof silicone 23. As a result, in the unlikely event of a fire, flames and smoke can be blocked to prevent the spread of fire.

  In addition, in this embodiment, although the laminated glass 100 which concerns on 1st embodiment is used, naturally it is also possible to fit the laminated glass 200 which concerns on 2nd embodiment in the frame 20, and to comprise fire prevention equipment. is there. An example of a method for manufacturing a fire prevention equipment is shown below, but the method is not limited to this method.

  First, a part of the frame 20 attached to the left and right side surfaces and the lower part of the laminated glass 100 is produced. A steel material (for example, an aluminum alloy plate, a hot dip galvanized steel plate, etc.) used for fire prevention equipment is processed into a long object having a U-shaped cross section, and a groove portion 21 for receiving the peripheral portion of the laminated glass 100 is formed inside. . A long object is combined so as to match the shape of the laminated glass 100, the laminated glass 100 is slid along the inner groove 21, and three sides of the laminated glass 100 are fitted into the frame body 20. Thereafter, a long object having a U-shaped cross-section, which is a part of the separately produced frame body 20, is fitted into the upper part of the laminated glass 100 to obtain a complete frame body 20. A fireproof silicone 23 is sealed in a gap generated between the peripheral edge of the laminated glass 100 and the groove 21 of the frame body 20. The fireproof silicone 23 is filled with, for example, SE5007 (manufactured by Toray Dow Corning), sealant 40N (manufactured by Shin-Etsu Silicone), sealant 74 (manufactured by Shin-Etsu Silicone) or the like using a caulking gun.

  Examples of the laminated glass of the present invention will be described. In constructing the laminated glass, according to the present invention, an adjusting agent for adjusting the color tone of the glass plate is included in the resin film or the adhesive. The color tone of the finished laminated glass was measured.

<Example 1>
The glass plate constituting the laminated glass has a final composition of SiO ₂ 67% by weight, Al ₂ O ₃ 20% by weight, Li ₂ O 4% by weight, ZrO ₂ 3% by weight, TiO ₂ 2% by weight. It is a heat-resistant crystallized glass obtained by forming a molten glass by a roll-out method, crystallizing at a maximum temperature of 900 ° C., and then polishing both surfaces. This heat-resistant crystallized glass has an average linear expansion coefficient of −3 × 10 ⁻⁷ / K in a temperature range of 30 to 750 ° C., and has a size of width 1200 mm × height 2400 mm × thickness 4 mm.
Two sheets of heat-resistant crystallized glass are prepared, a polycarbonate film with a thickness of 0.3 mm is arranged between them, and the three are bonded with an adhesive containing an ultraviolet curable resin mainly composed of an acrylic resin to obtain a laminated glass. It was. The adhesive layer was two layers, and the thickness of one layer was 0.2 mm. In the adhesive, as a regulator, C.I. which is a β crystal of copper phthalocyanine which is a blue pigment. I. Pigment Blue 15: 3 is added by 0.5% by weight. As a result, the color tone of the laminated glass was such that x of the reflected light was in the range of 0.300 to 0.317 in the xyY display system of the CIE chromatogram.

<Image Confirmation Test 1>
An observer was placed at a location 1 m away from one glass surface of the laminated glass, and a fluorescent lamp was installed at a location 1 m away from the other glass surface of the laminated glass. The observer confirmed the image of the fluorescent lamp through the laminated glass. The fluorescent lamp viewed through the laminated glass did not show a large difference in color tone as compared with the direct fluorescent lamp. Furthermore, the observer confirmed the reflection of the fluorescent lamp on the laminated glass from substantially the same position as the fluorescent lamp. As a result, almost no reflection of the fluorescent lamp on the laminated glass was confirmed.

<Example 2>
The same heat-resistant crystallized glass as in Example 1 was used. Two sheets of heat-resistant crystallized glass are prepared, a polycarbonate film with a thickness of 0.3 mm is arranged between them, and the three are bonded with an adhesive containing an ultraviolet curable resin mainly composed of an acrylic resin to obtain a laminated glass. It was. The adhesive layer was two layers, and the thickness of one layer was 0.2 mm. In the adhesive, as a regulator, C.I. I. Pigment Blue 15: 3 having improved dispersibility I. Pigment Blue 15: 4 is added at 1.0% by weight. As a result, the color tone of the laminated glass was such that x of the reflected light was in the range of 0.300 to 0.317 in the xyY display system of the CIE chromatogram.

<Image confirmation test 2>
An observer was placed at a location 1 m away from one glass surface of the laminated glass, and a fluorescent lamp was installed at a location 1 m away from the other glass surface of the laminated glass. The observer confirmed the image of the fluorescent lamp through the laminated glass. The fluorescent lamp viewed through the laminated glass did not show a large difference in color tone as compared with the direct fluorescent lamp. Furthermore, the observer confirmed the reflection of the fluorescent lamp on the laminated glass from substantially the same position as the fluorescent lamp. As a result, almost no reflection of the fluorescent lamp on the laminated glass was confirmed.

