JP6421592B2 - Fire door - Google Patents

Description

  The present invention relates to a fire door including a low radiation glass having a low radiation film formed on a surface thereof and a resin member.

  Fire doors are one of the building materials that have flame barrier performance to prevent the spread of fire in the event of a fire. For example, fire shutters, iron doors, windows using heat-resistant glass and meshed glass, and fire-treated wooden doors Etc. are used. The fire doors are divided into specific fire prevention facilities and fire prevention facilities according to the flame shielding performance. Fire prevention equipment refers to equipment that meets the standard value of the flame-proof performance test for judging whether or not to spread to the non-heated side when heated for 20 minutes so that the standard heating temperature curve specified in ISO 834 is achieved. The specific fire prevention equipment refers to equipment that prevents the spread of fire to the non-heated side for 60 minutes when the same test as the above fire prevention equipment is performed. Of the above fire doors, fire prevention equipment is often used on the outer walls of buildings to prevent the spread of fire from adjacent buildings, and does not burn or melt due to fire for a predetermined time and has a certain sealing property Things are required.

  In recent years, for the purpose of improving the cooling and heating efficiency, in a multi-layer glass laminated so as to form a hollow layer between two glass plates via a spacer, a low-radiation laminated film (hereinafter referred to as a glass layer) on the hollow layer side of the glass plate. Window glass using low emission glass on which a low emission film is sometimes formed) is becoming widespread.

  This low-emission glass incorporates visible light into the room and meets the daylighting requirements of window glass, while the low-emission film reflects light from the near-infrared region to the infrared region. Temperature rise can be suppressed. Moreover, in order to interrupt | block the transmission of the heat | fever from the room | chamber interior, the capability to heat-insulate and insulate a room | chamber interior is also high.

  Since glass with low emissivity can suppress the transmission of radiant heat due to fire to the non-fire side during a fire, it is also considered as a fire door. For example, Patent Document 1 discloses a glass on which a transparent film mainly composed of tin oxide or indium oxide having a low emissivity is formed. Patent Document 2 discloses a fireproof glass using an indium oxide film containing tin.

In recent years, low emission glass using Ag is becoming widespread. Since Ag is likely to be deteriorated by heat, moisture in the atmosphere, oxygen, halogen, sulfur, etc., for example, as in Patent Document 3, a low emission film in which an Ag protective film is formed on an Ag film has been studied. . In Patent Document 3, for example, SnO ₂ / ZnO / Ag / optional block layer / SnO ₂ / ZnSnO: Al or Sb, or SnO ₂ / ZnO / Ag / optional block layer / SnO ₂ / SiO ₂ / A low-emission film imparted with chemical durability against moisture and hydrochloric acid by forming a laminate characterized by the order of SnO ₂ / ZnSnO: Al or Sb is disclosed. In this document, the crystal structure of the ZnSnO layer is made dense by adding Al or Sb, and the above-mentioned chemical durability is imparted.

  Further, as described above, Ag is likely to be deteriorated by heat, and in the case of a low emission glass using Ag, Ag aggregation occurs due to heat at the time of fire, which may impair the low emission performance of the low emission film. . If the low radiation performance is impaired, there is a possibility that the expected fire resistance as described above may be lost.

  The deterioration of Ag due to heat is well known. For example, in Patent Document 4, in order to improve heat resistance, a silicon nitride film is formed on the outermost surface of a low-emission film including an Ag film, and the silicon nitride film is directly under the silicon nitride film. A low emission film in which an oxide dielectric film is formed is disclosed. In this document, it is possible to suppress deterioration when heat treatment is performed at 620 ° C. for 8 minutes.

JP-A-8-40747 JP 2002-308650 A JP-T-2002-528372 Special Table 2007-527328

J. Szczyrbowski, G. BraEuer, M. Ruske, H. Schilling, A. Zmelty, Thin Solid Films 351 (1999) 254-259

  As described above, although there is a concern about deterioration of Ag due to heat, it is expected that the low emission glass can be used for a fire door by applying a technique for improving the heat resistance of the low emission glass using Ag. . However, on the other hand, the window glass is sealed with a resin sealing material, a resin spacer or resin sash is attached to the periphery, and a resin sheet is affixed to the glass surface. Incorporated into. The resin member as described above has no problem in daily use. However, when the periphery of the opening becomes high due to a fire or the like, a reactive gas may be generated. When reaching the film, the low-emission film may be deteriorated.

  As a result of investigations by the present inventors, even a low radiation film excellent in chemical durability to a reactive gas at a temperature near room temperature or a low radiation film having sufficient heat resistance can be used in a high temperature environment. When the surface of the low radiation film is exposed to the reactive gas generated from the resin member, the low radiation film is eroded and changes in appearance as white turbidity of the film surface or discoloration of the film itself, and the low radiation performance is greatly impaired. It was newly found that there is a case.

