JP2019020052A - Laminate, door body of refrigerator, and refrigerator - Google Patents

Abstract

To provide a laminate capable of suppressing occurrence of rust at a metal plate even in a case where the laminate is arranged on a front face of a product such as a refrigerator.SOLUTION: A laminate has: a glass substrate 12; an adhesion layer 14 arranged on the glass substrate 12; a metal plate 16a arranged on a surface of the adhesion layer 14 and at a center part of the adhesion layer 14; and a peripheral layer 18a arranged on the surface of the adhesion layer 14 and around the metal plate 16a, and selected from a group consisting of a glass layer and a rustproof metal layer, wherein at least a part of a side surface of the metal plate 16a contacts with the peripheral layer 18a.SELECTED DRAWING: Figure 1

Description

  The present invention relates to a laminate, a refrigerator door, and a refrigerator.

In recent years, various devices such as household appliances have been diversified, and high-end models are required to have high performance and a high-quality appearance. In response to these trends, products with improved design are proposed by placing a glass substrate on the front of various devices such as refrigerator doors, with no irregularities on the surface, deep luster, and design. Yes.
For example, Patent Document 1 discloses a laminated structure having a metal plate having a predetermined shape, a glass plate matching the shape of the metal plate, and an adhesive layer for the purpose of application to the product as described above. Yes.

Patent No. 6054528

On the other hand, the present inventors have pasted the laminated structure described in Patent Document 1 on the front surface of various devices and evaluated its characteristics, and found that the end of the metal plate in the laminated structure is easily rusted. did.
This invention makes it a subject to provide the laminated body by which generation | occurrence | production of the rust of the metal plate was suppressed also when arrange | positioning in front of products, such as a refrigerator, in view of the said situation.
Moreover, this invention also makes it a subject to provide the door body of a refrigerator which has the said laminated body, and a refrigerator.

  As a result of intensive studies to solve the above problems, the present inventors have found that the above problems can be solved by the following configuration.

(1) a glass substrate;
An adhesion layer disposed on a glass substrate;
A metal plate disposed on the surface of the adhesion layer and in the center of the adhesion layer;
A peripheral layer selected from the group consisting of a glass layer and a rust-proof metal layer, disposed on the surface of the adhesion layer and around the metal plate;
A laminate in which at least a part of a side surface of a metal plate is in contact with a peripheral layer.
(2) The laminate according to (1), wherein the side surface of the metal plate and the peripheral layer are in contact with each other over the entire circumference of the metal plate.
(3) The laminate according to (1) or (2), wherein the peripheral layer is a glass layer.
(4) The laminated body according to any one of (1) to (3), wherein the width of the peripheral layer is 1 cm or more.
(5) The laminate according to any one of (1) to (4), wherein the adhesion layer is a silicone resin layer.
(6) The laminated body in any one of (1)-(5) whose thickness of a glass substrate is 1.5 mm or less.
(7) The laminate according to any one of (1) to (6), wherein the metal plate is an iron plate.
(8) A door body of a refrigerator having the laminate according to any one of (1) to (7).
(9) A refrigerator having the refrigerator door according to (8).

ADVANTAGE OF THE INVENTION According to this invention, even when arrange | positioning in front of products, such as a refrigerator, the laminated body by which generation | occurrence | production of the rust of the metal plate was suppressed can be provided.
Moreover, according to this invention, the door body of the refrigerator which has the said laminated body, and a refrigerator can be provided.

It is sectional drawing of one Embodiment of the laminated body which concerns on this invention. It is a top view of the laminated body described in FIG. It is a top view of other embodiment of the laminated body of FIG. It is sectional drawing of other embodiment of the laminated body which concerns on this invention. It is a top view of the laminated body of FIG. It is sectional drawing of one Embodiment of the door body of a refrigerator provided with the laminated body which concerns on this invention. It is an expanded sectional view of the V section in FIG. It is sectional drawing of one Embodiment of the door body of a refrigerator in a prior art. It is an expanded sectional view of the W section in FIG.

