JP3078230U - Glass for freezing / refrigeration and glass articles using the glass - Google Patents

Abstract

(57) [Summary] [Problem] To maintain the internal confirmability without shaving off a part of the product and adhering to the glass window even if the product hits the surface of the glass window when taking out the product. Can be frozen
Provided is a refrigerator glass and a glass article using the glass. SOLUTION: A glass plate 1 is mainly composed of soda-lime glass manufactured by a float method. A tin oxide film (SnO) is formed on the surface of the glass plate 1 as an alkali elution preventing layer.
₂ film) 2 is formed, said the SnO ₂ film 2 of the surface silicon oxide film (SiO ₂ film) 3 is formed as ZoToruso, further on the surface of the SiO ₂ film 3 SnO ₂ as a low emissivity layer: F film 4
Is formed, and a glass frit film 30 is formed on the surface of the SnO ₂ : F film 4 as a protective film.

Description

[Detailed description of the invention]

[0001]

[Technical field to which the invention belongs]

 The present invention relates to a glass for freezing / refrigerator and a glass article using the glass, and more particularly, to a glass for freezing / refrigerating used as a glass window that allows the inside state to be seen from the outside while maintaining heat insulation. Also, the present invention relates to a glass article such as a double-glazed glass having improved heat insulating properties as a glass window by using at least one glass.

[0002]

[Prior art]

 Freezers and refrigerators used in stores such as supermarkets and convenience stores are required to have a product display function for displaying products and a product selection function for consumers to freely select products. Glass windows with an opening and closing mechanism that can ensure transparency while maintaining heat insulation are used. In addition, consumers can immediately judge the stock status of frozen and refrigerated showcases for ice cream and frozen foods, and merchandise that can be easily viewed by the purchaser and the store owner can easily put products in and out. Similarly to the above, a so-called see-through type vending machine has been proposed in which a glass window capable of ensuring transparency while maintaining heat insulation properties has been proposed.

[0003]

[Problems to be solved by the invention]

 However, the oxide semiconductor film formed of a tin oxide film or the like formed on the surface of the glass window has an uneven surface and hardness, so that, for example, when a consumer takes out a product from a refrigerator or a freezer, it is difficult to remove the product. When the product was applied to the surface of the glass window, a part of the product was scraped off by the surface of the tin oxide film and adhered to the surface of the tin oxide film of the glass window. As a result, the glass window looks as if it were scratched, and the image of the product may be reduced due to the scratched deposit.

[0004] For example, in a glass for an ice cream showcase, when a basket containing ice cream hits the glass, the resin that protects the basket is peeled off, and the iron inside is exposed, and the iron is oxidized on the glass. In some cases, the tin film is scraped off and adheres to the surface and looks black.

The present invention has been made in view of such a problem, and even if a product hits the surface of a glass window at the time of taking out the product, a part of the product is cut off and adheres to the glass window. It is an object of the present invention to provide a refrigerator / refrigerator glass capable of maintaining the internal confirmation without performing the process and a glass article using the glass.

[0006]

[Means for Solving the Problems]

 As a result of intensive studies to achieve the above object, the present inventor has found that an intermediate layer including a first tin oxide film and a silicon oxide film formed on the surface of a glass plate facing the inside of a refrigerator / refrigerator; A low-emission layer including a second tin oxide film formed on a silicon oxide film is formed in this order on the oxide semiconductor film, which is covered with a glass frit film. It was found that even if the product hits the surface of the glass window, a part of the product would not be cut off and adhered to the glass window, and the internal confirmation could be maintained.

Therefore, the glass for freezing / refrigerator according to the present invention is a glass for freezing / refrigerating, which separates the first space at room temperature from the second space at lower temperature than room temperature. An intermediate layer including a first tin oxide film and a silicon oxide film sequentially formed on the surface of the glass on the space side, and a low emission layer including a second tin oxide film formed on the silicon oxide film. And a glass frit film coated on the oxide semiconductor film.

According to the above configuration, the following effects can be obtained.

By coating a glass frit film on an oxide semiconductor film, even if the product hits the surface of the oxide semiconductor film at the time of taking out the product, a part of the product is cut off and the surface of the oxide semiconductor film is removed. Because it does not adhere to the product, it is possible to maintain the internal confirmation of the refrigerator / freezer without lowering the product image.

[0010] The glass frit film covers the entire surface of the oxide semiconductor film, so that the oxide semiconductor film can be sufficiently protected.

[0011] In addition, since the glass frit film is covered with the predetermined pattern on the oxide semiconductor film, a portion not covered with the glass frit film is increased. It can be manufactured without reducing the quenching effect.

Further, since the second tin oxide film acts as a low-radiation layer, the emissivity for radiant heat is reduced between the second space (inside of the refrigerator) and the surface of the low-radiation layer, and radiant heat transfer is performed. Not only improves the heat insulation of the glass window, but also raises the surface temperature of the low-emissivity layer, and the atmosphere in the first space (outside the warehouse) is changed to the second space when taking out or refilling goods from the warehouse. (Even inside the refrigerator) and when the surface of the low emissivity layer is touched, dew condensation hardly occurs on the surface of the low emissivity layer. In addition, the temperature of the second space and the surface temperature of the low emissivity layer The difference increases so that convective heat transfer is likely to occur, so that air on the surface of the low-emissivity layer is also easily replaced, and even if dew condensation occurs, it can be eliminated in a short time.

Further, since an intermediate layer made of an inorganic substance including the first tin oxide film and the silicon oxide film is interposed between the low-emissivity layer and the glass plate, this intermediate layer functions as a refractive index adjusting layer. As a result, the reflection color tone of the refrigerator / refrigerator glass can be easily adjusted to an achromatic color that exhibits a natural color, that is, a neutral color, and is used for a refrigerator / refrigerated showcase or a see-through vending machine. Even in such a case, high transparency can be maintained with a neutral reflection color tone. Since the above-mentioned inorganic substance is composed of a tin oxide film and a silicon oxide film, it does not impair the physical durability of the low-emissivity layer.

Further, since the intermediate layer includes the first tin oxide film and the silicon oxide film, the first tin oxide film acts as an alkali ion release preventing layer, thereby preventing a decrease in low radiation performance. In addition, since the silicon oxide film acts as the permeability increasing layer, the visible light transmittance is increased, and the internal confirmability can be improved.

The low emissivity layer can be easily manufactured by a chemical vapor deposition (hereinafter, referred to as “CVD”) method in a float glass manufacturing process, is suitable for mass production, and is inexpensive. And a tin oxide film that can be manufactured. Since the tin oxide film is an oxide semiconductor film having excellent physical and chemical durability, the work of cleaning the low-emissivity layer can be easily performed, and the usability is improved at a low cost. In addition, since the characteristics do not deteriorate even when the heat treatment is performed, the heat treatment can be performed after the film formation, thereby simplifying the entire process and performing the heat treatment at a low cost and quickly. it can. The low-emissivity layer can not only be constantly exposed to a low-temperature atmosphere in a refrigerator / refrigerator, but also maintain durability even if a sudden change in temperature occurs due to the intrusion of a room temperature atmosphere outside the refrigerator. When the inside of the freezer / refrigerator is cleaned, it can be prevented from being worn by being rubbed, and the ingress and egress of goods and the careless contact of the purchaser with the low radiation layer can be prevented.

The tin oxide film constituting the low-emissivity layer preferably contains fluorine in order to increase the conductivity of the film and improve the heat insulating performance. Hereinafter, the tin oxide film containing fluorine is also referred to as “SnO ₂ : F film”.

[0017] The total thickness of the oxide semiconductor film is preferably 250 to 750 nm. When the total film thickness is less than 250 nm, the vertical emissivity is increased to prevent an increase in the surface temperature of the glass frit film, and when the total film thickness exceeds 750 nm, the transmittance is reduced.

Preferably, the thickness of the first tin oxide film is 10 to 50 nm, the thickness of the silicon oxide film is 10 to 100 nm, and the thickness of the low emissivity layer is 200 to 600 nm. No.

The glass for refrigerators and refrigerators of the present invention has a heat transmission coefficient of 4 to improve heat insulation. It is preferably at most 00 W / m ² · K.

Further, the glass for freezing and refrigerator of the present invention has a visible light transmittance of 75% or more in order to sufficiently confirm the inside of the product inside the freezing / refrigerator from the outside at room temperature. And more preferably 80% or more, and it is necessary to select a glass plate having such visible light transmittance as a material.

Furthermore, the glass for freezing / refrigerator of the present invention minimizes radiation heat exchange between the inside of the freezing / refrigerator and the surface of the low radiation layer while maintaining high transparency as a glass window, thereby reducing radiation heat. It is necessary to reduce the emissivity, and for that purpose, the vertical emissivity of the oxide semiconductor film is preferably set to 0.15 or less.

