JP2012121760A - Heat ray-reflecting glass that has water-absorbing film - Google Patents

Abstract

Provided is a heat ray reflective glass having wear resistance and moisture resistance, which enables a silver-based heat ray reflective film formed on a single glass substrate to function with durability without deterioration or deterioration. .
SOLUTION: At least one surface of a glass substrate has a heat ray reflective film having a layer containing silver as a main component, and the surface preferably has a water absorption of 5 to 150 mg / cm ³ in saturated water absorption. A heat-reflective glass having a water-absorbing coating composed mainly of a resin.
[Selection] Figure 1

Description

  The present invention relates to a heat ray reflective glass having a water absorbing film, and more particularly to a heat ray reflecting glass having a water absorbing film having wear resistance and moisture resistance.

  Conventionally, a heat ray reflective film, generally a heat ray reflective film having a layer mainly composed of silver (hereinafter sometimes referred to as a silver-based heat ray reflective film) is used to impart heat insulation performance to a glass plate. A method, a method of applying a heat insulating type that absorbs heat, and the like have been adopted. Here, heat-absorbing type heat-insulating coatings can be applied to single-plate glass substrates, but silver-based heat ray reflective films can be used on a single plate for durability such as mechanical strength and deterioration of silver due to moisture. Have been used by providing them on the inside of laminated glass in which a plurality of glass plates are laminated.

  However, the laminated glass structure requires time and labor for assembling and manufacturing, and the cost is great. Therefore, an attempt is made to obtain a glass with a metal film having durability while being formed on a single glass substrate. Attempts have been made.

  For example, in Patent Document 1, in a glass with a conductive film in which a plurality of thin film layers including a metal film are formed on at least one surface of a glass substrate, and a metal compound film is disposed on the outermost layer, a film thickness is further formed on the surface. A glass with a conductive film formed by depositing a glassy thick film made of a low melting point glass of 2 μm or more is disclosed. However, when the method of depositing the glassy thick film is applied to the silver-based heat ray reflective film, it cannot be said that the single plate glass substrate has sufficient durability.

JP 2000-133987 A

  The present invention has been made to solve the above-described problems, and enables a silver-based heat ray reflective film formed on a single glass substrate to function with durability without deterioration or deterioration. An object of the present invention is to provide a heat ray reflective glass with a protective film having wear resistance and moisture resistance.

Since the silver-based heat ray reflective film is vulnerable to moisture, it is considered that the provision of a water-absorbing film promotes the deterioration of the silver-based heat ray reflective film. However, the present inventor has found that a heat ray reflecting glass having a water absorbing film having wear resistance and moisture resistance can be obtained by providing a water absorbing film on the silver-based heat ray reflecting film.
That is, this invention provides the heat ray reflective glass which has the structure of the following [1]-[11].
[1] A heat ray reflective glass having a heat ray reflective film having a layer mainly composed of silver on at least one surface of a glass substrate, and further having a water absorbent film mainly comprising a water absorbent resin on the surface thereof.
[2] The heat ray reflective glass according to [1], wherein the water absorption resin has a saturated water absorption amount of 5 to 150 mg / cm ³ .
[3] A heat ray reflective glass having the water absorbing film according to [1] or [2], wherein the water absorbing film has a thickness of 5 to 50 μm.
[4] The heat ray reflective glass according to any one of [1] to [3], wherein the water-absorbing resin is a crosslinked resin obtained by a reaction between a polyepoxide and a curing agent.
[5] The water-absorbent resin according to any one of [1] to [3], wherein the water-absorbent resin is a cross-linked resin obtained by a reaction between a cross-linkable vinyl polymer having a cationic group and a cross-linkable group and a cross-linking agent. Heat ray reflective glass.
[6] The heat ray reflective glass according to any one of [1] to [3], wherein the water absorbent resin is hydroxypropyl cellulose, polyvinyl alcohol, polyvinyl acetal, polyvinyl pyrrolidone, or polyvinyl acetate.
[7] The heat ray reflective glass according to [4], wherein the polyepoxide is a glycidyl ether-based polyepoxide.
[8] The glycidyl ether-based polyepoxide is one or more selected from the group consisting of glycerin polyglycidyl ether, diglycerin polyglycidyl ether, polyglycerin polyglycidyl ether, and sorbitol polyglycidyl ether. Heat ray reflective glass.
[9] The heat ray reflective glass according to [6], further having a water repellent coating on the surface of the water absorbing coating.
[10] In the 70-rotation wear test using a CS-10F wear wheel with a load of 500 g based on JIS-R3212 (1998) on the surface of the water-absorbent coating, peeling of the heat ray reflective film from the glass substrate occurred. There is no heat-reflective glass which has a water-absorbing film in any one of [1]-[9] characterized by the above-mentioned.
[11] In a moisture resistance test in which the entire heat ray reflective glass is maintained for 500 hours under conditions of a temperature of 80 ° C. and a relative humidity of 85%, no white spots are generated in the heat ray reflective film. ] The heat ray reflective glass which has a water absorptive film in any one of.