<Example 3>
The same heat-resistant crystallized glass as in Example 1 was used. Two sheets of heat-resistant crystallized glass are prepared, a polycarbonate film with a thickness of 0.3 mm is arranged between them, and the three are bonded with an adhesive containing an ultraviolet curable resin mainly composed of an acrylic resin to obtain a laminated glass. It was. The adhesive layer was two layers, and the thickness of one layer was 0.2 mm. The polycarbonate film has a blue pigment C.I. I. Pigment Blue 15: 4 is added at 1.0% by weight. As a result, the color tone of the laminated glass was such that x of the reflected light was in the range of 0.300 to 0.317 in the xyY display system of the CIE chromatogram.

<Image confirmation test 3>
An observer was placed at a location 1 m away from one glass surface of the laminated glass, and a fluorescent lamp was installed at a location 1 m away from the other glass surface of the laminated glass. The observer confirmed the image of the fluorescent lamp through the laminated glass. The fluorescent lamp viewed through the laminated glass did not show a large difference in color tone as compared with the direct fluorescent lamp. Furthermore, the observer confirmed the reflection of the fluorescent lamp on the laminated glass from substantially the same position as the fluorescent lamp. As a result, almost no reflection of the fluorescent lamp on the laminated glass was confirmed.

<Example 4>
The same heat-resistant crystallized glass as in Example 1 was used as the heat-resistant crystallized glass. A thickness comprising a copolymer (THV) of 40% by weight of tetrafluoroethylene (TFE), 20% by weight of hexafluoropropylene (HEP) and 40% by weight of vinylidene fluoride (VBF) between the two heat-resistant crystallized glasses. A 0.5 mm resin film was placed and bonded by thermocompression bonding to obtain a laminated glass. The THV film has a blue pigment C.I. I. Pigment Blue 15: 4 is added at 1.0% by weight. As a result, the color tone of the laminated glass was such that x of the reflected light was in the range of 0.300 to 0.317 in the xyY display system of the CIE chromatogram.

<Image confirmation test 4>
An observer was placed at a location 1 m away from one glass surface of the laminated glass, and a fluorescent lamp was installed at a location 1 m away from the other glass surface of the laminated glass. The observer confirmed the image of the fluorescent lamp through the laminated glass. The fluorescent lamp viewed through the laminated glass did not show a large difference in color tone as compared with the direct fluorescent lamp. Furthermore, the observer confirmed the reflection of the fluorescent lamp on the laminated glass from substantially the same position as the fluorescent lamp. As a result, almost no reflection of the fluorescent lamp on the laminated glass was confirmed.

  The laminated glass according to the present invention and the fire prevention equipment provided with the laminated glass are used for fire prevention safety glass and fire prevention in commercial facilities such as department stores, supermarkets, city halls, hospitals, public facilities such as station buildings, and private facilities such as large office buildings. It can be used as equipment.

10 (10a, 10b) Glass plate 11 Resin film 12 Adhesive layer 20 Frame body 21 Groove part 22 Ceramic fiber blanket 23 Fireproof silicone 100,200 Laminated glass 300 Fireproof equipment

Claims (8)

A laminated glass in which a plurality of glass plates including at least one heat-resistant plate glass composed of crystallized glass are bonded with an adhesive via a resin film,
Laminated glass in which an adjusting agent for adjusting the color tone of the glass plate is contained in at least one of the resin film and the adhesive. The average linear expansion coefficient of the crystallized glass is in the temperature range of 30-750 ° C., laminated glass according to claim 1 which is -10~10 × ^{10 -7} / K.   The resin film is selected from the group consisting of tetrafluoroethylene (TFE) -hexafluoropropylene (HFP) -vinylidene fluoride (VDF) copolymer (THV), polycarbonate (PC), and polyethylene terephthalate (PET). The laminated glass according to claim 1, wherein the laminated glass is at least one.   The laminated glass according to any one of claims 1 to 3, wherein the adhesive is a photocurable adhesive mainly composed of an ultraviolet curable resin. Between a plurality of glass plates containing at least one heat-resistant plate glass composed of crystallized glass, a laminated glass that is heat-sealed by sandwiching a resin film,
Laminated glass in which an adjusting agent for adjusting the color tone of the glass plate is contained in the resin film.   The laminated glass according to claim 5, wherein the resin film is tetrafluoroethylene (TFE) -hexafluoropropylene (HFP) -vinylidene fluoride (VDF) copolymer (THV).   The regulator is at least one blue pigment selected from the group consisting of aluminum-cobalt oxide, aluminum-zinc-cobalt oxide, silicon-cobalt oxide, silicon-zinc-cobalt oxide, and phthalocyanine compounds. The laminated glass according to any one of claims 1 to 6. The laminated glass according to any one of claims 1 to 7,
A frame for fitting the laminated glass;
With
The frame body is provided with a groove portion for receiving the peripheral edge portion of the laminated glass, and in a state where the laminated glass is fitted into the frame body, a gap generated between the peripheral edge portion of the laminated glass and the groove portion is heat-resistant. Fireproofing equipment sealed with a conductive material.