The thickness of the glass plate of the refrigerator / refrigerator glass of the present invention is preferably 2 to 4 mm from the viewpoint of weight reduction and from the viewpoint of ensuring the strength of the glass.

[0023] The glass for refrigerators and refrigerators of the present invention is preferably tempered by air cooling in order to increase the strength.

[0024] The glass for refrigerators and refrigerators of the present invention may be subjected to a predetermined heat treatment at a predetermined temperature after the low emissivity layer is formed.

[0025] The freezing / refrigerating glass may be subjected to a predetermined heat treatment in order to improve the strength or bend the glass, and the heat treatment is necessary even in the coating of a substance having a hydrophilic / photocatalytic activity or the antibacterial treatment. However, when heat treatment is performed after the formation of the low-emissivity layer, the entire process can be performed quickly and at low cost, and the semiconductor oxide film forming the low-emissivity layer is resistant to heat treatment. Therefore, the characteristics do not deteriorate.

Further, in the case of the refrigerator / refrigerator glass of the present invention, when an intermediate layer having a hydrophilicity / water retention function is formed on the surface of the low emissivity layer, the contact angle of water droplets can be reduced. Even if water condenses on the intermediate layer, dew condensation hardly occurs and transparency is not easily impaired.From the viewpoint of maintaining high chemical and physical durability, the glass for refrigerators and refrigerators of the present invention is made of silicon, aluminum, and titanium. It is preferable that an intermediate layer mainly composed of a composite oxide or a mixed oxide containing at least one of the above elements is formed on the surface of the low-emissivity layer.

The thickness of the intermediate layer is preferably as low as possible provided that a desired hydrophilicity / water retention function is ensured so as not to impair the low emissivity of the low emissivity layer, ie, the high infrared reflection performance. It is preferably thin, specifically, 0.5 nm to 1000 nm, and most preferably 1 nm to 300 nm.

Further, since the inside of the refrigerator / refrigerator is often illuminated with lighting equipment such as a fluorescent lamp, it is preferable that the intermediate layer contains a photocatalytically active substance. As a result, the organic dirt on the glass surface can be decomposed, and the hydrophilic / water retaining function can be maintained for a long period of time.

When the refrigerator / freezer is used for storing and displaying food, antibacterial treatment is applied to at least one of the inner surface and the outer surface of the refrigerator / fridge from the viewpoint of hygiene. Is preferred. In the case of silver-based treatment, which is often performed as an antibacterial treatment, the antibacterial property is unlikely to occur at low temperatures, and the glass of the present invention, which can maintain a high internal surface temperature of the glass, is suitable for the antibacterial treatment. ing.

The refrigeration / refrigerator glass of the present invention has a greater convective heat transfer effect when installed so as to look upward into the refrigerator from below, as compared with the case where the glass is installed vertically. The effect is small, but conversely, if the freezer / fridge glass is installed at an angle not more than a predetermined angle with respect to the horizontal direction so that the inside of the refrigerator can be seen from diagonally above or from above, It is difficult for not only radiative heat transfer but also convective heat transfer to occur with the glass frit film surface, and the surface temperature of the low radiant layer further rises, and more effectively preventing the glass plate from fogging. Becomes possible.

That is, the freezing / refrigerating glass of the present invention has a freezing surface in which the glass surface is horizontal and the inclination angle is 0 to 135 ° with respect to a state in which the glass frit film is provided on the lower surface in the vertical method. It is preferably attached to the refrigerator body, and preferably, the inclination angle is 0 ° to 60 °.

In addition, conventionally, a double-layer glass as a glass article in which a hollow layer such as an air layer, a heat-insulating gas layer, or a pressure-reducing layer is interposed between a plurality of glass plates exhibits an extremely excellent heat-insulating action and effect. However, when the above-described glass for a refrigerator / refrigerator of the present invention is incorporated in a double-glazed glass, it is possible to further improve the heat insulation performance while preventing the occurrence of dew condensation.

The glass article according to the present invention is arranged such that a plurality of glasses including at least one of the above glasses are opposed to each other so that the glass frit film side faces a space in a low-temperature atmosphere lower than room temperature. A hollow layer is formed between a plurality of glasses, and the hollow layer is any one of an air layer, a heat-insulating gas layer, and a reduced pressure layer.

When producing a glass article including a reduced pressure layer, it is preferable to perform degassing by heating to 150 ° C. or more so as to maintain the reduced pressure state of the reduced pressure layer for a long period of time. The oxide semiconductor film forming the low-emissivity layer is preferable because characteristics do not deteriorate.

Further, the glass article of the present invention is a transparent glass having a low-emission layer or a low-emission substance on at least one of the plurality of glasses facing each other, the surface facing the hollow layer. A film is formed, or a low-emission layer or a transparent film containing a low-emission substance is disposed in the hollow layer at a distance from the surface of the glass. Thereby, the heat insulation can be further improved.

Further, the glass article of the present invention is arranged such that a plurality of glasses including the above-mentioned glass for freezing / refrigeration face the glass frit film side to a space in a low-temperature atmosphere lower than room temperature via a transparent resin layer. It is also preferable to form a so-called laminated glass which is overlaid on each other.

Further, it is also preferable to select two pieces of double-glazing from the above-mentioned double-glazing and to overlap the two pieces of double-glazing with a transparent resin layer interposed therebetween.

In addition, the above-mentioned double-glazed glass and laminated glass are preferably subjected to antibacterial treatment from the viewpoint of hygiene, similarly to the above-mentioned glass for freezing and refrigerators.

[0039]

[Embodiment of the invention]

 Next, embodiments of the present invention will be described in detail with reference to the drawings.

FIG. 1 is a sectional view schematically showing a first embodiment of the glass for freezing / refrigerator according to the present invention.

In FIG. 1, reference numeral 1 denotes a glass plate mainly composed of soda-lime glass manufactured by a float method. The thickness of the glass plate 1 is preferably 2 to 4 mm.

[0042] surface of the glass plate 1, a tin oxide film as an alkali dissolution preventive layer (hereinafter, referred to as "Sn O ₂ film") 2 is formed, silicon oxide as ZoToruso on the surface of the SnO ₂ film 2 An element film (hereinafter, referred to as “SiO ₂ film”) 3 is formed. The SnO ₂ film 2 and the SiO ₂ film 3 constitute an intermediate layer 5, and a SnO ₂ : F film 4 is formed on the surface of the intermediate layer 5 as a low radiation layer. The intermediate layer 5 and the SnO ₂ : F film 4 constitute a laminated film 6 (oxide semiconductor film), and a glass frit film 30 is formed on the laminated film 6 as a protective film.

In the present embodiment, the side on which the film is not formed faces the outside (first space) of the room temperature atmosphere, and the side on which the glass frit film 30 is formed has an atmosphere lower than room temperature. It is installed as a glass window on the refrigerator (refrigerator / refrigerator) for supermarkets and convenience stores, especially for ice cream showcases and frozen food displays, facing the inside of the refrigerator (second space).

The glass frit film 30 is made of a glass material having a lower melting point than that of the glass plate 1, and is formed by applying a powder of the glass in a paste form and heating and firing in a firing furnace. Further, the glass frit film 30 is preferably coated (coated) on the entire surface of the laminated film (oxide semiconductor film) 6, and in particular, a predetermined pattern of 2 mm φ dots at a pitch of 5 mm by a screen printing method. May be coated. The screen specification is preferably from 165 mesh to 200 mesh. The thickness of the glass frit film 30 is preferably 10 μm.

When the above-mentioned glass for freezing / refrigerator is used by being attached to a freezing / refrigerator in a supermarket, a convenience store, or the like, goods are frequently taken in and out and replenished, so that the glass can be easily read from outside the refrigerator. The glass plate 1 should have a visible light transmittance of 75% or more, and more preferably 80% or more. Is selected and used. Further, the freezers and refrigerators for glass viewpoint et improving heat insulating property is preferably heat transmission coefficient is less than 4.00W / m ² · K, the glass plate, 4.00W / m ² · A composition having a heat transmission coefficient of K or less is selected and used.

The thickness of each of the laminated films 6 is adjusted as follows. (1) SnO _2: F film 4 having a thickness of SnO _2: F film 4 is a thin film doped with fluorine (containing) in tin oxide, conductive thin film by doping fluorine in an acid tin As a result, light in the infrared wavelength range (5.5 μm to 50 μm) can be effectively reflected to improve the heat insulation performance. In the heat transfer between the inside of the refrigerator and the refrigerator, there are radiant heat transfer and convective heat transfer. However, the SnO ₂ : F film 4 suppresses the radiant heat transfer by lowering the emissivity to the radiant heat. As a result, the temperature of the glass surface inside the refrigerator rises, thereby preventing the occurrence of dew condensation. The low emissivity can be evaluated by the vertical emissivity (JIS R3106). In order to secure a desired low emissivity, the vertical emissivity is desirably 0.15 or less. In the present embodiment, the thickness of the SnO ₂ : F film 4 needs to be set to 200 nm or more as a range in which such a vertical emissivity can be obtained. On the other hand, the greater the thickness of the SnO ₂ : F film 4, the lower the emissivity can be. However, it is desirable to set the thickness to 600 nm or less, preferably 500 nm or less due to the restrictions on the cost of production equipment.