  DESCRIPTION OF EMBODIMENTS Hereinafter, embodiments for carrying out the present invention will be described with reference to the drawings. However, the present invention is not limited to the following embodiments, and the following embodiments are not deviated from the scope of the present invention. Various modifications and substitutions can be made.

FIG. 1 is a cross-sectional view of an embodiment of a laminate according to the present invention. FIG. 2 is a top view of the laminate of FIG. In FIG. 2, the left-right direction on the drawing is the x-axis direction, and the up-down direction is the y-axis direction.
As shown in FIG. 1, the laminated body 10 a is disposed on the glass substrate 12, the adhesion layer 14 disposed on the glass substrate 12, the metal plate 16 a disposed on the adhesion layer 14, and the adhesion layer 14. And a peripheral layer 18a.
As shown in FIG. 1, the adhesion layer 14 is disposed on the entire surface of one main surface of the glass substrate 12.
Further, two of the metal plate 16a and the peripheral layer 18a are disposed on the adhesion layer 14, and the side surface of the metal plate 16a and the peripheral layer 18a are in contact with each other over the entire circumference of the metal plate 16a. In other words, the peripheral layer 18a is disposed so as to surround the metal plate 16a, and the side surface of the peripheral layer 18a and the side surface of the metal plate 16a are in contact with each other.

As shown in FIGS. 1 and 2, in the laminated body 10 a, the metal plate 16 a is disposed at the central portion of the adhesion layer 14. In other words, the metal plate 16 a is disposed on the adhesion layer 14 so that a peripheral region that does not contact the metal plate 16 a remains on the surface of the adhesion layer 14.
As shown in FIG. 2, the widths of the metal plate 16a in the x-axis direction and the y-axis direction are smaller than the widths of the glass substrate 12 in the x-axis direction and the y-axis direction, respectively.
The peripheral layer 18a is a frame-like layer disposed on the surface of the adhesion layer 14 and in a peripheral region where the metal plate 16a is not disposed. When the laminated body 10a is observed from the normal direction of the surface of the laminated body 10a, the peripheral edge of the glass substrate 12a and the peripheral edge of the peripheral layer 18a coincide with each other. In other words, when the laminated body 10a is observed from the normal direction of the surface of the laminated body 10a, the shape of the glass substrate 12a and the shape of the layer composed of the metal plate 16a and the peripheral layer 18a coincide with each other. .
As will be described in detail later, in the laminate 10a, the side surface of the metal plate 16a and the peripheral layer 18a are in contact with each other so as to cover the side surface of the metal plate 16a over the entire circumference of the metal plate 16a. As a result, rust on the side surface of the metal plate 16a hardly occurs.
Hereinafter, each member which comprises the laminated body 10a is explained in full detail.

<Glass substrate>
The glass substrate 12 has a role of improving the designability of the article on which the laminate is disposed. Usually, when a laminated body is arrange | positioned in the front surface of articles | goods, the glass substrate 12 is arrange | positioned at the most visual recognition side.
The type of glass of the glass substrate 12 is not particularly limited, but non-alkali borosilicate glass, borosilicate glass, soda lime glass, high silica glass, and other oxide-based glass mainly containing silicon oxide are preferable. As the soda lime glass, a physical tempered glass or a chemically tempered glass is preferable in terms of high cracking resistance. As the oxide glass, a glass having a silicon oxide content of 40 to 90% by mass in terms of oxide is preferable.
Specific examples of the glass substrate 12 include a glass substrate made of chemically tempered glass of soda lime glass (trade name “Leoflex” manufactured by Asahi Glass Co., Ltd.).

  The thickness of the glass substrate 12 is preferably 1.5 mm or less, and more preferably 1.2 mm or less, from the viewpoint of reduction in thickness and / or weight. The lower limit is preferably 0.5 mm or more from the viewpoint of handleability.