  ADVANTAGE OF THE INVENTION According to this invention, the water-absorbing film which has abrasion resistance and moisture resistance which enables the silver-type heat ray reflective film formed on the glass plate of a single plate to function with durability, without deteriorating and deteriorating. It is possible to provide a heat ray reflective glass having the following.

It is sectional drawing which shows an example of the heat ray reflective glass which has the water absorbing film of this invention. It is sectional drawing which shows an example of the glass substrate with a silver type heat ray reflective film. It is sectional drawing which shows another example of the glass substrate with a silver type heat ray reflective film. It is an optical microscope photograph which shows the moisture-proof test result of the heat ray reflective glass obtained by the Example and the comparative example. (A) is a photograph of an example (Example 1), and (B) is a photograph of a comparative example (Example 4).

  The embodiment of the heat ray reflective glass having the water-absorbent coating of the present invention will be described below. The present invention is not construed as being limited to the following description.

  FIG. 1 is a cross-sectional view showing an example of a heat ray reflective glass having a water-absorbent coating according to the present invention. A heat ray reflective glass 10 shown in FIG. 1 has a heat ray reflective film 2 having a layer mainly composed of silver on the upper surface of a glass substrate 1, and further has a water absorbing film 3 on the surface thereof. Hereinafter, each component which comprises the heat ray reflective glass of this invention is demonstrated.

<Glass substrate>
As the glass substrate 1 used in the present invention, ordinary soda lime glass (also referred to as soda lime silicate glass), borosilicate glass, non-alkali glass, quartz glass and the like are used without particular limitation. Of these, soda lime glass is particularly preferred. Although it does not specifically limit about a shaping | molding method, For example, the float plate glass shape | molded by the float glass method etc. is preferable. In addition, in this invention, the kind of glass substrate is not specifically limited, Various glass plates, such as a soda lime glass plate and a heat ray absorption glass plate, can be used, and thickness is not limited.

<Heat ray reflective film>
As the heat ray reflective film 2 which the heat ray reflective glass of the present invention has on at least one surface of the glass substrate 1, a heat ray reflective film having a layer mainly composed of silver is used. As such a silver-based heat ray reflective film, specifically, a layer containing silver as a main component (also referred to as a heat ray reflective layer) is provided between a dielectric layer (also referred to as an antireflective layer) having an antireflection ability. Examples thereof include a silver-based multilayer heat ray reflective film having a structure laminated so as to be sandwiched. 1-4 may be sufficient as the number of layers of a heat ray reflective layer, However, 2-3 are preferable. The number of dielectric layers is the number obtained by adding 1 to the number of heat ray reflective layers.

Hereinafter, the configuration of the silver-based heat ray reflective film used in the present invention will be described with reference to FIGS. 2 and 3, but the configuration of the silver-based heat ray reflective film is not limited thereto.
FIG. 2 is a cross-sectional view showing an example of a glass substrate with a silver-based heat ray reflective film in which a silver-based heat ray reflective film is formed on a glass substrate. A glass substrate 20 with a silver-based heat ray reflective film is composed of a glass substrate 1 and a silver-based multilayer heat ray reflective film 2 formed on the glass substrate 1. The silver-based multilayer heat ray reflective film 2 has two heat ray reflective layers 110 and 120, and has three dielectric layers 210, 220, and 230 laminated so as to sandwich the two layers. One layer (hereinafter referred to as “bottom dielectric layer”) 210 outside the dielectric layer is in contact with the glass substrate 1. The other layer (hereinafter referred to as “top dielectric layer”) 230 outside the dielectric layer is a layer on which a water-absorbing film described later is formed. Hereinafter, the dielectric layer 220 having the heat ray reflective layers on both sides is referred to as a central dielectric layer in distinction from the other two layers.