(2) Thickness of SnO ₂ Film 2 and SiO ₂ Film 3 It is desirable in appearance that the refrigerator / refrigerator glass is a neutral type which not only has a high visible light transmittance but also exhibits a natural reflection color tone. . In other words, the reflection color tone of an object such as a glass window is quantitatively expressed on a chromaticity diagram by the chromaticness index a *, b * of the L * a * b * color system specified by the International Commission on Illumination (CIE). (JIS Z8729). In order to obtain a neutral reflection color tone, the chromaticness indices a * and b * are | a * | ≦ 10, | b * | ≦ 10, more preferably | a * | ≦ 5, | b * | It is preferred that ≦ 5.

However, the adjustment of the reflection color tone is limited only by the SnO ₂ : F film 4, and there is a possibility that a rainbow-colored reflection color is exhibited due to light interference.

Therefore, in the present embodiment, the intermediate layer 5 having a double structure of the SnO ₂ film 2 and the SiO ₂ film 3 as inorganic substances which does not impair the physical durability of the SnO ₂ : F film 4 is made of glass. The reflection color tone is adjusted so as to be a neutral system by interposing between the plate 1 and the SnO ₂ : F film 4. That is, the glass plate 1 and the SnO _2: When interposing a SnO ₂ film 2 and the SiO ₂ film 3 between the F layer 4, the SnO ₂ film 2 and the SiO ₂ film 3 acts as a refractive index adjusting layer, which As a result, the reflection color tone of the glass for freezing / refrigeration can be easily adjusted to an achromatic color system exhibiting a natural color tone, that is, a neutral color system.

In the present embodiment, as a range in which such a color tone adjustment can be performed, the thickness of the SnO ₂ film 2 is 10 to 50 mm, and the thickness of the SiO ₂ film 3 is 10 to 100 nm. preferable. The total thickness of the laminated film 6 is preferably from 250 to 750 nm. When the total film thickness is 250 or less, the vertical emissivity decreases and contributes to an increase in the surface temperature of the glass. When the total film thickness is large, the scratch resistance of the film is improved. At times, the permeability is below the acceptable range.

In the present embodiment, the intermediate layer 5 has a two-layer structure including the SnO ₂ film 2 and the SiO ₂ film 3, but the intermediate layer 5 is interposed for the purpose of adjusting the color tone as described above. Therefore, the present invention is not limited to the two-layer structure as long as such color tone adjustment is possible, and may be a one-layer structure or a three- or more-layer structure as long as the low radiation performance is not impaired. Alternatively, it may be a gradient composition layer in which a specific film component (for example, Si or Sn) is distributed in a gradient in the film.

As described above, in this embodiment, since the SnO ₂ : F film 4 which is a low-emission layer is formed on the glass plate 1 facing the inside of the refrigerator, the space inside the refrigerator / freezer and the glass The emissivity for radiant heat decreases between the inside and the inside of the cabinet, radiative heat transfer is suppressed, and convective heat transfer becomes dominant. As a result, not only the heat insulation of the glass window is improved, but also the The surface temperature of the inside of the refrigerator rises, and consequently, even when the outside atmosphere enters the refrigerator and touches the inside surface of the glass when removing or refilling products from the freezer or refrigerator, dew condensation occurs. It is unlikely to occur, and even if it occurs, the transparency can be restored in a short time.

In the present embodiment, since the radiant heat transfer is suppressed, the surface temperature of the glass frit film 30 approaches the surface temperature of the glass plate outside the refrigerator, and the surface temperature of the glass frit film 30 rises. However, this also prevents the occurrence of dew condensation, and can prevent loss of transparency.

Further, since the surface temperature of the glass frit film 30 rises, the difference between the temperature of the internal space and the surface temperature of the glass frit film 30 increases, so that convective heat transfer easily occurs. The air is easily exchanged, and even if dew condensation occurs, it can be eliminated in a short time.

Further, in the present embodiment, since the rise in the surface temperature of the inside of the glass of the glass is caused by the influence of the ambient temperature of the outside of the glass, there is no need to use a heater or the like that requires electric power. It is economical and can contribute to energy saving.

When the glass for freezing / refrigeration of the present invention is used as a glass window for a showcase for ice cream, for displaying frozen foods, etc., the glass itself of the present invention is provided with an opening / closing mechanism to provide the glass. It is also preferable to attach it to the case, and when fitting the main glass to the window frame, provide an opening / closing mechanism such as a so-called pulling mechanism, single pulling mechanism, and opening mechanism on the window frame, and attach the main glass to the showcase so that it can be opened and closed freely. Is also preferred.

FIG. 2 is a view showing an example of a mounting mode when the present freezing / refrigerating glass is mounted on a freezing / refrigerator main body. In the figure, the X axis is horizontal and the Y axis is vertical. Is shown.

That is, as shown in FIG. 2C, the freezing / refrigerating glass 7 is horizontal, and the laminated film 6 on which the glass frit film 30 and the low radiation layer 4 are formed faces downward. The glass frit film 30 is attached to the refrigerator / refrigerator body 8 so as to face the inside of the refrigerator at an inclination angle θ.

As shown in FIG. 2A, the inclination angle θ is 135 even if the freezing / refrigerator glass 7 is attached to the freezing / refrigerator body 8a so that the inside of the refrigerator is looked up from outside. 2 ° or less, and preferably 60 ° or less as shown in FIG. 2 (b), and the best mounting mode is as shown in FIG. This is a case where the application glass 7 is mounted horizontally.

That is, as shown in FIGS. 2B and 2C, the freezing / refrigerating glass 7 of the present invention is installed on the freezing / refrigerating body 8 in a form obliquely above or from above. In this case, not only radiative heat transfer but also convective heat transfer hardly occurs between the glass frit film 30 on the SnO ₂ : F film 4 which is a low radiation layer and the space in the refrigerator / freezer. The surface temperature of the frit film 30 approaches a room temperature atmosphere outside the refrigerator, whereby the surface temperature of the glass frit film 30 increases, and the occurrence of dew condensation can be more effectively prevented.

Next, a method for producing the present freezing / refrigerating glass will be described.

As a method for manufacturing the present refrigerator / refrigerator glass by forming the laminated film 6 on the glass plate 1, a vacuum deposition method, a sputtering method, a coating method, or the like can be used. It is most preferable to manufacture by a CVD method which can easily form a film, is suitable for mass production and is inexpensive.

FIG. 3 is a schematic configuration diagram schematically showing a CVD film forming apparatus. The CVD film forming apparatus is provided with a heater 9 for heating the glass plate 1 to a predetermined temperature, and is conveyed in the direction of arrow A. A plurality of film forming material supply units 10 (in the present embodiment, first to fifth film forming material supply units 10a to 10e) arranged in a row so as to cover the width direction of the resulting glass plate 1. I have.

In the CVD film forming apparatus, the glass plate 1 cut into a predetermined shape is heated to a predetermined high temperature by a heater 9, conveyed on a mesh belt, and passed through the inside of the apparatus. The raw material for film formation is supplied to the surface of the glass plate 1, and the raw material for film formation is thermally decomposed on the glass plate 1 through the thermal energy of the glass plate 1, and a desired thin film is deposited on the glass plate 1. . For example, when producing the laminated film 6 as shown in FIG. 1 above, a mixed gas composed of a tin compound, oxygen, water vapor, and nitrogen is supplied to the surface of the glass plate 1 from the first film forming material supply unit 10a. The SnO ₂ film 2 is formed as a first layer by being supplied, and a silicon compound, oxygen, and nitrogen are supplied onto the glass plate 1 from a second film forming material supply unit 10b to form a second layer. SiO ₂ film 3 is formed. Further, a mixed gas composed of a tin compound, oxygen, water vapor, nitrogen, and a fluorine compound is supplied from the third film forming material supply unit 10c and, if necessary, the fourth and fifth film forming material supply units 10d and 10e. The SnO ₂ : F film 4 serving as a third layer is formed on the glass plate 1. That is, when forming a thick film, as described above, the same film forming material is supplied in a plurality of stages (for example, three stages of the third to fifth film forming material supply units 10c to 10e) as described above. And supplied onto the glass plate 1.