  Accordingly, an object of the present invention is to obtain a fire door using low radiation glass that suppresses erosion of the low radiation film by a reactive gas in a high temperature environment.

  As a result of further studies on the above-mentioned problems, a reactive gas containing halogen or sulfur is generated from the resin member of the fire door placed in a high temperature environment, and the halogen or sulfur contained in the reactive gas It was found that the low-emission film deteriorates significantly. In the above deterioration, the reactive gas corrodes the film formed on the outermost surface and deteriorates from the surface of the low emission film, and the film inside the low emission film passes through the film formed on the outermost surface. In either case, it was found that the low radiation film deteriorates within a few minutes from the time of exposure to gas in a high temperature environment, and the low radiation performance deteriorates.

That is, the present invention provides a first layer composed of a dielectric from the glass substrate side, a second layer composed of a metal mainly composed of Ag, and a third composed of a dielectric on the glass substrate. A layer, a fourth layer composed of a metal mainly composed of Ag, and a fifth layer composed of a dielectric, a low radiation glass having a low radiation film laminated in this order, and halogen or sulfur. In a fire door provided with a resin member containing,
The third layer includes a mixed oxide film of Zn and Sn having a Sn content of 15 to 80 wt% with respect to the total amount of Zn, and the thickness of the mixed oxide film is 40 to 120 nm,
The fifth layer includes two or more dielectric films, a mixed oxide film of Zn and Sn, and a TiO ₂ film on the surface of the mixed oxide film, and the TiO ₂ film includes the glass substrate. It is a film farthest away from the material, and the mixed oxide film is a fire door characterized in that the content of Sn is 15 to 80 wt% with respect to the total amount of Zn.

  Since the “resin member” is often a frame material such as a resin sash, and low emission glass is often incorporated into a double-layer glass, a double-layer glass resin spacer, a resin seal material, etc. may be mentioned. .

  The sash and spacer are members used when glass is incorporated into a window frame, and are provided on the periphery of the glass. Conventionally, aluminum with high thermal conductivity has been used for sashes and spacers, but in recent years, resins and resin composites with low thermal conductivity, aluminum / resin composites, etc. are made of aluminum in order to improve heat insulation. It is being used as an alternative material. Examples of the resin to be used include a resin mainly composed of vinyl chloride to which a phthalic acid compound or a phosphoric acid compound is added as a plasticizer and a metal organic acid compound is added as a stabilizer.

  Moreover, resin is conventionally used for the sealing material of multilayer glass, and polysulfide resin, silicone resin, polyisobutylene resin, etc. are mentioned as resin used.

  The second layer and the fourth layer are metal films containing Ag as a main component, and are Ag films or Ag alloy films containing Ag as a main component. The Ag alloy may contain a metal such as Pd, Au, Pt, Ni and Cu within a range of 5% by mass or less. Here, “main component” refers to a substance containing 90% by mass or more of Ag.

  The first layer, the third layer, and the fifth layer are made of a dielectric. The layer adjusts the optical characteristics of the low-emission film such as reflection and transmission. In particular, the metal film plays a role of protecting the metal film, and is made of Zn, Sn, Al, Ti, Si, and In. It is preferable to use a transparent thin film of an oxide, nitride, or oxynitride containing at least one metal selected from the group consisting of:

  Here, “fireproof” in the present specification is a characteristic evaluated by the flameproof performance as the opening as described above. The flameproof performance test is not a single glass but a test that is assembled as a window, and the quality of the glass, such as meshed glass and heat-resistant tempered glass, which constitutes the double-glazed glass together with the low radiation glass, and spacer Since various factors such as the type of the multi-layer glass constituent member such as the sealing material and the end face state of the glass base material are affected, the durability of the low emission film to the reactive gas cannot be determined directly. Therefore, in this study, the low emission glass was exposed to a reactive gas caused by the resin member at a temperature similar to that during the flame shielding performance test, and changes in the appearance of the low emission film were observed.

  In the 20-minute flameproof performance test, the ultimate temperature of the low emission glass is about 250 to 450 ° C. It is presumed that the reactive gas generated from the resin member deteriorates the low radiation film in the temperature range or in the process until reaching the temperature range. Therefore, using a sample in which the performance of the low radiation film was maintained even after the 20-minute flame-shielding performance test, the environment for simulating the flame-shielding performance test was examined. However, when the holding time was further extended, the appearance of the low-emission film changed to appear cloudy, and the sheet resistance increased and the heat ray reflection performance decreased. all right.

  Therefore, in the present invention, a test sample and a sample obtained by pulverizing vinyl chloride resin are placed on a hot plate heated to 300 ° C., covered with a stainless steel lid, and held for 5 minutes, and then the sheet resistance is 20 Ω / sq. The following were judged to be fireproof.