In FIG. 1, the shape of the glass substrate 12 is a rectangular shape, but is not particularly limited, and may be a square shape or a polygonal shape other than a rectangular shape.
Further, the surface on the viewing side of the glass substrate 12 may be smooth or uneven. If there are irregularities, simple swell at the time of glass molding may be used, but the pattern may be formed by frost treatment, sand blast treatment, CO ₂ laser processing, or the like.

  The glass substrate 12 may be composed of two or more layers. In this case, the material for forming each layer may be the same material or a different material. In this case, “the thickness of the glass substrate 12” means the total thickness of all the layers.

  The manufacturing method in particular of the glass substrate 12 is not restrict | limited, Usually, a glass raw material is fuse | melted and it is obtained by shape | molding molten glass in plate shape. Examples of such a molding method include a float method, a fusion method, and a slot down draw method.

<Adhesion layer>
The adhesion layer 14 has a role of bringing the glass substrate 12 into contact with the metal plate 16a and the peripheral layer 18a.
The type of the adhesion layer 14 is not particularly limited, and may be an organic layer made of a resin or the like, an inorganic layer made of an inorganic material, or a multilayer. Hereinafter, each case will be described in detail.

(Organic layer)
The organic layer is preferably a resin layer containing a predetermined resin. The type of resin that forms the resin layer is not particularly limited, and examples thereof include silicone resin, polyimide resin, acrylic resin, polyolefin resin, polyurethane resin, and fluorine resin. Several types of resins can be mixed and used. Of these, silicone resins, polyimide resins, and fluorine resins are preferable, and silicone resins are more preferable.

The silicone resin is a resin containing a predetermined organosiloxy unit and is usually obtained by curing curable silicone. The curable silicone is classified into an addition reaction type silicone, a condensation reaction type silicone, an ultraviolet ray curable type silicone, and an electron beam curable type silicone depending on the curing mechanism, and any of them can be used. Among these, addition reaction type silicone or condensation reaction type silicone is preferable.
As the addition reaction type silicone, a curable composition which contains a main agent and a crosslinking agent and cures in the presence of a catalyst such as a platinum-based catalyst can be suitably used. Curing of the addition reaction type silicone is accelerated by heat treatment. The main component in the addition-reactive silicone is preferably an organopolysiloxane having an alkenyl group (such as a vinyl group) bonded to a silicon atom (that is, an organoalkenylpolysiloxane, preferably a straight chain). These are the cross-linking points. The cross-linking agent in the addition reaction type silicone is preferably an organopolysiloxane having a hydrogen atom (hydrosilyl group) bonded to a silicon atom (that is, an organohydrogenpolysiloxane, preferably linear). Hydrosilyl groups and the like serve as crosslinking points.
The addition reaction type silicone is cured by an addition reaction between the main agent and the crosslinking agent. In addition, it is preferable that the molar ratio of the hydrogen atom couple | bonded with the silicon atom of organohydrogen polysiloxane with respect to the alkenyl group of organoalkenyl polysiloxane is 0.5-2.

When an addition reaction type silicone is used, a catalyst (in particular, a platinum group metal catalyst) may be further used as necessary.
The platinum group metal catalyst (platinum group metal catalyst for hydrosilylation) is used to promote and accelerate the hydrosilylation reaction between the alkenyl group in the organoalkenylpolysiloxane and the hydrogen atom in the organohydrogenpolysiloxane. It is a catalyst. Examples of the platinum group metal-based catalyst include platinum-based, palladium-based, and rhodium-based catalysts, and it is particularly preferable to use a platinum-based catalyst from the viewpoints of economy and reactivity.

The condensation reaction type silicone includes a hydrolyzable organosilane compound as a monomer or a mixture thereof (monomer mixture), or a partial hydrolysis condensate obtained by subjecting a monomer or monomer mixture to a partial hydrolysis condensation reaction (organopolysiloxane). Can be suitably used.
A silicone resin can be formed by proceeding a hydrolysis / condensation reaction (sol-gel reaction) using this condensation reaction type silicone.