When the glass frit film 30 is formed on the laminated film 6, a paste-like glass frit is applied on the entire surface of the laminated film 6 or printed and applied by a predetermined pattern by a screen printing method. After heating and firing in a firing furnace, air cooling is performed. The heating temperature is preferably 580 ° C to 800 ° C because the glass frit material is a low melting point glass. Further, when the glass frit is applied to the entire surface of the laminated film 6, the quenching degree of the glass in the air-cooling strengthening step is weakened, so that the effect of the glass strengthening does not increase. Therefore, it is preferable that the glass frit is printed and applied in a predetermined pattern, for example, a dot shape so as to have an exposed portion of the glass.

The tin raw material for forming the SnO ₂ film 2 includes monobutyltin trichloride, tin tetrachloride, dimethyltin dichloride, dibutyltin dichloride, dioctyltin dichloride, tetramethyltin, tetrabutyltin, tetrabutyltin Tin compounds such as laoctyl tin can be used, and oxygen, steam, dry air, etc. can be used as the oxidizing material.

Further, silicon materials for forming the SiO ₂ film 3 include monosilane, disilane, trisilane, monochlorosilane, dichlorosilane, 1,2-dimethylsilane, 1,1,2-trimethyldisilane, Silane compounds such as 1,1,2,2-tetramethyldisilane, tetramethylorthosilicate, tetraethylorthosilicate, and the like can be used. Oxidation materials such as oxygen, steam, dry air, carbon dioxide, Carbon oxide, nitrogen dioxide, ozone and the like can be used.

Further, as the fluorine compound for forming the SnO ₂ : F film 4, trifluoroacetate, hydrogen fluoride, bromotrifluoromethane, chlorodifluoromethane, difluoroethane and the like can be used.

As described above, the freezing / refrigerating glass of the present invention can be easily formed into a film during the float glass manufacturing process, and can be mass-produced at low cost.

The SnO ₂ : F film 4 is hardly deteriorated by heat treatment, and a strengthening process, a bending process, a degassing process, and the like can be performed after the SnO ₂ : F film 4 is formed. Can be simplified, and can be performed quickly and at low cost.

[0071] For example, in order to improve the strength of glass by air cooling tempering through heat tempering furnace or the like, SnO a low emissivity layer _2: SnO ₂ by heat treatment after the formation of the F film 4: Characteristics of the F film 4 It can be performed quickly and at low cost without causing deterioration.

That is, the tempered glass is generally obtained by using a heat strengthening furnace having a heater portion and an air cooling portion. In such a case, first, the glass on which the SnO ₂ : F film 4 is formed is firstly heated. After heating to 600 ° C. or higher in the air-cooling section, the air-cooling section discharges compressed air at normal temperature from the compressor and supplies the compressed air to the glass surface, whereby the glass surface is heated. Upon cooling, a compressive stress is generated, and the air cooling is strengthened. As a result, tempered glass having a surface compressive stress of 60 MN / m ² or more and a crushing number of 40 or more specified in JIS R3206 can be quickly obtained at low cost.

Further, by adjusting the air cooling rate of the glass by the same method, a double strength glass having a surface compressive stress of 20 to 60 MN / m ² specified in JIS R3222 can be obtained.

Similarly, also in the case of performing the bending process, the heat treatment at 700 ° C. or more after the formation of the glass frit film 30 deteriorates the characteristics of the SnO ₂ : F film 4 as a low-emission layer. A curved glass can be obtained by performing a bending process without the need.

In the case where degassing is performed, for example, during the production of a double glazing having a hollow layer as a reduced pressure layer, the SnO ₂ : F film 4 is formed, and then a heat treatment is performed at 150 ° C. or more, so that the SnO ₂ : F ₂ : A desired degassing process can be performed without deteriorating the characteristics of the F film 4 as a low radiation layer.

In addition, refrigerators and refrigerators in supermarkets and convenience stores are generally used for storage and display of foods. In order to prevent the propagation of pathogenic bacteria such as Escherichia coli and O157 from the viewpoint of hygiene, silver colloids are used. It is preferable that an antibacterial agent such as a dispersion is applied to the surfaces of the glass plate 1 and the glass frit film 30 to perform an antibacterial treatment.

Next, FIG. 4 is a cross-sectional view schematically showing a second embodiment of the glass for freezing / refrigerator according to the present invention.

In the same drawing, in the second embodiment, an SnO ₂ film 2, a SiO ₂ film 3 and a SnO ₂ : F film 4 are sequentially formed on the surface of a glass plate 1 as in the first embodiment. It has been. The SnO _2: TiO ₂ film 11 on the surface of the F layer 4 is photocatalytically active layer is formed, SiO ₂ film (hereinafter the surface containing aluminum (Al) of the TiO ₂ film 11, "SiO _2: Al film "hereinafter) 12 is formed, these TiO ₂ film 11 and the Si O _2: the intermediate layer 13 is formed in the Al film 12, the intermediate layer 13 is have a hydrophilic-holding water. On the surface of the intermediate layer 13, a glass frit film 30 is formed as a protective film.

That is, when the intermediate layer 13 having a hydrophilicity / water retention function is formed on the inner surface of the glass frit film 30, even if water droplets adhere to the glass frit film 30, the glass frit film 30 has an effect of reducing the contact angle. Even when moisture condenses on the glass frit film 30, condensation hardly occurs, so that it is possible to avoid sintering and impairing the transparency. However, in the second embodiment, since the intermediate layer 13 having the hydrophilicity / water retention function includes the TiO ₂ film 11 which is a photocatalytic active layer, the inside of the freezer / freezer is a fluorescent lamp or the like. Even when illuminated by lighting equipment, it can decompose organic dirt on the surface of the refrigerator / fridge glass and maintain the hydrophilicity / water retention function for a long period of time.

The intermediate layer 13 needs to be formed so as not to impair the high-infrared reflection performance of the low-emissivity layer. To this end, it is necessary to consider the balance between the hydrophilic / water-retaining function and the low-emission performance. It is desirable to be as thin as possible, and the total thickness of the intermediate layer 13 is 0.5 to 1000 nm or less, preferably 0.5 to 700 nm or less, more preferably 1 to 500 nm or less, and still more preferably 1 to 300 nm or less. It is preferred that

In the intermediate layer 13 having the hydrophilic / water retaining function, the fifth layer SiO ₂ : Al film 12 can be omitted, and is constituted by a single layer of the fourth layer TiO ₂ film 11 alone. It is good.

The intermediate layer 13 can be manufactured by a vacuum evaporation method, a sputtering method, a CVD method, a coating method, or the like. In order to activate the photocatalytic substance, heat treatment is performed during or after film formation. It is effective to apply.

Next, a case where the intermediate layer 13 is manufactured by the sputtering method will be described.

FIG. 5 shows a load-lock type in-line type magnetron sputtering apparatus (hereinafter referred to as “sputtering apparatus”) for forming an intermediate layer 13 on the surface of the SnO ₂ : F film 4. It has a load lock chamber 15 and a film forming chamber 16, and the film forming chamber 16 is provided with first and second cathodes 17 and 18 and a heater 19.

For example, when the film formation of the intermediate layer 13 as shown in FIG. 4 is performed, the freezing / refrigerator glass 7 having the laminated film 6 formed on the surface thereof in the first embodiment is load-locked. After being transported to the chamber 15 and evacuated to a predetermined pressure, it is transported to the film formation chamber 16 as shown by the arrow B. Then, a sputtering gas is supplied from a gas supply port 20 to the film forming chamber 16, and the freezing / refrigerating glass 7 is heated to a predetermined temperature, and is supplied to a first cathode 17 on which titanium as a target substance is set. A voltage is applied, which causes reactive sputtering with oxygen at a predetermined high temperature, and the refrigerating / refrigerating glass 7 reciprocates under the first cathode 17 so that the laminated film 6 The TiO ₂ film 11 as a fourth layer is formed on the surface. Also, silicon to which Al is added is set as a target on the second cathode 18, and the refrigerator / refrigerator glass 7 is transported in the direction of arrow C after the TiO ₂ film 11 is formed. 2 is reciprocated under the cathode 18, and a SiO ₂ : Al film 12 is formed as a fifth layer on the surface of the TiO ₂ film 11 by reactive sputtering. Can be made. The thickness of the intermediate layer 13 is controlled by adjusting the number of reciprocations and the moving speed of the freezing / refrigerator glass 7.

FIG. 6 is a cross-sectional view of a principal part showing a first embodiment of a double glazing as a glass article using the above-mentioned glass 7 for freezing / refrigerator. The formed freezing / refrigerating glass 7 and the float plate glass 27 as a single glass plate made of soda-lime glass or the like are arranged so that the laminated film 6 is exposed to the outside air, and are disposed near both ends thereof. A spacer member 21 containing a desiccant is interposed, and both ends are thermally fused and sealed with a sealing material 22 such as butyl rubber. Thus, the hollow layer 23 is defined by being surrounded by the freezing / refrigerating glass 7, the float plate glass 27, the spacer member 21, and the sealing material 22.