In addition, the mixed oxide film of Zn and Sn is not necessarily a film in which the ratio of Zn: Sn: O is 1: 1: 1, and may be referred to as Zn _x Sn _y O _z hereinafter ( x, y and z are integers of 1 or more). In general, when a Zn _x Sn _y O _z film is formed by a sputtering method at room temperature, which is a general method for producing a low-emission film, it has a different structure depending on the ratio of Zn and Sn. In the study by the present inventors, when the Sn content is less than about 15 wt% with respect to the total amount with Zn, a crystal structure derived from zinc oxide is shown, but when the Sn content is 15 wt% or more, It was found that most of them showed an amorphous structure, and a dense film without a clear grain boundary was obtained.

  In this specification, “amorphous” is measured by X-ray diffraction using CuKα rays using an X-ray diffractometer (Rint-ultima III, manufactured by Rigaku Corporation) as in Reference Examples described later. And a film in which no clear peak is observed in the obtained diffraction pattern.

  According to the present invention, it is possible to obtain a fire door using low radiation glass that has heat resistance and suppresses erosion of the low radiation film by a reactive gas in a high temperature environment.

It is a cross-sectional schematic diagram showing one Embodiment of the low radiation film | membrane used for this invention. It is a cross-sectional schematic diagram showing one Embodiment of the fire door of this invention. 4 is an X-ray diffraction spectrum of a Zn _x Sn _y O _z film obtained in Reference Examples 1 to 4. FIG.

As described above, when a fire door including a resin member is placed in a high temperature environment, a reactive gas containing halogen or sulfur is generated, and the low radiation film is significantly deteriorated. In order to suppress the deterioration of the low emission film due to the reactive gas, a layer formed on the uppermost surface of the low emission film (hereinafter sometimes referred to as “the outermost layer”) above the metal film, Suppresses corrosion caused by reactive gas (hereinafter sometimes referred to as “corrosion resistance”) and suppresses penetration of reactive gas into the interior (hereinafter sometimes referred to as “gas barrier”) Both membranes are essential. Incidentally, the corrosion by the reactive gas means that the film is deteriorated by being exposed to the reactive gas, and the penetration of the reactive gas into the inside means that the reactive gas permeates the film. . As a result of investigations by the present inventors, it is possible to suppress deterioration of the low radiation film by laminating a TiO ₂ film on a Zn _x Sn _y O _z film that is a mixed oxide film of Zn and Sn. I found out that Furthermore, as a result of further investigations, it becomes clear that the third layer has a great influence on the suppression of the deterioration, and the use of a Zn _x Sn _y O _z film for the third layer further deteriorates the low radiation film. It turned out that it became possible to suppress.

In addition, TiO ₂ film is conventionally used for Ag protective film and is known to have excellent chemical durability, so TiO ₂ film has the effect of inhibiting corrosion even under high temperature environment. Is estimated to be relatively high. In addition, when the Zn _x Sn _y O _z film is amorphous, no clear grain boundary is observed, so that it is presumed that the reactive gas hardly permeates in a high temperature environment. However, on the other hand, when the Zn _x Sn _y O _z film as described above is formed on the TiO ₂ film, or when only one of the above two types is used, fire resistance becomes insufficient. .

That is, the present invention provides a first layer composed of a dielectric from the glass substrate side, a second layer composed of a metal mainly composed of Ag, and a third composed of a dielectric on the glass substrate. A layer, a fourth layer composed of a metal mainly composed of Ag, and a fifth layer composed of a dielectric, a low radiation glass having a low radiation film laminated in this order, and halogen or sulfur. In a fire door provided with a resin member containing,
The third layer includes a mixed oxide film of Zn and Sn having a Sn content of 15 to 80 wt% with respect to the total amount of Zn, and the thickness of the mixed oxide film is 40 to 120 nm,
The fifth layer includes two or more dielectric films, a mixed oxide film of Zn and Sn, and a TiO ₂ film on the surface of the mixed oxide film, and the TiO ₂ film includes the glass substrate. It is a film farthest away from the material, and the mixed oxide film is a fire door characterized in that the content of Sn is 15 to 80 wt% with respect to the total amount of Zn.

  Although the glass substrate used in the present invention is not particularly limited, for example, a commonly used float plate glass or an inorganic transparent glass plate such as soda lime glass produced by a roll-out method is used. it can. Examples of the glass substrate include non-alkali glass and highly transmissive glass. Moreover, the shape of the glass substrate is not particularly limited, and various tempered glasses such as flat glass, bent plate glass, air-cooled tempered glass, and chemically tempered glass, and netted glass can also be used. Various glass substrates such as borosilicate glass, low expansion glass, zero expansion glass, low expansion crystallized glass, and zero expansion crystallized glass can be used.

  The second layer and the fourth layer are metal films containing Ag as a main component, and are Ag films or Ag alloy films containing Ag as a main component. The Ag alloy may contain a metal such as Pd, Au, Pt, Ni and Cu within a range of 5% by mass or less. Here, “main component” refers to a substance containing 90% by mass or more of Ag.