  The thickness of the organic layer is not particularly limited, but is preferably 1 to 100 μm, more preferably 5 to 50 μm, and further preferably 7 to 30 μm. When the thickness of the organic layer is within such a range, the glass substrate 12 and the metal plate 16a are sufficiently adhered.

(Inorganic layer)
The material constituting the inorganic layer is not particularly limited, but preferably includes at least one selected from the group consisting of oxides, nitrides, oxynitrides, carbides, carbonitrides, silicides, and fluorides.
Examples of the oxide (preferably metal oxide), nitride (preferably metal nitride), and oxynitride (preferably metal oxynitride) include, for example, Au, Cu, Fe, Pt, Mo, W C, Si, Hf, Zr, Ta, Ti, Y, Nb, Na, Co, Al, Zn, Pb, Mg, Bi, La, Ce, Pr, Sm, Eu, Gd, Dy, Er, Sr, Sn And oxides, nitrides, and oxynitrides of one or more elements selected from In and Ba. More specifically, silicon nitride oxide (SiN _x O _y ), titanium oxide (TiO ₂ ), indium oxide (In ₂ O ₃ ), indium cerium oxide (ICO), tin oxide (SnO ₂ ), zinc oxide (ZnO) ), Gallium oxide (Ga ₂ O ₃ ), indium tin oxide (ITO), indium zinc oxide (IZO), zinc oxide tin (ZTO), and gallium-doped zinc oxide (GZO).

Examples of the carbide (preferably metal carbide) and carbonitride (preferably metal carbonitride) include, for example, carbide of one or more elements selected from Ti, W, Si, Zr, and Nb, and carbonitride Products and carbonates. An example is silicon carbide oxide (SiCO).
The carbide may be a so-called carbon material, for example, a carbide obtained by sintering a resin component such as a phenol resin.
Examples of silicides (preferably metal silicides) include silicides of one or more elements selected from Mo, W, and Cr.
Examples of fluorides (preferably metal fluorides) include fluorides of one or more elements selected from Mg, Y, La, and Ba. An example is magnesium fluoride (MgF ₂ ).

The thickness of the inorganic layer is not particularly limited, but is preferably 5 to 5000 nm, and more preferably 10 to 500 nm.
The surface roughness (Ra) of the inorganic layer is preferably 2.0 nm or less, and more preferably 1.0 nm or less. The lower limit is not particularly limited, but 0 is most preferable. If it is the said range, adhesiveness with a metal plate will become more favorable.
Ra is measured according to JIS B 0601 (revised 2001).

The adhesion layer 14 may be a plasma polymerization film.
When the adhesion layer 14 is a plasma polymerized film, materials for forming the plasma polymerized film are CF ₄ , CHF ₃ , C ₂ H ₆ , C ₃ H ₆ , C ₂ H ₂ , CH ₃ F, C ₄ H _8, etc. Fluorocarbon monomers, methane, ethane, propane, ethylene, propylene, acetylene, benzene, toluene and other hydrocarbon monomers, hydrogen, SF _{6 and the} like. In particular, a plasma polymerization film made of a fluorocarbon monomer or a hydrocarbon monomer is preferable. These may use only 1 type and may mix and use 2 or more types.
The thickness of the plasma polymerized film is preferably 1 to 100 nm, more preferably 1 to 50 nm, and even more preferably 1 to 10 nm from the viewpoint of scratch resistance.

<Metal plate>
The metal plate 16a has a role of reinforcing the strength of the glass substrate 12.
The kind in particular of metal plate 16a is not restrict | limited, For example, an iron plate, an aluminum plate, a SUS board, a copper plate etc. are mentioned.
Although the thickness in particular of the metal plate 16a is not restrict | limited, 0.1-2.0 mm is preferable and 0.3-1.0 mm is more preferable at the point of the balance of the intensity | strength of a laminated body, and the weight of a laminated body.
The surface of the metal plate 16a on the glass substrate 12 side may be treated for decorative purposes, and may be subjected to, for example, brushing, acid etching, sand blasting, or the like.