It is said that this type of double glazing can improve the heat insulating performance even more than a single glass plate. Therefore, the use of the freezing / refrigerating glass 7 of the present invention is considered. Accordingly, it is possible to prevent the occurrence of dew condensation and to further improve the heat insulating performance. The hollow layer 23 is preferably an air layer or an insulating gas layer filled with argon gas or the like from the viewpoint of enhancing the heat insulating performance, and the hollow layer 23 is in a dry state from the viewpoint of preventing dew condensation. Is preferred. In order to keep the hollow layer 23 in a dry state and a clean state, it is preferable that both ends are completely sealed with the sealing material 22 as described above, but the sealing state is incomplete. Even if a device for replacing the gas in the hollow layer 23 is provided, it is sufficient that the heat insulating property and the transparency of the double-glazed glass are not adversely affected.

Further, from the viewpoint of ensuring the desired heat insulating performance of the hollow layer 23, it is preferable that the interval t between the freezing / refrigerating glass 7 and the float plate glass 27 is set to 4 mm or more.

FIG. 7 is a cross-sectional view of a principal part showing a second embodiment of a double glazing. The double glazing is obtained by applying a low radiation coating to the glass plate 1 in contact with the hollow layer 23, The low emissivity layer 24 is formed by attaching a transparent film containing a radioactive substance, and the heat insulating property is further improved.

FIG. 8 is a cross-sectional view of a principal part showing a third embodiment of a double-layer glass. The double-layer glass is configured such that the laminated film 6 is exposed to the outside air and the hollow layer 23 has a distance t. Is set to 0.2 mm to 1 mm, and a predetermined reduced pressure state is set. Further, both ends are sealed with low melting point glass 25, and the freezing / refrigerating glass 7 and the flat plate glass A minute spacer member 26 for adjusting the distance from the space 27 is provided.

[0091] By configuring the hollow layer 23 with a reduced pressure layer in this manner, the same operation and effect as described above can be achieved.

Note that the present invention is not limited to the above embodiment, and can be similarly applied to so-called laminated glass. That is, a plurality of glasses including one or more glasses for freezing / refrigerating glass face each other via a transparent resin such as polyvinyl butyral such that the low radiation layer side faces the space of a low-temperature atmosphere lower than room temperature. It is also preferable that the glass is adhered to improve safety when the glass is broken.

In addition, the present invention provides a double-layer glass having two or more hollow layers, or a transparent film in a hollow layer separated from a glass surface facing each other (including a case where a low-emission substance is contained). It is also preferable that the present invention can be applied to a glass article in which a multi-layer glass and a laminated glass are combined.

In the above embodiment, a planar glass plate has been described, but the present invention can be similarly applied to a curved glass plate.

[0095]

【Example】

 Next, embodiments of the present invention will be specifically described.

The present inventor washed and dried a float plate glass having a thickness of 3 mm, and laminated the float plate glass on the glass plate 1 using a CVD film forming apparatus (see FIG. 3). Film 6 was formed. That is, the glass plate 1 is conveyed by an open-to-atmosphere mesh belt, and the surface temperature of the glass plate 1 is heated to about 650 ° C. by the heater 9. In the meantime, a predetermined film forming material is supplied from the film forming material supply unit 10 onto the glass plate 1 to cause a chemical reaction on the glass plate 1 to precipitate a solid phase, and the SnO ₂ film 2, the SiO ₂ film 3 and a SnO ₂ : F film 4 were sequentially laminated on the glass plate 1.

Further, a glass frit is coated on the SnO ₂ : F film 4 to form a glass plate 1 / SnO ₂ film 2 / SiO ₂ film 3 / SnO ₂ : F film 4 / glass frit film 30 (FIG. 1) (see Examples 1 and 2).

Specifically, a paste-like coating liquid was prepared by mixing a low-melting glass frit on a powder (manufactured by Nippon Electric Glass: Model No. PLS3 162S) and an organic solvent. This coating solution was printed and applied on the SiO ₂ : F film 4 in a predetermined pattern of ₂ mmφ dots at a pitch of 5 mm by screen printing (Examples 1 and 2), and was applied on the entire surface (Example 1). The glass frit powder was melted and thinned by firing in a firing furnace at 520 to 600 ° C. for about 10 to 20 minutes. The specifications of the screen used for screen printing are 165 to 200 mesh.

For forming the laminated film 6, monobutyltin trichloride (hereinafter referred to as “MBTC”) is used as a tin raw material, and the MBTC is heated to 150 ° C. to convert the vapor of the MBTC into 1 mol of nitrogen. Nitrogen is transported as a carrier gas at a concentration of 0.001 mol / mol and supplied to the first film forming material supply unit 10a, and oxygen as an oxidizing gas is supplied to the first film forming material supply unit 10a by another system. And a pyrolysis reaction and an oxidation reaction were caused on the glass plate 1 to form an SnO ₂ film 2 having a thickness of 25 nm on the glass plate 1 to form a first layer. Next, using monosilane as a silicon raw material, monosilane gas is directly supplied from a cylinder to the second film forming material supply unit 10b, and oxygen as an oxidizing gas is supplied from another system in the same manner as in the formation of the SnO ₂ film 2 described above. It is supplied to the film-forming raw material supply unit 10b, by causing thermal decomposition reaction and oxidation reaction by laminating SiO ₂ film 3 having a thickness of 25nm on the SnO ₂ film 2 on SnO ₂ film 2, forming a second layer did. Next, using MTBC as a tin raw material and trifluoroacetate as a fluorine raw material, the third to fifth film forming raw material supply units 10c to 10e inject the film forming raw material to form a 350 nm thick film on the SiO ₂ film 3. An SiO ₂ : F film 4 was laminated to form a third layer. That is, since the thickness of the SiO ₂ : F film 4 is as thick as 350 nm, the supply of the film forming material onto the SiO ₂ film 3 was performed in a plurality of stages. Specifically, the MBTC is heated to about 150 ° C., and the vapor of the MBTC is transported at a concentration of 0.01 mol per mol of nitrogen with nitrogen as a carrier gas, and steam is promoted to promote the decomposition of MTBC. Nitrogen is transported as a carrier gas at a concentration of 5 mol per mol of nitrogen, and trifluoroacetate is heated to about 150 ° C., and the vapor of the trifluoroacetate is transported from another system using nitrogen as a carrier gas, and MTBC vapor is conveyed. , Water vapor and trifluoroacetate vapor are supplied to the third to fifth film forming raw material supply units 10c to 10e, and the third to fifth film forming raw material supply units 10c to 10e are supplied as oxidizing gas. Was supplied from a separate system. And, the vapor of MTBC vapor trifluoroacetate, water vapor, oxygen is supplied onto the S iO ₂ film 3 cause thermal decomposition reaction and oxidation reaction, SiO ₂ on the SiO ₂ film 3: F film 4 were laminated to form a third layer (Example 1).

In addition, the present inventor produced a glass for a refrigerator / refrigerator having different specifications of the glass frit film 30 and also manufactured a film having a different thickness of the laminated film 6 in Examples 2 to 4 of the present invention and a comparative example. 1 and 2. They are shown in Table 1.

[0101]

[Table 1] The present inventors rubbed the steel surface of the above-mentioned test piece with a household steel scourer 100 times so as to draw a circle having a diameter of about 20 cm, and visually checked whether or not scratches occurred, and measured the scratch resistance. . As a result, the test piece was judged to be defective when scratches were formed on the film surface and could be visually confirmed, and judged to be good when no scratches were observed.

Further, the inventor of the present invention puts the test piece (Examples 1 to 4 and Comparative Examples 1 and 2) into a freezer with the glass frit film 30 facing the inside of the refrigerator as a glass window of a vertical door which can be opened and closed. The temperature of the glass frit film 30 (hereinafter, referred to as “inside surface temperature”) and the surface temperature of the glass sheet 1 (hereinafter, “outside of the refrigerator”) are set at a temperature of −20 ° C. inside the refrigerator and 20 ° C. outside the refrigerator. Surface temperature ”), and the heat transmission coefficient, which is a measure of the heat insulation performance, was measured in accordance with JIS A4710. However, natural convection was used for both the inside of the heating box on the constant temperature room side and the low temperature room side without using an air flow stirrer.

Further, the present inventor sets Comparative Example 3 in which the float plate glass alone was attached to the above refrigerator, and further, the glass frit film 30 of the test piece of Example 1 above was directed to the outside of the refrigerator, and was placed in a freezer. The attached one was set as Comparative Example 4, and the inside surface temperature, outside surface temperature, and heat transmission coefficient were measured under the inside temperature of −20 ° C. and outside temperature of 20 ° C. as described above.