  Moreover, it is preferable to form a sacrificial layer on the surface of each metal film for the purpose of preventing the Ag of the metal film from deteriorating during the formation process. The sacrificial layer can protect Ag from the gas and plasma derived from the gas when the dielectric film is formed above the metal film in an atmosphere containing an oxidizing gas or the like. As the sacrificial layer, Zn, Sn, Ti, Al, NiCr, Cr, Zn alloy, Sn alloy and the like are preferable. In addition, it is preferable to use a sacrificial layer that is transparent by being oxidized or nitrided by the above gas when forming the dielectric film, since the visible light transmittance is not impaired more than necessary. Since the sacrificial layer only needs to prevent the metal film directly under the film from being deteriorated or denatured during film formation, the physical film thickness should be 1 nm or more, preferably 2 nm or more. On the other hand, when the thickness exceeds 4 nm, oxidation or nitridation with a reactive gas tends to be insufficient.

  The first layer, the third layer, and the fifth layer are made of a dielectric. The layer is a film that adjusts the optical characteristics of the low-emission film such as reflection and transmission, and plays a role of protecting the metal film, particularly when formed on the metal film, and includes Zn, Sn, Al, Ti, It is preferable to use a transparent thin film of oxide, nitride, or oxynitride containing at least one metal selected from the group consisting of Si and In.

As shown in FIG. 1, the third layer 8 is a layer made of a dielectric, and preferably has two or more dielectric films. The total thickness of the third layer 8 is preferably 70 to 125 nm. One of the dielectric films constituting the third layer 8 is a mixed oxide film of Zn and Sn (Zn _x Sn _y O _z ) whose Sn content is 15 to 80 wt% with respect to the total amount of Zn. 6), and the Zn _x Sn _y O _z film 6 can suppress the permeation of the reactive gas.

The film thickness of the Zn _x Sn _y O _z film 6 is 40 to 120 nm. If it is less than 40 nm, improvement in fireproof performance tends to be insufficient. Further, even if the film is formed to exceed 120 nm, the fireproof performance is not always improved in proportion to the film thickness, which is not preferable for production. Further, the film thickness is preferably 50 to 100 nm. The third layer 8 preferably uses another dielectric film 2 ′ in addition to the Zn _x Sn _y O _z film 6. Of the dielectric film 2 ′, the film formed immediately below the fourth metal film 3 is a film having a crystalline zinc oxide structure for improving the crystallinity of Ag contained in the metal film 3. Is preferably arranged.

In the third layer 8, examples of the dielectric film 2 ′ used in addition to the Zn _x Sn _y O _z film include an Al-doped ZnO film, a SnO ₂ film, and a Si ₃ N ₄ film. As described above, when the fourth layer is formed on the surface of the Zn _x Sn _y O _z film 6, Ag crystallinity is deteriorated and optical characteristics are deteriorated. Therefore, the Zn _x Sn _y O _z film 6 and the fourth layer It is desirable to form a dielectric film 2 'having a crystalline zinc oxide structure such as an Al-doped ZnO film therebetween. The thickness of the dielectric film 2 'is not particularly limited. However, for example, by setting the thickness to 10 nm or more, it is preferable because the crystallinity of the Ag film formed thereon can be improved.

  The fifth layer is a layer formed on the fourth layer and has two or more dielectric films. The fifth layer is a layer that suppresses the deterioration of the second layer and the fourth layer by the reactive gas, and the total film thickness is not particularly limited as long as the optical characteristics of the low emission film are not impaired. However, it is good also as 15-50 nm, for example.

Further, the fifth layer has three or more dielectric films, a SnO ₂ film, a mixed oxide film of Zn and Sn on the surface of the SnO ₂ film, and a TiO ₂ film on the surface of the mixed oxide film. It is preferable that the TiO ₂ film is a film farthest away from the glass substrate. It was found that fire resistance is further improved by forming the SnO ₂ film between the fourth layer and the Zn _x Sn _y O _z film that is a mixed oxide film of Zn and Sn. Further, it was also found that the fireproof performance is lowered when the order of stacking is changed, for example, Zn _x Sn _y O _z film, SnO ₂ film, TiO ₂ film. Therefore, when using the SnO ₂ film for the fifth layer, it is desirable to use it under the Zn _x Sn _y O _z film.

For example, as shown in FIG. 1, the fifth layer 4 is formed by laminating the SnO ₂ film 5, the Zn _x Sn _y O _z film 6, and the TiO ₂ film 7 in this order, and the TiO ₂ film. 7 is the film farthest from the glass substrate 1. In addition, the low emission film used in the present invention has a metal film 3 mainly composed of Ag under the fifth layer 4, and an arbitrary dielectric film or metal film is provided between the metal film 3 and the metal film 3. You may do it.