  As the layers (heat ray reflective layers) 110 and 120 containing silver as a main component, a silver (Ag) metal layer or an alloy layer containing silver as a main component can be used. The heat ray reflective layer contains Ag as a main component and contains, for example, Pd, Au, Cu, Pt, etc. as other metal elements in an amount of 0.3 to 10 atomic% with respect to the total amount of Ag and other metal elements. A layer is preferred. By containing a metal element other than Ag in this range, an effect of stabilizing Ag can be obtained. In particular, when a layer containing Ag as a main component contains Pd, it is possible to immobilize Ag atoms (that is, to reduce migration of Ag), and to provide a layer excellent in stability and chemical durability at high temperatures. Can be formed. When the content of Pd increases, the film formation rate decreases and the visible light transmittance also decreases. In addition, the selective blocking property between visible light and near infrared rays (performance for transmitting visible light and blocking near infrared rays) tends to deteriorate. For this reason, the content of Pd is suitably 5.0 atomic% or less. In particular, 0.3 to 2.0 atomic% is preferable.

In the silver-based multilayer heat ray reflective film 2, the dielectric layers 210, 220, and 230 sandwiching the heat ray reflective layers 110 and 120 are layers made of a material mainly composed of metal oxide, nitride, oxynitride, or the like. The metal oxide, _{specifically, Bi 2 O 3, SnO 2} , ZnO, Ta 2 O 5, Nb 2 O 5, WO 3, TiO 2, Al 2 O 3, ZrO 2, In 2 O 3 Or a mixture thereof, ZnO containing Sn, Al, Cr, Ti, Si, B, Mg, In, Ga, or In ₂ O ₃ containing Sn.
Specifically, as the nitride, a nitride of at least one element selected from Si, Al and B, or a mixture of these nitrides and a nitride of Zr or Ti (composite nitriding) Etc.).

  The material used for the dielectric layer of the silver-based multilayer heat ray reflective film is selected so that the refractive index is approximately 1.7 to 2.6, particularly 1.8 to 2.6. Each dielectric layer of the silver-based multilayer heat ray reflective film may be a single layer or multiple layers. In the silver-based multilayer heat ray reflective film 2 shown in FIG. 2, the bottom dielectric that is in contact with the glass substrate 1 is used. The layer 210, the top dielectric layer 230 on which a water-absorbing film is formed, is composed of two layers, and the central dielectric layer 220 is composed of a single layer.

  In the case of a dielectric layer composed of heat ray reflective layers on both sides, such as the central dielectric layer 220, the heat ray reflective layer can be stably and highly crystalline among the dielectric layers made of the various materials. The dielectric layer is a Zn oxide layer or a Zn oxide layer containing at least one element selected from Sn, Al, Cr, Ti, Si, B, Mg, In and Ga. A single layer made of an oxide layer is preferable. In particular, an oxide layer of Zn containing Al and / or Ti is preferable.

  In addition, the dielectric layer located between the heat ray reflective layer and the glass substrate or the water-absorbing film, such as the bottom dielectric layer 210 and the top dielectric layer 230, has a Zn oxide layer (on the side in contact with the heat ray reflective layer). In FIG. 2, the layer indicated by 211 constituting the bottom dielectric layer 210 and the layer indicated by 231 constituting the top dielectric layer 230), nitride on the side in contact with the glass substrate or the water-absorbing coating. 2 layers (in FIG. 2, the layer indicated by 212 constituting the bottom dielectric layer 210 and the layer indicated by 232 constituting the top dielectric layer 230).

  Note that the nitride in the nitride-based layer is preferably a mixed nitride containing Al. In the mixed nitride containing Al, the ratio of atoms X other than Al to Al, X / Al, It is preferable that it is 0.05 or more. When the dielectric layer has a layer mainly composed of mixed nitride containing Al, it prevents diffusion of ions such as oxygen and sodium ions from the glass substrate and the water-absorbing coating into the silver multilayer heat ray reflective film. It works effectively.

  The silver-based multilayer heat ray reflective film used in the present invention basically has a structure in which the heat ray reflective layer is sandwiched between dielectric layers, but if necessary, at least one side of the heat ray reflective layer. It is also possible to provide a thin barrier layer. FIG. 3 is a cross-sectional view showing an example of a glass substrate with a silver-based heat ray reflective film in which a silver-based heat ray reflective film having a barrier layer is formed on a glass substrate. The silver-based heat ray reflective film 2 shown in FIG. 3 is the same as the silver-based heat ray reflective film shown in FIG. 2 except that barrier layers 311, 312, 321, 322 are formed so as to sandwich the two heat ray reflective layers 110, 120. Same as 2.