The surface temperature was measured by using the infrared radiation temperature corrected by the emissivity of the glass surface and the low radiation layer. The heat transmission coefficient was 5 m / sec for the external wind speed, 20 ° C. for the outside air, and 20 ° C. Inner wind speed Measured under the conditions of natural convection and an internal temperature of 0 ° C.

Further, since the glass for freezing / refrigeration is required to have excellent transparency, the visible light transmittance is measured in accordance with JIS R3106, and further, the vertical dimension which is a measure of low radiation performance is measured. The emissivity was measured according to JIS R3106.

Table 1 shows the measurement results of Examples 1 to 4 and Comparative Examples 1 to 4.

In Table 1, the scratch resistance characteristics of Examples 1 to 4 were better than those of Comparative Examples 1 to 4 because the glass frit film 30 as the protective film was formed on the surface. Further, in Examples 1 to 4, it was found that there was no difference between the case where the glass frit film 30 was entirely coated on the surface and the case where the glass frit film 30 was coated in a dot shape.

In Comparative Example 1, the visible light transmittance was 83 because the thickness of the third layer SnO ₂ : F film 4 was less than 200 nm and the thickness of the laminated film 6 was less than 250 nm. . The internal confirmation temperature was good at 4%, but the surface temperature inside the refrigerator was 1.80 ° C and the surface temperature outside the refrigerator was 2.30 ° C, which caused surface dew condensation, and the heat transmission rate was 4.6W / m. ^The heat insulation was high at ² · K, and was poor.

In Comparative Example 2, since the thickness of the third layer SnO ₂ : F film 4 exceeds 750 nm and the thickness of the multilayer film 6 exceeds 600 nm, the heat transmission coefficient is 3.68 W / m ^2. -Low K and good heat insulation. The inside surface temperature of the refrigerator was 3.80 ° C and the outside surface temperature of the product was 4.30 ° C. No surface condensation occurred, but the visible light transmittance was 74.5. %, The internal confirmation was poor.

In Comparative Example 3, since the float plate glass alone was used, the visible light transmittance was 90.1% and the internal confirmation was good, but the internal surface temperature of the refrigerator was 0.50 ° C., and the external surface temperature was 0.50 ° C. However, since the surface dew condensation was as low as 1.10 ° C. and no low-emission layer was formed, the heat transmission coefficient was as high as 4.60 (W / m ² · K), and the heat insulating property was poor.

Further, in Comparative Example 4, since a low radiation layer (SiO ₂ : F film 4) was formed, the heat transmission coefficient was as low as 3.60 W / m ² · K, and the heat insulating property was good. And the inside surface temperature was -3.20 ° C and the outside surface temperature was -2.70 ° C, and surface dew condensation occurred.

On the other hand, in Examples 1 to 4, the first layer of the SnO ₂ film 2 has a thickness of 10 to 50 nm, the second layer of the SiO ₂ film has a thickness of 10 to 100 nm, and the third layer has a thickness of 10 to 100 nm. Since the thickness of the SnO ₂ : F film 4 is 200 to 600 nm and the layer thickness of the laminated film 6 is 250 to 750 nm, the internal surface temperature of the chamber is 3.20 to 3.82 ° C. The outside surface temperature is 4.10 ° C to 4.30 ° C and the surface temperature inside and outside the room is high and no surface condensation occurs, and it is possible to prevent clouding or dew condensation on the window glass. However, it was confirmed that visibility from the outside to the refrigerator / refrigerator can be prevented from being impaired. Moreover, the heat transmission coefficient was 3.68 to 3.78 W / m ² · K, and the desired heat insulating performance was able to be secured.

Further, in Examples 1 to 4, the visible light transmittance was 75% or more, sufficient transparency was secured, and the vertical emissivity was 0.15 or less. It can be seen that the radiant heat exchange between them is suppressed and the emissivity for radiant heat is reduced, contributing to the rise in surface temperature.

Since it is preferable that the reflection color is neutral, the reflectance spectrum from the thin film surface side of Example 1 was measured in accordance with JIS R3106, and in accordance with JIS Z8729. The chromaticity indices a * and b * were calculated, and the reflection color tone was evaluated. As a result, the chromaticness indices a * and b * are “−1.5” and “−1.0”, respectively, and are therefore in the range of | a * | ≦ 5, | b * | ≦ 5, and are neutral. It was confirmed to have a system reflection color tone.

As is clear from Table 1, in Examples 1 to 4, the thicker the SiO ₂ : F film 4 is, the lower the emissivity to radiant heat is. It was found to be effective in prevention.

Second Embodiment Next, the present inventor performed heat treatment using a test piece having the same film configuration as that of the above-described first embodiment, to produce a reinforced glass.

Specifically, the test piece was heated at a heating temperature of 700 ° C. for 10 minutes by adjusting the amount of air flowing into the upper portion in the heater portion of the heat strengthening furnace in order to enhance convection heating, and then the compressor in the air cooling portion. To supply normal temperature compressed air to the test piece to produce a good tempered glass having a surface compressive stress of 80 MN / m ^{2 and} no appearance distortion.

Note that JIS R3206 does not specify a tempered glass for a glass plate having a thickness of 3 mm, but in this embodiment, the number of crushed pieces is 40 or more according to the method specified in JIS R3206, Was determined.

The visible light transmittance and the vertical emissivity of the tempered glass were measured, and were 83% and 0.13, respectively, and there was no change before and after the heat treatment.

That is, it was confirmed that the glass for freezing / refrigeration of the present invention can obtain a tempered glass which is not impaired in terms of performance even when subjected to heat treatment, and thus has excellent heat insulation performance and does not impair transparency. Was done.

Note that the same measuring instrument as in the first embodiment was used as the measuring instrument for calculating the visible light transmittance and the vertical emissivity.

Third Embodiment Next, the present inventor performed an antibacterial treatment using a test piece having the same film configuration as that of the above-described first embodiment.

That is, the test piece was heated to about 300 ° C., and a dispersion of silver colloid (concentration: 0.1%) was sprayed on both sides of the test piece to perform antibacterial treatment.

Then, for the test piece of the third embodiment subjected to the antibacterial treatment as described above, the film adhesion method of the antibacterial force test method I (1998 version) proposed by the Antibacterial Product Technology Council was When the film was changed to 0.1 ml with no film for glass, the antimicrobial properties were observed on both sides of the test piece.

The visible light transmittance and the vertical emissivity of the test piece of the third example were measured to be 83% and 0.13, respectively, and the chromaticness index of the reflection color tone was measured. a * and b * were "-1.5" and "-1.0", respectively, and there was no change before and after the antibacterial treatment.

The same measuring device as that of the first embodiment was used for calculating the visible light transmittance, the vertical emissivity, and the reflection color tone.

Next, the present inventor attached the test piece of the third embodiment to a freezer with the glass frit film 30 facing the inside of the refrigerator as a glass window of a vertical door which can be freely opened and closed. When the inside surface temperature, outside surface temperature, and heat transfer coefficient were measured at -5 ° C and outside temperature of 20 ° C, they were 10.1 ° C, 10.4 ° C, and 3.4 (W / m ^{2, respectively).}・ K), it was found that it has sufficient heat insulation performance and can prevent the occurrence of dew condensation inside and outside the refrigerator, which deteriorates the transparency.

The measurement of the inner surface temperature, the outer surface temperature, and the heat transmission coefficient was performed using the same measuring apparatus as in the first embodiment.

Fourth Embodiment Next, as shown in FIG. 2B, the present inventor raised and lowered a door on the upper surface of a refrigerator / refrigerator body 8b inclined by 20 ° (= θ) with respect to the horizontal direction. Glass and float plate glass of the present invention were attached as the glass for use, and the transparency was confirmed.

That is, a test piece having the same film configuration as in Example 1 was used for one glass of the door glass, and a float glass alone was used for the other glass, and the glass frit film was used for the test piece. 30 was attached to the freezer / refrigerator body 8b facing the inside of the refrigerator.

[0131] Then, the inside temperature of the refrigerator was set to -30 ° C, the ambient temperature outside the refrigerator was set to 20 ° C, and the product was put into the refrigerator and the opening / closing door was opened and closed. In contrast to the fogging of the simple substance, the visibility of the product inside deteriorated, whereas the test piece of the present invention generated only a slight fogging, did not affect the visibility, and therefore did not impair the transparency It was confirmed that.

Fifth Embodiment Next, the present inventor used a sputtering apparatus (see FIG. 5) to stack an intermediate layer 13 on a test piece having the same film configuration as in Example 1, Is a test piece of glass plate 1 / SnO ₂ film 2 / SiO ₂ film 3 / SnO ₂ : F film 4 / TiO ₂ film 11 / SiO ₂ : Al film 12 / glass frit film 30 (see FIG. 4) (Example 11) ) Was prepared.