The SnO ₂ film 5 is a film that suppresses corrosion by reactive gas, and may contain C, N, etc. for the purpose of stress relaxation. The film thickness of the SnO ₂ film 5 is preferably 5 to ₂₀ nm. Less than 5 nm is less effective. Moreover, although it may exceed 20 nm, as a result, the thickness of the entire fifth layer increases, and there is a possibility of affecting the color of the appearance, so in the present invention, it is preferably 20 nm or less. It is.

The Zn _x Sn _y O _z film 6 has a Sn content of 15 to 80 wt% with respect to the total amount of Zn. When it is less than 15 wt%, the Zn _x Sn _y O _z film has a crystal structure derived from zinc oxide, and thus has a gas barrier property inferior to that of an amorphous film. On the other hand, when it exceeds 80 wt%, a structure similar to tin oxide is obtained. Therefore, although it has an amorphous structure, there is a clear grain boundary, and the gas barrier property is also lowered. Preferably it is good also as 20-70 wt%. The Zn _x Sn _y O _z film 5 preferably has a thickness of 6 to 40 nm. In terms of improving the gas barrier performance, if it is less than 6 nm, it tends to be insufficient, and if it exceeds 40 nm, the thickness of the entire fifth layer increases as a result, which may affect the appearance color and the like. Therefore, in the present invention, the thickness is preferably 40 nm or less. More preferably, it may be 10 to 30 nm.

The TiO ₂ film 7 is a film that is located farthest from the glass substrate 1 and is a film having corrosion resistance. For the purpose of stress relaxation and the like, C, N and the like may be contained. The film thickness of the TiO ₂ film 7 is preferably 3 to 10 nm. If the thickness is less than 3 nm, the corrosion resistance tends to be insufficient, and the TiO ₂ film has a lower deposition rate than the SnO ₂ film or the Zn _x Sn _y O _z film. there is a possibility.

  If a resin sash is used as the resin member, the proportion of the resin in the volume of the entire fire door increases, and the amount of reactive gas generated increases. Further, when a resin is used for the spacer, a reactive gas is generated on the surface in contact with the low radiation film. The low emission glass of the present invention can be used particularly effectively when a resin sash or a resin spacer is used. That is, it is preferable that the resin member is a resin sash or a resin spacer.

  The fire door is a member attached to the opening, and includes at least a glass substrate, a low radiation film, and a sash frame. Moreover, when using as a multilayer glass, a spacer and a sealing material are included above. An example of the fire door will be described below with reference to FIG. FIG. 2 shows a multilayer glass using a low emission glass, but is not limited to this.

  That is, according to one preferred embodiment of the present invention, the fire door includes the low emission glass and a glass substrate disposed through at least a spacer, the low emission glass, the glass substrate, and the spacer. Each of which has a multilayer glass having an adhesive interposed therebetween and a sealing material for sealing the multilayer glass, and the multilayer glass is in contact with the sash frame of the opening through the resin material. It is a fire door characterized by being.

  The double-glazed glass is one in which two glass substrates 1 are used and arranged through a spacer 11 so as to form a hollow layer 10. At this time, the low radiation film 9 is installed so as to face the hollow layer 10 in order to suppress damage. The spacer 11 is at the peripheral edge of the glass substrate 1, and a primary sealing material 13 is interposed as an adhesive between the spacer 11 and the glass substrate 1. A secondary sealing material 14 is embedded in the peripheral portion of the glass substrate 1 in order to seal the hollow layer 10.

  The spacer 11 has a desiccant 12 inside, and is fixed to the peripheral portion of the glass substrate by the primary sealant 13 as described above. The spacer 11 is widely made of aluminum, but may be made of resin as described above. The primary sealing material 13 is for bonding the glass substrate 1 and the spacer 11, and polyisobutylene resin or the like is used. The secondary sealing material 14 is a sealing material, and a polysulfide resin, a silicone resin, or the like is used.

  When the multilayer glass is installed in an opening of a building, a member such as a sash is provided on the periphery in order to incorporate the multilayer glass into a window frame. A simple sash frame is shown in FIG. 2, and the surface of the glass substrate 1 is in contact with the sash frame 17 through the backup material 15. Further, the glass substrate 1 and the secondary sealing material 14 are in contact with the sash frame 17 via the setting block 16.

  The backup material 15 is a resin material provided between the glass base material 1 and the sash frame 17 and fixes the glass base material 1. As the backup material 15, polyethylene foam, foamed rubber or the like is used. The setting block 16 is provided inside the sash frame 17 and supports the weight of the glass substrate 1. As the setting block 16, chloroprene rubber, EPDM (ethylene propylene diene rubber), silicone, vinyl chloride resin or the like is used.