In FIG. 1, the shape of the metal plate 16 a is a rectangular shape, but is not particularly limited, and may be a square shape or a polygonal shape other than a rectangular shape.
Usually, the outer shape of the metal plate 16 a is smaller than the outer shape of the glass substrate 12. Therefore, when the metal plate 16 a is disposed on the adhesion layer 14, a peripheral region that is not in contact with the metal plate 16 a can be formed on the surface of the adhesion layer 14.

<Peripheral layer>
The peripheral layer 18a is a layer disposed on the adhesion layer 14 and disposed so as to contact the side surface of the metal plate 16a over the entire circumference of the metal plate 16a. The presence of the peripheral layer 18a in contact with the side surface of the metal plate 16a suppresses the generation of rust from the side surface of the metal plate 16a.
In FIG. 2, the peripheral layer 18a is described as a single member, but may be composed of a plurality of members. For example, as shown in FIG. 3, the peripheral layer surrounding the metal plate 16a includes a peripheral layer 181a that contacts the side surface of one edge of the metal plate 16a and a peripheral layer 182a that contacts the side surface of one edge of the metal plate 16a. And a peripheral layer 183a that contacts the side surface of one edge of the metal plate 16a and a peripheral layer 184a that contacts the side surface of one edge of the metal plate 16a.

  The peripheral layer 18a is selected from the group consisting of a glass layer and a rust-proof metal layer, and a glass layer is preferable in terms of handling properties and rust-proof properties of the metal plate 16a.

  The width W of the peripheral layer 18a is not particularly limited, but is preferably 1.0 mm or more and more preferably 2.0 mm or more from the viewpoint that the rust prevention property of the metal plate 16a is more excellent. Although an upper limit in particular is not restrict | limited, 20 mm or less is preferable and 10 mm or less is more preferable from the point which the effect of this invention is saturated.

The thickness of the peripheral layer 18a is not particularly limited, but usually it is preferably equal to or greater than the thickness of the metal plate 16a. When the thickness of the peripheral layer 18a is equal to or greater than the thickness of the metal plate 16a, the side surface of the metal plate 16a is further suppressed from being exposed.
Specifically, the thickness of the peripheral layer 18a is preferably 0.1 mm or more, and more preferably 1.0 mm or more. Although an upper limit in particular is not restrict | limited, 10 mm or less is preferable and 5.0 mm or less is more preferable.

The kind in particular of glass which comprises the glass layer which is the peripheral layer 18a is not restrict | limited, The kind of glass of the glass substrate 12 mentioned above is mentioned.
The antirust metal layer which is the peripheral layer 18a is a metal layer having antirust properties. As a metal layer which has rust prevention property, the layer formed from the metal which has rust prevention property is mentioned. The metal having rust preventive properties is a metal that hardly causes rust, and examples thereof include stainless steel and aluminum. Moreover, as a metal layer which has rust prevention property, the metal layer to which the rust prevention process was given may be sufficient.

<Other members>
The laminated body may have other layers other than the glass substrate, the adhesion layer, the metal plate, and the peripheral layer described above as necessary.
For example, the laminate may further include a colored layer having a function of improving design properties. Note that the colored layer is disposed, for example, between a glass substrate and a metal plate.