That is, the glass 7 having the same film configuration as in Example 1 was washed, evacuated to a predetermined pressure in the load lock chamber 15, and then transferred to the film formation chamber 16 as shown by the arrow B. Then, oxygen is supplied from the gas supply port 20 so that the pressure in the film forming chamber 16 becomes 0.3 Pa, the glass 7 is heated to about 350 ° C. by the heater 19, and then titanium as a target substance is set. A DC voltage of 440 V is applied to the first cathode 17, which causes reactive sputtering with oxygen, and the glass 7 reciprocates under the first cathode 17, whereby the SnO ₂ : F film 4 A TiO ₂ film 11 having a thickness of 250 nm was laminated on the surface to form a fourth layer. Next, after turning off the power of the heater 19, the same reactive sputtering as described above was caused by using the second cathode 18 set with silicon to which 10 wt% of Al was added as a target, and the test piece was removed. By reciprocating below the second cathode 18, the SiO ₂ : Al film 12 having a thickness of 10 nm was laminated to form a fifth layer. Further, a glass frit film 30 was formed on the fifth layer in the same manner as in Example 1 (Example 11).

The obtained glass was measured for the scratch resistance and the vertical emissivity in the same manner as in the first example, and the contact angle of a water droplet and the photocatalytic activity test were performed.

As a result, the scratch resistance was as good as in Examples 1 to 4. The vertical emissivity was 0.13 as in the case of Example 1. Therefore, no performance deterioration due to the formation of the intermediate layer 13 was observed. It was also confirmed that the contact angle of the water droplet could be as small as 5 °. Further, the photocatalytic activity test was carried out by applying triolein to the surface of the intermediate layer 13 and irradiating it with ultraviolet rays, and good results were obtained.

Next, the present inventor confirmed the transparency when the present test piece (Example 11) was used as a glass window of a double door installed in the vertical direction of a freezer.

That is, the test piece of Example 11 was used for one glass window of the double door glass, and the float glass alone as a comparative example was used for the other glass window (Comparative Example 11). The piece was attached to the freezer body with the middle layer 13 facing the inside of the refrigerator.

The temperature inside the refrigerator is set to −20 ° C., the ambient temperature outside the refrigerator is set to 20 ° C., the inside of the refrigerator is turned on from 9 to 20 o'clock, and the door is opened and closed periodically for 30 days. A door open / close test was thus conducted.

Table 2 shows the measurement results of Example 11 and Comparative Example 11.

[0140]

[Table 2] As is clear from Table 2, the opening and closing of the door fogged the float plate glass alone and lowered the transparency, and the result of the opening and closing test was poor. Days), no fogging occurred and good results were obtained.

Thus, it was confirmed that even when the inside of the refrigerator / refrigerator was illuminated with a fluorescent lamp or the like, organic dirt on the surface could be decomposed and the hydrophilicity / water retention function could be maintained for a long period of time. Further, among the fourth and fifth layers having a hydrophilic / water retaining function shown in Table 2, the same result as described above was obtained even when the fifth layer was omitted and the fourth layer was constituted only by the fourth layer.

Sixth Example Next, the present inventor produced three different types of double-glazed glass (Examples 21 to 23) using the test piece of Example 1.

That is, as shown in FIG. 6, a float plate glass made of the test piece of the present invention, the freezing / refrigerating glass (hereinafter referred to as “the present invention glass”) 7 and the soda-lime glass, which are the test pieces of the first embodiment. 27, the glass 7 of the present invention and the float glass 27 are arranged so as to face each other such that the surface on which the laminated film 6 of the test piece is formed is located outside, and the hollow glass 23 is filled with air. Produced. The interval t between the hollow layers 23 was adjusted to 12 mm by the spacer member 21 made of aluminum (Example 21).

Next, similarly to the above, using the glass 7 of the present invention and the float plate glass 27, a double glazing in which an argon gas as a heat insulating gas was sealed in the hollow layer 23 was produced. The introduction of argon gas was carried out by penetrating two holes in the aluminum spacer member 21 and supplying argon gas to the hollow layer 23 from one of the holes by means of a cylinder. The gas inside the hollow layer 23 was replaced with argon gas by sealing the two holes with a sealing material. The interval t between the hollow layers 23 was adjusted to 6 mm by the spacer member 21 (Example 22).

Next, as shown in FIG. 8, the present invention glass 7 and the float plate glass 27 are used, and the present invention glass 7 and the float glass 6 are arranged such that the surface of the test piece where the laminated film 6 is formed is located outside. The float glass plate 27 is arranged to face the same, and the minute spacer member 26 made of metal is sandwiched between the glass 7 of the present invention and the float glass plate 27 to adjust the interval t between the hollow layers 23 to 0.2 mm. Both upper and lower ends were sealed with a melting point glass 25. That is, a small hole is provided in the float glass sheet 27, and the glass sheet 7 and the float glass sheet 27 are heated to about 350 ° C. to fuse the low-melting glass 25 to about 250 ° C. After the layer 23 was put in a reduced pressure state, the layer 23 was sealed off, and the hollow layer 23 was made a reduced pressure layer. The pressure in the reduced pressure layer was 1 Pa or less (Example 23).

Next, after measuring the visible light transmittance of the test piece of each of the above examples, the present inventors set the present invention glass 7 inside the refrigerator as a glass window of a vertical door that can be freely opened and closed. The inside surface temperature was set at -20 ° C and the outside temperature was set at 20 ° C, and the inside surface temperature, outside surface temperature, and heat transfer coefficient were measured.

Further, in the same manner as described above, a comparative example in which the hollow layer 23 was used as an air layer, an argon gas layer, and a reduced pressure layer using two float plate glasses (Comparative Examples 21 to 23). In the same manner as in the above, it was attached to a freezer as a glass window of a vertical door, and the same measurement as in Examples 21 to 23 was performed. The measurement was performed using the same device as in the first embodiment.

[0148] Table 3 shows the measurement results of each of the examples and the comparative examples.

[0149]

[Table 3] As is apparent from Table 3, Comparative Examples 21 to 23 have a visible light transmittance of 80% or more and a heat transmission coefficient of 2.5 (W / m ² · K) or less, and thus have a poor heat insulating performance. Is excellent, but since the low radiation layer is not formed, the surface temperature inside and outside the refrigerator is low, fogging and dew condensation easily occur on the glass, and the transparency is impaired.

On the other hand, in Examples 21 to 23, since the low emissive layer was formed, the heat insulation performance was excellent and the surface temperatures inside and outside the refrigerator were higher than those of Comparative Examples 21 to 23. However, it was confirmed that the loss of visibility could be avoided as much as possible.

[0151]

[Effect of the invention]

 As described in detail above, according to the refrigerator / refrigerator glass of the present invention, the glass frit film acts as a protective film for the oxide semiconductor film, so that the product can be placed on the surface of the glass window when the product is taken out. Even if it hits, the internal confirmation can be maintained without the part of the product being cut off and sticking to the glass window.

[0152] Since the glass frit film covers the entire surface of the oxide semiconductor film, the oxide semiconductor film can be sufficiently protected.

[0153] In addition, since the glass frit film is covered with a predetermined pattern over the oxide semiconductor film, the glass can be manufactured without lowering the quenching effect in the air-cooling strengthening step.

Further, since the second tin oxide film acts as a low-radiation layer, the emissivity for radiant heat is reduced between the second space (inside of the refrigerator) and the surface of the low-radiation layer, and radiant heat transfer is performed. Not only improves the heat insulation of the glass window, but also raises the surface temperature of the low-emissivity layer, and the atmosphere in the first space (outside the warehouse) is changed to the second space when taking out or refilling goods from the warehouse. (Even inside the refrigerator) and when the surface of the low emissivity layer is touched, dew condensation hardly occurs on the surface of the low emissivity layer. In addition, the temperature of the second space and the surface temperature of the low emissivity layer The difference increases so that convective heat transfer is likely to occur, so that air on the surface of the low-emissivity layer is also easily exchanged.

Further, since an intermediate layer made of an inorganic substance including the first tin oxide film and the silicon oxide film is interposed between the low-emission layer and the glass plate, this intermediate layer functions as a refractive index adjusting layer. As a result, the reflection color tone of the glass for freezing / refrigeration can be easily adjusted to an achromatic color, which exhibits a natural color, that is, a neutral color, and is used for a refrigerator / refrigerated showcase or a see-through vending machine. Even in such a case, high transparency can be maintained with a neutral reflection color tone. Since the above-mentioned inorganic substance is composed of a tin oxide film and a silicon oxide film, it does not impair the physical durability of the low-emissivity layer.

Further, since the intermediate layer includes the first tin oxide film and the silicon oxide film, the first tin oxide film acts as an alkali ion release preventing layer, thereby preventing a decrease in low radiation performance. In addition, since the silicon oxide film acts as the permeability increasing layer, the visible light transmittance is increased, and the internal confirmability can be improved.