  One of the preferred embodiments of the present invention is a low radiation film, wherein the first layer is formed by laminating two or more dielectric films, and the third layer is composed of six or more dielectric films, One layer and the third layer are fire doors in which different dielectric films are in contact with each other.

  In this embodiment, by increasing the number of laminated dielectric films constituting the first layer and the third layer, a plurality of interfaces of the dielectric films are present to further suppress the permeation of the reactive gas. Therefore, it is preferable that different dielectric films are in contact with each other at the interface of the laminated film.

The phrase “different dielectric films are in contact with each other” means that the films in contact with each other have different components or different component ratios. For example, when a third component is included in the film, such as a ZnO film containing 3 wt% of Al, the difference between the film containing the third component and the film not containing is only the content of the third component. If there is no change in the above, it is excluded from the above-mentioned configuration where “different dielectrics are in contact with each other”. In addition, for example, when films having different Sn contents in a Zn _x Sn _y O _z film are in contact with each other, if there is no change in physical properties or the like due to only the content ratio of the components, the above-mentioned “different dielectrics are in contact with each other” "Is excluded from the configuration.

  The method for forming the low emission film of the present invention will be described below. The low emission film is preferably formed by a sputtering method, an electron beam vapor deposition method, an ion plating method, or the like, but the sputtering method is suitable because it is easy to ensure productivity and uniformity.

  The formation of the low radiation film by the sputtering method is performed while the transparent substrate is transported in the apparatus in which the sputtering target as the material of each layer is installed. At this time, a gas used for sputtering is introduced into a vacuum chamber for film formation provided in the apparatus, and a negative potential is applied to the target to generate plasma in the apparatus to perform sputtering. .

  In addition, a method for obtaining a desired film thickness is not particularly limited because it varies depending on the type of the sputtering apparatus, but a method for controlling the film thickness by changing the film formation rate by adjusting the power input to the target or the introduction gas condition, A method of controlling the film thickness by adjusting the substrate conveyance speed is widely used.

When forming the dielectric film, the target to be used may be either a ceramic target or a metal target. In any case, the gas conditions to be used are not particularly limited, and the gas type and the mixing ratio may be appropriately determined from Ar gas, O ₂ gas, and N ₂ gas according to the target film. Further, as the gas to be introduced into the vacuum chamber, Ar gas, O ₂ gas, may include any third component other than N ₂ gas.

  In the case of forming a metal film containing Ag as a main component, an Ag target or an Ag alloy target is used as a target to be used. Ar gas is preferably used as the gas introduced at this time, but different types of gases may be mixed as long as the optical properties of the Ag film are not impaired.

  The plasma generation source may be a DC power supply, an AC power supply, or a power supply in which AC and DC are superimposed, but if abnormal discharge is likely to occur when forming a dielectric film, use an AC power supply or a DC power supply. It is preferable to use a power supply to which a pulse is applied.

1. Study of Zn _x Sn _y O _z Film First, the Sn content of the Zn _x Sn _y O _z film used in Examples and Comparative Examples was examined. The glass substrate was held by a substrate holder, and an alloy target in which Zn and Sn were mixed at a predetermined ratio was placed in a vacuum chamber. The Sn content of the alloy target was 9 wt% (Reference Example 1), 12 wt% (Reference Example 2), 24 wt% (Reference Example 3), and 65 wt% (Reference Example 4). The alloy target has a magnet disposed on the back side. Next, the inside of the vacuum chamber was evacuated by a vacuum pump. The atmosphere gas in the vacuum chamber was introduced with oxygen gas at 10 sccm, the pressure was adjusted to 0.5 Pa, and 100 W power was applied from the DC power source through the power cable to obtain a Zn _x Sn _y O _z film of 30 nm each. It was.

The obtained Reference Examples 1 to 4 were measured by X-ray diffraction using CuKα rays using an X-ray diffractometer (Rint-ultima III, manufactured by Rigaku Corporation). The obtained spectrum is shown in FIG. From FIG. 3, it was found that Reference Examples 1 and 2 were derived from the (002) plane of ZnO and had a peak in the vicinity of 33 to 34 °, and Reference Examples 3 and 4 were amorphous. Therefore, in the examples and comparative examples, a Zn _x Sn _y O _z film containing 50 wt% Sn is used as an amorphous Zn _x Sn _y O _z film, and a Zn _x Sn _y O _z film containing 10 wt% Sn is used. It was decided to use it as a crystalline Zn _x Sn _y O _z film.

2. Production of Low Emission Film Examples and comparative examples of the present invention are shown below. Table 1 shows the film thicknesses of the dielectric films and the metal films of Examples 1 to 4 and Comparative Examples 1 to 6. In both Examples and Comparative Examples, a film was formed on soda lime glass having a thickness of 3 mm using a magnetron sputtering apparatus. Each film obtained the film thickness described in Table 1 by adjusting the conveyance speed of a glass substrate. Moreover, the said conveyance speed used the speed | rate calculated for every kind of film | membrane previously forming the single layer film | membrane. In any of the examples and comparative examples, a sacrificial layer (not shown in Table 1) is formed on the second layer and the fourth layer, and the step of heating the base material and the film is not performed. Except for the case where the substrate temperature rose due to the above, the substrate and the film were not heated.