The laminated body of the present invention is not limited to the form of FIG. 1 and is not particularly limited as long as at least a part of the side surface of the metal plate is in contact with the peripheral layer. For example, a laminate as shown in FIGS. 4 and 5 may be used. 4 shows a cross-sectional view of another embodiment of the laminate, and FIG. 5 shows a top view of the laminate of FIG. 4 of the laminate. In FIG. 5, the left-right direction on the drawing is the x-axis direction, and the up-down direction is the y-axis direction.
A laminated body 10b shown in FIGS. 4 and 5 is disposed on the glass substrate 12, the adhesion layer 14 disposed on the glass substrate 12, the metal plate 16b disposed on the adhesion layer 14, and the adhesion layer 14. And a peripheral layer 18b. The stacked body 10b has the same configuration as the above-described stacked body 10a except that the arrangement position of the peripheral layer 18b is different.
In the laminated body 10b, the peripheral layer 18b is disposed so as to come into contact with the side surfaces of two opposing edges (side parts) of the metal plate 16b.
As shown in FIG. 5, the width of the metal plate 16b in the x-axis direction is smaller than the width of the glass substrate 12 in the x-axis direction, but the width of the metal plate 16b in the y-axis direction is the width of the glass substrate 12 in the y-axis direction. Is the same.
As shown in FIGS. 4 and 5, in the laminated body 10 b, the metal plate 16 b is disposed at the center of the adhesion layer 14. More specifically, the metal plate 16 b is disposed on the adhesion layer 14 so that two end regions that do not contact the metal plate 16 b remain on the surface of the adhesion layer 14.
The peripheral layer 18b is a layer disposed on the surface of the adhesion layer 14 and in an end region where the metal plate 16a is not disposed.

<Method for producing laminate>
The manufacturing method in particular of a laminated body is not restrict | limited, A well-known method is employable. For example, an adhesion layer is formed on a glass substrate, and a metal plate is disposed on the central portion of the adhesion layer. Next, a method of producing a laminate by placing a glass plate that can be a glass layer or a rust-preventing metal plate that can be a rust-preventing metal layer on the surface of the adhesion layer on which the metal plate is not disposed is mentioned. .

The method for forming the adhesion layer on the glass substrate is not particularly limited. For example, when the adhesion layer is an organic layer, the composition for forming an organic layer is applied on the glass substrate to form a coating film. And a method of subjecting the coating film to a curing treatment. Moreover, when the adhesion layer is an inorganic layer, a method of providing an inorganic layer made of a predetermined component on a glass substrate by a vapor deposition method, a sputtering method, or a CVD method can be used.
As another method, there may be mentioned a method in which an adhesion layer is once formed on a temporary support, and the formed adhesion layer is transferred from the temporary support onto a glass substrate. Moreover, the precursor layer of the adhesion layer is formed on the temporary support, the precursor layer of the adhesion layer formed is transferred from the temporary support to the glass substrate, and then the adhesion layer is formed on the glass substrate. The method of doing is also mentioned.

The method for laminating the metal plate on the adhesion layer is not particularly limited, and a known method can be adopted.
For example, a method of stacking a metal plate on the surface of the adhesion layer under a normal pressure environment can be mentioned. If necessary, after the metal plate is stacked on the surface of the adhesion layer, the metal plate may be pressure-bonded to the adhesion layer using a roll or a press. Air bubbles mixed between the adhesion layer and the metal plate are relatively easily removed by pressure bonding using a roll or a press, which is preferable.

When pressure bonding is performed by a vacuum laminating method or a vacuum pressing method, it is more preferable because it suppresses mixing of bubbles and secures good adhesion. By press-bonding under vacuum, even if minute bubbles remain, there is an advantage that the bubbles do not grow by heating and are not likely to cause distortion of the metal plate.
When laminating metal plates, it is preferable that the surface of the metal plate in contact with the adhesion layer is sufficiently washed and laminated in an environment with a high degree of cleanliness. The higher the degree of cleanness, the better the flatness of the metal plate.
In addition, after laminating | stacking a metal plate, you may perform a pre-annealing process (heat processing) as needed.

  A method of laminating a glass plate that can be a glass layer or a rust-proof metal plate that can be a rust-proof metal layer on the adhesion layer is not particularly limited, and a known method can be adopted. Is mentioned.

<Application>
The said laminated body can be applied to various uses, for example, household appliance use, furniture use, and a building use are mentioned. Examples of household appliances include refrigerator doors.
Hereinafter, the door body of the refrigerator which has the said laminated body is explained in full detail.