  These barrier layers work to prevent the heat ray reflective layer from being oxidized by forming a dielectric layer, and at least a part of the barrier layer is made of an unoxidized silver material. This is a layer remaining in the multilayer heat ray reflective film. The barrier layer is a layer provided to prevent oxidation of the dielectric layer due to heat treatment such as bending and strengthening performed thereafter.

  Specifically, the barrier layer is a material selected from at least one of metals such as Ti, Ta, Nb, Ni, Cr, Zn, and Sn, or a stainless steel alloy, Al—Zn alloy, or Ni—Cr alloy. And at least a part of the oxide is composed mainly of an unoxidized oxide. Thereafter, when the glass substrate with a silver-based multilayer heat ray reflective film is subjected to heat treatment, the material constituting the barrier layer is oxidized to an oxide.

  When the barrier layer contains the same material as the mixed oxide as the dielectric layer (especially the adjacent dielectric layer), it becomes easy to manage the target and control the film formation state. In addition, the adhesion between the layers may be increased, and the mechanical durability of the silver-based multilayer heat ray reflective film may be improved.

  In addition, in the silver-based multilayer heat ray reflective film, when there are a plurality of heat ray reflective layers, dielectric layers, and barrier layers constituting the same, the heat ray reflective layers, the dielectric layers, and the barrier layers may be the same. , May be different.

  The layer thickness of each layer of the silver-based multilayer heat ray reflective film used in the present invention depends on the number of layers constituting the heat ray reflective film and the type of material, but is generally 5 to 100 nm for the dielectric layer, and the heat ray reflective layer. Is preferably 5 to 20 nm, and the barrier layer in the case of having a barrier layer is preferably 0.1 to 3 nm. Further, the film thickness of the entire heat ray reflective film is preferably in the range of 50 to 400 nm, and more preferably in the range of 150 to 300 nm.

  The heat ray reflective film having such a laminated structure is provided on at least one surface of the glass substrate by using any known technique such as magnetron sputtering, electron beam evaporation, vacuum evaporation, chemical vapor deposition, or the like. . Each layer can be formed by the same method or by different methods.

  In addition, when using the glass substrate with a silver type multilayer heat ray reflective film having a barrier layer, such as the glass substrate with a silver type multilayer heat ray reflective film shown in FIG. 3, the silver type multilayer heat ray reflective film is subjected to heat treatment. It is preferable to form the following water-absorbing film on top. The heat treatment includes, for example, heat treatment associated with bending work, strengthening work, and the like, and specifically includes heat treatment that is held in the atmosphere at a temperature of about 570 to 700 ° C. for 3 to 15 minutes.

  Moreover, in this invention, it is also possible to use the commercial item of such a glass substrate with a silver type multilayer film. Specific examples of commercially available products include SUNGATE (registered trademark, manufactured by PGW).

<Water-absorbing film>
The heat ray reflective glass 10 having a water absorbent film of the present invention has a water absorbent film 3 mainly composed of a water absorbent resin on the surface of the silver-based heat ray reflective film 2. The water-absorbing film can impart antifogging performance by the water-absorbing action of the water-absorbing resin mainly constituting the water-absorbing film, and at the same time, the water-absorbing film functions as a protective film that protects the silver-based heat ray reflective film from abrasion. The water-absorbing coating is preferably composed of only a water-absorbing resin from the viewpoint of water absorption, but depending on the type of resin used, from the viewpoint of wear resistance, a material having excellent mechanical strength while ensuring water absorption The coating may be formed in combination.

(Water absorbent resin)
The water-absorbing resin used is not particularly limited as long as it has anti-fogging performance when the water-absorbing film is formed, and protects the silver-based heat ray reflective film from abrasion. If Shimese the water of such water-absorbent resins Specifically, the saturated water absorption amount measured by the following method, is preferably in the range of 5 to 150 mg / cm ^3, is 10-100 mg / cm ³ It is more preferable.