Example 1
First, a glass substrate was held on a substrate holder, and a desired target was placed in a vacuum chamber. The target has a magnet disposed on the back side. Next, the inside of the vacuum chamber was evacuated by a vacuum pump. The sacrificial layer is formed by Zn and Al alloy target with 4 wt% Al added to the target, argon gas is introduced at 100 sccm as the atmospheric gas in the vacuum chamber, and the pressure is adjusted to 0.6 Pa. It was. The power supplied from the DC power source was 200W.

(First layer)
A Zn _x Sn _y O _z film was formed on a glass substrate. An alloy target of Zn and Sn added with 50 wt% of Sn was used as a target, and 1100 W of power was supplied from a DC power source through a power cable. At this time, while continuously operating the vacuum pump, oxygen gas was introduced into the vacuum chamber at 60 sccm and the pressure was adjusted to 0.3 Pa.

Next, an AZO film was formed on the Zn _x Sn _y O _z film. The target was an alloy target of Zn and Al to which 2 wt% of Al was added, oxygen gas was introduced at 60 sccm as the atmospheric gas in the vacuum chamber, and the pressure was adjusted to 0.3 Pa. The power input from the DC power source was 2100W.

(Second layer)
An Ag film was formed on the AZO film. The target was an Ag target, and the atmosphere gas in the vacuum chamber was introduced as a mixed gas of argon gas 45 sccm and oxygen gas 2.5 sccm, and the pressure was adjusted to 0.3 Pa. The power supplied from the DC power source was 360 W.

(3rd layer)
A Zn _x Sn _y O _z film was formed on the second layer on which the sacrificial layer was formed. The film forming conditions were the same as those of the first Zn _x Sn _y O _z film except that the conveyance speed was adjusted to obtain a desired film thickness.

Next, an AZO film was formed on the Zn _x Sn _y O _z film. The film forming conditions were the same as those of the first AZO film except that the conveyance speed was adjusted to obtain a desired film thickness.

(Fourth layer)
An Ag film was formed on the AZO film. The film forming conditions were the same as those for the second Ag film except that the conveyance speed was adjusted to obtain a desired film thickness.

(5th layer)
An SnO ₂ film was formed on the fourth layer on which the sacrificial layer was formed. An Sn target was used as the target, and 1100 W of electric power was supplied from the DC power source through the power cable to the Sn target. At this time, while continuously operating the vacuum pump, oxygen gas was introduced into the vacuum chamber at 60 sccm and the pressure was adjusted to 0.3 Pa.

Next, a Zn _x Sn _y O _z film was formed on the SnO ₂ film. The film forming conditions were the same as those of the first Zn _x Sn _y O _z film except that the conveyance speed was adjusted to obtain a desired film thickness.

Next, TiO ₂ was formed on the Zn _x Sn _y O _z film. A Ti target was used as a target, and power of 3100 W was supplied from a DC power source to the Ti target through a power cable. At this time, while continuously operating the vacuum pump, oxygen gas was introduced into the vacuum chamber at 80 sccm and the pressure was adjusted to 0.4 Pa.

Examples 2 and 3
A low emission film was obtained in the same manner as in Example 1 except that the fifth layer was formed in the order as described in Table 1. In Example 2, no SnO ₂ film was formed, and a Zn _x Sn _y O _z film was formed on the fourth layer on which the sacrificial layer was formed.

Example 4
A low emission film was obtained in the same manner as in Example 1 except that the first layer was an AZO film.

Comparative Examples 1-3
A low emission film was obtained in the same manner as in Example 1 except that the fifth layer was formed in the order as described in Table 1.

Comparative Examples 4 and 5
A low radiation film was obtained in the same manner as in Example 4 except that the third layer was formed by adjusting the conveyance speed so as to have the film thickness shown in Table 1.

Comparative Example 6
In the formation of the Zn _x Sn _y O _z film, a low emission film was obtained in the same manner as in Example 4 except that a Zn and Sn alloy target in which Sn was added to the target at 10 wt% was used.

3. Evaluation of Low Radiation Film Tests simulating the flameproof performance test environment shown below for test samples in which the low radiation films of Examples 1 to 4 and Comparative Examples 1 to 6 were formed on a glass plate of 25 mm × 25 mm × 3 mm Carried out.