<Refrigerator door>
FIG. 6 is a cross-sectional view of an embodiment of a refrigerator door having a laminate according to the present invention. As shown in FIG. 6, the door body 20 of the refrigerator is filled in a frame member 22, a laminated body 10 a fixed to the front surface of the frame member 22, and an interior surrounded by the frame member 22 and the laminated body 10 a. And a foam insulation 24.
The method for fixing the laminated body 10a to the frame member 22 is not particularly limited, and examples thereof include a method in which the laminated body 10a is fixed to the frame member 22 through an adhesion layer (not shown). The adhesion layer may be an adhesive layer or an adhesive layer.
Moreover, the filling method of the foam heat insulating material 24 is not particularly limited. For example, a stock solution of the foam heat insulating material 24 such as urethane foam is injected from an injection port (not shown) provided in a part of the frame member 22, and the frame member 22 is injected. And a method of foaming and growing in a space surrounded by the laminate 10a.

FIG. 7 is an enlarged cross-sectional view of a portion V in FIG. As shown in FIG. 7, the laminated body 10a is fixed to the frame member so that the surface of the laminated body 10a on the side where the peripheral layer 18a is disposed faces the frame member 22 side.
As shown in FIG. 7, when the peripheral layer 18a is disposed at the end portion in the laminated body 10a, the peripheral layer 18a is disposed between the frame member 22 and the metal plate 16a, and thus the metal plate 14a. Is suppressed from coming into contact with moisture and oxygen in the atmosphere, and as a result, the effects of the present invention are obtained.

In addition, in FIG. 8, it is sectional drawing of one Embodiment of the door body of a refrigerator in a prior art. As shown in FIG. 8, the door body 200 of the refrigerator is filled in the frame member 22, the laminated body 100 fixed to the front surface of the frame member 22, and the interior surrounded by the frame member 22 and the laminated body 100. And a foam insulation 24.
FIG. 9 is an enlarged cross-sectional view of a portion W in FIG. As shown in FIG. 9, the laminated body 100 does not have a peripheral layer, and therefore the metal plate 16 c is in direct contact with the frame member 22. Therefore, rust tends to occur on the side surface of the edge of the metal plate 16c on the frame member 22 side.

  EXAMPLES The present invention will be specifically described below with reference to examples and the like, but the present invention is not limited to these examples.

  In the following examples and comparative examples, a chemically tempered glass substrate made of soda lime (length: 350 mm, width: 300 mm, plate thickness: 1.1 mm, trade name “Leoflex” manufactured by Asahi Glass Co., Ltd.) was used as the glass substrate. . Moreover, as the metal plate 1, an iron plate (length: 330 mm, width: 280 mm, plate thickness: 0.4 mm) was used. Moreover, as the metal plate 2, an iron plate (length: 350 mm, width: 300 mm, plate thickness: 0.4 mm) was used.

<Example 1>
First, an alkenyl group-containing organopolysiloxane (number average molecular weight: 2000, number of alkenyl groups: 2 or more) (100 parts by mass) and hydrogen polysiloxane (number average molecular weight: 2000, number of hydrosilyl groups: 2) Or more) (6.7 parts by mass). The mixing molar ratio of the alkenyl group in the alkenyl group-containing organopolysiloxane and the hydrosilyl group in the hydrogen polysiloxane (number of moles of hydrosilyl group / number of moles of alkenyl group) was 0.4 / 1. It was. Furthermore, 300 ppm of the catalyst (platinum-based catalyst) was added to the total mass (100 parts by mass) of the alkenyl group-containing organopolysiloxane and hydrogen polysiloxane. Let this liquid be the curable resin composition X.
This curable resin composition X is coated on the main surface of a temporary support (PET) using a die coater to temporarily support a coating film containing uncured alkenyl group-containing organopolysiloxane and hydrogen polysiloxane. Provided on the body.
Next, the glass substrate was cleaned with pure water, and further cleaned by UV cleaning.
Next, the temporary support on which the coating film is formed and the glass substrate are laminated so that the coating film formed on the temporary support is in contact with the glass substrate. Was transferred onto a glass substrate.
Next, the glass substrate on which the coating film is disposed is heated to 140 ° C. in the air for 3 minutes, and then heated and cured at 230 ° C. for 20 minutes in the air to form a silicone resin layer having a thickness of 30 μm on the glass substrate. It formed and obtained the glass substrate with a silicone resin layer.
The silicone resin layer was disposed on the entire surface of the glass substrate.