[0157] The low-emissivity layer includes a tin oxide film. Since the tin oxide film is an oxide semiconductor film having excellent physical and chemical durability, the low-emissivity layer can be easily cleaned. It is possible to improve the usability at a low cost, and since the characteristics do not deteriorate even if the heat treatment is performed, the heat treatment can be performed after the film formation. Heat treatment can be performed quickly at a low cost with simplification. The durability can be maintained even if the low-emission layer is constantly exposed to the low-temperature atmosphere in the freezer / refrigerator, even if a sudden change in temperature occurs due to the intrusion of the room temperature atmosphere outside the refrigerator. When the inside of the freezer / refrigerator is cleaned, it can be prevented from being rubbed and worn, and the ingress and egress of goods and the careless contact of the purchaser with the low radiation layer can be prevented.

[0158] Since the tin oxide film constituting the low-emissivity layer contains fluorine, the conductivity of the film can be increased and the heat insulating performance can be improved.

[0159] Since the total thickness of the oxide semiconductor film is 250 to 750 nm, the vertical emissivity can be kept low to increase the surface temperature of the low-emissivity layer, and the film has anti-scratch characteristics. And the transparency can be maintained. Since the heat transmission coefficient of the glass for refrigerators and refrigerators of the present invention is 4.00 W / m ² · K or less, the heat insulation can be improved.

[0160] Further, since the refrigerator / refrigerator glass of the present invention has a visible light transmittance of 75% or more, it is possible to sufficiently secure the internal confirmation of the product inside the refrigerator / refrigerator from the outside at room temperature. it can.

[0161] Furthermore, the refrigerator / refrigerator glass of the present invention has an oxide semiconductor film having a vertical emissivity of 0.2. Since it is 15 or less, radiant heat exchange between the inside of the freezer / refrigerator and the surface of the low radiation layer can be minimized while maintaining high transparency as a glass window.

Further, when the intermediate layer 13 mainly composed of a composite oxide or a mixed oxide containing at least one element of silicon, aluminum and titanium is formed on the surface of the low-emissivity layer, 13 has a hydrophilicity / water retention function, and can reduce the contact angle even if water droplets adhere to it. Therefore, even if water condenses on the intermediate layer 13, it is difficult for dew condensation to occur and transparency is impaired. It can be avoided as much as possible. In particular, when the photocatalytically active substance is contained in the intermediate layer 13, the organic dirt on the surface can be decomposed to maintain the hydrophilicity / water retention function for a long period of time.

Further, the double-glazing or laminated glass using the glass for freezing / refrigerator of the present invention has excellent transparency, so that the glass for freezing / refrigeration is insulated while maintaining the desired transparency. The performance can be further improved.

[Brief description of the drawings]

FIG. 1 is a cross-sectional view schematically showing a first embodiment of a refrigerator / refrigerator glass according to the present invention.

FIG. 2 is a view showing an example of a state in which the glass for freezing / refrigerator of the present invention is attached to a freezing / refrigerator body.

FIG. 3 is a schematic configuration diagram schematically showing a CVD film forming apparatus.

FIG. 4 is a cross-sectional view schematically showing a second embodiment of the glass for a refrigerator / refrigerator according to the present invention.

FIG. 5 is a schematic configuration diagram schematically showing a sputtering apparatus.

FIG. 6 is a cross-sectional view schematically showing the first embodiment of the glass article according to the present invention.

FIG. 7 is a cross-sectional view schematically illustrating a second embodiment of the glass article according to the present invention.

FIG. 8 is a sectional view schematically showing a third embodiment of the glass article according to the present invention.

[Explanation of symbols]

REFERENCE SIGNS LIST 1 glass plate 2 SnO ₂ film 3 SiO ₂ film 4 SnO ₂ : F film (low emission layer) 5,13 intermediate layer 6 laminated film (oxide semiconductor film) 11 TiO ₂ film (photocatalytic active layer) 12 SiO ₂ : Al Film 30 Glass frit film

──────────────────────────────────────────────────続 き Continued on front page (51) Int.Cl. ⁷ Identification code FI F25D 23/06 F25D 23/06 Z

Claims (26)

[Utility model registration claims] 1. A refrigerating / refrigerating glass partitioning a first space in a room temperature atmosphere and a second space in an atmosphere lower than room temperature, wherein a second space formed on a surface of the glass on the second space side in order. 1
An intermediate layer including a tin oxide film and a silicon oxide film, and an oxide semiconductor film including a low-emission layer including a second tin oxide film formed on the silicon oxide film; and covering the oxide semiconductor film. A refrigerator / refrigerant glass, comprising: a glass frit film. 2. The refrigerator / refrigerator glass according to claim 1, wherein the glass frit film is coated on the entire surface of the oxide semiconductor film. 3. The glass for refrigerators and refrigerators according to claim 1, wherein the glass frit film is coated on the oxide semiconductor film in a predetermined pattern. 4. The glass for a refrigerator or refrigerator according to claim 3, wherein the predetermined pattern is a dot having a pitch of 5 mm and a diameter of 2 mm. 5. The glass for a refrigerator or refrigerator according to claim 1, wherein the low-emissivity layer contains fluorine. 6. The total thickness of the oxide semiconductor film is 250.
The glass for a refrigerator / refrigerator according to any one of claims 1 to 5, wherein the thickness is from 750 to 750 nm. 7. The film thickness of said first tin oxide film is 10-5.
0 nm, and the thickness of the silicon oxide film is 10 to 100.
and the thickness of the low-emissivity layer is 200 to 600 nm.
The freezing / refrigerating glass according to any one of claims 1 to 6, wherein 8. The refrigerating / refrigerating glass according to claim 1, wherein the heat transmission coefficient is 4.00 W / m ² · K or less. 9. The freezing / refrigerating glass according to claim 1, wherein a visible light transmittance is 75% or more. 10. The refrigerator / refrigerator glass according to claim 1, wherein the vertical emissivity of the oxide semiconductor film is 0.15 or less. 11. The freezing and refrigerator glass according to claim 1, wherein the thickness of the glass plate is 2 to 4 mm. 12. The freezing / refrigerating glass according to claim 1, wherein the glass is strengthened by air cooling. 13. The refrigerator / refrigerator glass according to claim 1, wherein a predetermined heat treatment is performed at a predetermined temperature after the formation of the low-emissivity layer. 14. An intermediate layer mainly composed of a composite oxide or a mixed oxide containing at least one element of silicon, aluminum, and titanium is formed on the low-emissivity layer. The freezing / refrigerating glass according to any one of claims 1 to 13. 15. The film thickness of the intermediate layer is 0.5 to 1000.
15. The glass for refrigerators and refrigerators according to claim 14, wherein 16. The refrigerator / refrigerator glass according to claim 14, wherein the intermediate layer contains a photocatalytically active substance. 17. The surface for the first space and the second space.
2. A predetermined antibacterial treatment is applied to at least one of the surfaces to the space.
17. The glass for freezing / refrigeration according to any one of items 16 to 16. 18. A refrigerator / refrigerator body having a horizontal glass surface and a tilt angle of 0 to 135 ° with respect to a state where the oxide semiconductor film is provided on a lower surface in a vertical direction. 2. The method according to claim 1, wherein:
8. The glass for freezing / refrigeration according to any one of 7 above. 19. The glass for a refrigerator / refrigerator according to claim 18, wherein the inclination angle is 0 ° to 60 °. 20. A plurality of glasses including the glass for freezing / refrigeration according to claim 1, wherein a surface of the glass plate on which the glass frit film is formed is positioned on the second space side. A glass article characterized in that the glass article is opposed to the glass sheet and a hollow layer is formed between the plurality of glasses. 21. The glass article according to claim 20, wherein the hollow layer is one of an air layer, a heat insulating layer, and a reduced pressure layer. 22. A transparent film containing a low-emitting layer or a low-emitting substance is formed on a surface of at least one glass facing the hollow layer among the plurality of glasses facing each other. The glass article according to claim 20 or 21, wherein 23. The hollow layer according to claim 20, wherein a low-emissivity layer or a transparent film containing a low-emissivity substance is disposed in the hollow layer at a distance from the surface of the glass. A glass article according to claim 1. 24. A plurality of glasses including the refrigerator / refrigerator glass according to claim 1, wherein a surface of the glass plate on which the glass frit film is formed is placed on the second space side. A glass article characterized by being overlapped with each other via a transparent resin layer. 25. A glass article, wherein the two glass articles according to claim 20 are overlapped via a transparent resin layer. 26. A surface for said first space and said second space.
3. A predetermined antibacterial treatment is applied to at least one of the surfaces to the space.
The glass article according to any one of 0 to 25.