  First, the hot plate was heated to 300 ° C., and the test sample was placed thereon with the low radiation film surface facing up. Next, 1 g of the pulverized vinyl chloride resin was placed on a hot plate in the same manner as the test sample, and then a stainless steel lid was placed over the test sample and the vinyl chloride resin. The test sample was taken out when 5, 10, 15, 20 minutes passed after the cover was put on, and the sheet resistance value was measured. The sheet resistance value was measured using a 4-probe resistance measuring device (Resistest VIII, manufactured by Napson). Moreover, in order to verify higher fireproof performance, the heating temperature of the hot plate was set to 340 ° C. by the same method as described above, and evaluation was performed when 3, 4, 5, 7, and 10 minutes passed.

  ○ when the sheet resistance is 20Ω / sq or less on the entire surface of the sample, x when the entire surface of the sample is infinite or exceeds the upper limit of measurement, and there is an area where the sheet resistance can be measured on a part of the sample, and part of the sheet When there was a region where the resistance exceeded 20 Ω / sq, it was marked as Δ. When the sheet resistance is 20 Ω / sq or less, the emissivity is expected to be 0.23 or less (see Non-Patent Document 1), and therefore, it has an effect of suppressing the radiant heat due to the flame from being transmitted to the non-heating side as a low radiation film. it is conceivable that. The evaluation results are shown in Table 2.

Examples 1 to 4 and Comparative Examples 1 and 4 were found to exhibit high fire resistance in the above test at 300 ° C. On the other hand, Comparative Example 2 that did not use the Zn _x Sn _y O _z film for the fifth layer and Comparative Example 3 that did not use the TiO ₂ film for the outermost surface did not show fire resistance that could withstand the 300 ° C. test. . From the above, it has been found that by having a TiO ₂ film on the outermost surface of the low radiation film and a Zn _x Sn _y O _z film therebelow, excellent fire resistance is exhibited. In Comparative Example 5, the thickness of the third layer Zn _x Sn _y O _z film is thin. In Comparative Example 6, the amount of Sn contained in the Zn _x Sn _y O _z film is 10 wt%. Both were inferior in fire resistance.

In Comparative Example 1, in the test at 340 ° C., the film was completely deteriorated after 3 minutes. In other words, when the SnO ₂ film is interposed between the Zn _x Sn _y O _z film and the TiO ₂ film, it can be said that the durability is insufficient when used under more severe conditions. Moreover, also about the comparative example 4, when it was used on more severe conditions, it resulted in that durability was insufficient.

In addition, since Examples 1 and 4 are superior to Example 2 in the test at 340 ° C., by using the SnO ₂ film under the Zn _x Sn _y O _z film, further fire resistance can be achieved. It was found that improvement can be expected.

1 glass substrate 2, 2 'dielectric film 3 a metal film 4 fifth layer 5 SnO ₂ film 6 _Zn x _Sn y _{O z} layer 7 TiO ₂ film 8 third layer 9 low emissivity film 10 hollow layer 11 spacer 12 desiccant 13 Primary sealing material 14 Secondary sealing material 15 Backup material 16 Setting block 17 Sash frame

Claims (6)

On the glass substrate, the first layer composed of a dielectric from the glass substrate side, the second layer composed of a metal mainly composed of Ag, the third layer composed of a dielectric, mainly Ag A low radiation glass having a low radiation film in which a fourth layer composed of a metal as a component and a fifth layer composed of a dielectric are laminated in this order; and a resin member containing halogen or sulfur; In a fire door equipped with
The third layer includes a mixed oxide film of Zn and Sn having a Sn content of 15 to 80 wt% with respect to the total amount of Zn, and the thickness of the mixed oxide film is 40 to 120 nm,
The fifth layer includes two or more dielectric films, a mixed oxide film of Zn and Sn, and a TiO ₂ film on the surface of the mixed oxide film, and the TiO ₂ film includes the glass substrate. A fire door which is a film farthest on the side opposite to the material, and the mixed oxide film has a Sn content of 15 to 80 wt% with respect to the total amount of Zn. The fifth layer has three or more dielectric films, a SnO ₂ film, a mixed oxide film of Zn and Sn on the surface of the SnO ₂ film, and a TiO ₂ film on the surface of the mixed oxide film The fire door according to claim 1, wherein the TiO ₂ film is a film farthest away from the glass substrate. The fire door according to claim 1 or 2, wherein a thickness of the mixed oxide film of Zn and Sn in the fifth layer is 6 to 40 nm. The fire door according to any one of claims 1 to 3, wherein the resin member is a resin sash or a resin spacer. The first layer is a laminate of two or more dielectric films, and the third layer is a laminate of six or more dielectric films, and the first layer and the third layer are in contact with different dielectric films. The fire door according to any one of claims 1 to 4. A glass substrate in which the fire door is disposed with at least a spacer through the low emission glass, an adhesive interposed between the low emission glass and the glass substrate and the spacer, and the multilayer glass; A double-glazed glass having a sealing material for sealing
The fire door according to any one of claims 1 to 5, wherein the multi-layer glass is in contact with a sash frame of an opening through a resin material.

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