Next, the glass substrate with a silicone resin layer obtained above and the metal plate 1 were bonded together by a vacuum press at room temperature so that the silicone resin layer and the metal plate were in close contact with each other. When the metal plate 1 is disposed on the silicone resin layer, the metal plate 1 is laminated on the silicone resin layer so that a peripheral region that does not contact the metal plate 1 remains in the silicone resin layer (FIGS. 1 and 2). reference).
Next, the glass plate was bonded together on the peripheral area | region which has not contact | adhered the metal plate 1 of the contact | adherence layer surface, and the laminated body 1 which has a glass layer was obtained (refer FIG. 1 and 2). In the obtained laminated body, as shown in FIGS. 1 and 2, the side surface of the metal plate 1 and the glass layer were in contact with each other over the entire circumference of the metal plate 1.
In addition, the width W (refer FIG. 1) of the glass layer was 10 mm.

<Comparative Example 1>
A glass substrate with a silicone resin layer was obtained in the same manner as in Example 1.
Next, the laminated body 3 was obtained by using the metal plate 2 instead of the metal plate 1. In the laminate 3, the metal plate 2 is disposed on the entire surface of the adhesion layer, and the glass plate or the silicone resin is not exposed in the peripheral region of the metal plate 2 and is in an exposed state.

<Evaluation>
Salt spray according to JIS Z2371: 2015, except that an evaluation sample in which the end of the laminate was fitted into a polystyrene frame member as shown in FIG. 6 (Examples 1 and 2) or FIG. 8 (Comparative Example 1) was used. The test was conducted. After spraying with salt water for 1000 hours, the laminate was taken out from the polystyrene frame member, the corrosion area ratio was visually confirmed from the glass plate surface side of the laminate, and evaluated according to the following evaluation criteria. The corrosion area ratio represents the ratio of the corroded area to the observed area (main surface area) of the metal plate.
A: The corrosion area ratio was 0.02% or less.
B: Corrosion area ratio was more than 0.02% and 0.05% or less.
C: Corrosion area ratio was more than 0.05% and 1% or less.
D: Corrosion area ratio was more than 1%.

As shown in Table 1 above, it was confirmed that the occurrence of rust was suppressed with the laminate of the present invention.
In Comparative Example 1, the corrosion area ratio exceeded 10%.

10a, 10b Laminated body 12 Glass substrate 14 Adhesion layers 16a, 16b, 16c Metal plates 18a, 18b, 181a, 182a, 183a, 184a Peripheral layer 20 Refrigerator door body 22 Frame member 24 Foam insulation

Claims (9)

A glass substrate;
An adhesion layer disposed on the glass substrate;
A metal plate disposed on the surface of the adhesion layer and in the center of the adhesion layer;
A peripheral layer selected from the group consisting of a glass layer and a rust-proof metal layer, disposed on the surface of the adhesion layer and around the metal plate;
A laminate in which at least a part of a side surface of the metal plate is in contact with the peripheral layer.   The laminate according to claim 1, wherein a side surface of the metal plate and the peripheral layer are in contact with each other over the entire circumference of the metal plate.   The laminate according to claim 1 or 2, wherein the peripheral layer is the glass layer.   The laminated body of any one of Claims 1-3 whose width | variety of the said surrounding layer is 1 cm or more.   The laminate according to any one of claims 1 to 4, wherein the adhesion layer is a silicone resin layer.   The laminated body of any one of Claims 1-5 whose thickness of the said glass substrate is 1.5 mm or less.   The laminate according to any one of claims 1 to 6, wherein the metal plate is an iron plate.   The door body of a refrigerator which has a laminated body of any one of Claims 1-7.   A refrigerator having the refrigerator door according to claim 8.