(Measurement method of saturated water absorption)
A 3.3 cm × 10 cm × 2 mm thick soda lime glass substrate is provided with a water-absorbing coating as a specimen, and this is left in an environment of 20 ° C. and 50% relative humidity for 1 hour. Immediately after exposure to warm water vapor at 0 ° C. and the distortion of the perspective image due to cloudiness or a water film on the surface, the moisture content (I) of the entire substrate having a water-absorbing coating is measured using a micro moisture meter. Further, the moisture content (II) is measured for the above substrate only by the same procedure. The value obtained by subtracting the amount of moisture (II) from the amount of moisture (I) divided by the volume of the water-absorbing film is taken as the saturated water absorption. The moisture content is measured as follows using a trace moisture meter FM-300 (manufactured by Kett Science Laboratory Co., Ltd.). The measurement sample is heated at 120 ° C., the moisture released from the sample is adsorbed to the molecular sieve in the micro moisture meter, and the mass change of the molecular sieve is measured as the moisture content. The end point of the measurement is when the amount of change in mass per minute becomes 0.02 mg or less.

  Depending on the thickness of the water-absorbing film and the content of the water-absorbing resin contained in the film, the saturated water absorption of the water-absorbing resin used takes the above values, so that the durability of the film can be ensured while ensuring sufficient water absorption. It is possible to prevent the decrease. Since the water-absorbent coating has sufficient water absorption, an antifogging effect on the glass substrate can be expected.

  Here, the water-absorbent coating composed mainly of the water-absorbent resin is such that the proportion of the water-absorbent resin (in the case of a curable resin, the main agent and the curing agent) is 70 to 100 mass with respect to the total amount of the water-absorbent coating. %, And the ratio is preferably 80 to 100% by mass.

  In the present invention, as the water-absorbing resin mainly constituting the water-absorbing film, a resin having a hydrophilic group or a hydrophilic chain (polyoxyethylene group or the like) is used without particular limitation. The water-absorbing resin may be a linear polymer or a non-linear polymer, but a resin that is a non-linear polymer having a three-dimensional network structure is preferable from the viewpoint of durability and the like.

Specific examples of the water-absorbing resin comprising a linear polymer include hydroxypropyl cellulose, polyvinyl alcohol, polyvinyl acetal, polyvinyl pyrrolidone, and polyvinyl acetate.
Examples of the resin that is a non-linear polymer having a three-dimensional network structure include a cured product of a curable resin and a crosslinked resin in which a crosslinkable resin is crosslinked. Usually, the hardened | cured material of curable resin and crosslinked resin are not distinguished.

  In this specification, the hardened | cured material of curable resin and crosslinked resin are used by the same meaning. Hereinafter, a cured product of a curable resin (hereinafter also referred to as a cured resin) is used in the sense of including a crosslinked resin, and the curable resin is used in a sense of including a crosslinkable resin. The curable component refers to a combination of a compound having a reactive group (monomer, oligomer, polymer, etc.) and a curing agent. One reactive compound of the curable resin may be referred to as a main agent. The curing agent refers to the other reactive compound that reacts with the main agent, and also means what is called a reaction initiator such as a radical generator that reacts an addition polymerizable unsaturated group and a reaction catalyst such as a Lewis acid.

  Here, since the saturated water absorption amount of the cured resin is proportional to the amount of the hydrophilic group in the cured resin, the saturated water absorption amount of the resin can be controlled by adjusting the amount of the hydrophilic group. Examples of the hydrophilic group include a hydroxyl group, a carboxyl group, a sulfonyl group, an amide group, an amino group, a quaternary ammonium base, and an oxyalkylene group. The amount of the hydrophilic group in the curable resin can be controlled by adjusting the amount (for example, hydroxyl value) of the hydrophilic group contained in the main agent and / or the curing agent. In the case where a hydrophilic group is formed by a curing reaction, the saturated water absorption can be controlled by adjusting the number of functional groups and the degree of crosslinking of the main agent and / or the curing agent.

  The saturated water absorption also depends on the degree of crosslinking in the cured resin. If the number of crosslinking points contained in the cured resin per unit amount is large, the cured resin has a dense three-dimensional network structure, and a space for water retention is reduced, so water absorption is considered to be low. On the other hand, if the number of cross-linking points contained per unit amount is small, it is considered that the space for water retention becomes large and the water absorption becomes high. The glass transition point of the curable resin is closely related to the number of crosslinking points in the curable resin. In general, a resin having a high glass transition point is considered to have a large number of crosslinking points per unit amount.

  Therefore, in general, it is preferable to control the glass transition point of the cured resin to be low in order to increase water absorption and antifogging performance, and to control the glass transition point of the cured resin to be high in order to increase durability. Considering these, the glass transition point of the water-absorbing cured resin forming the water-absorbing film is preferably 10 to 110 ° C., more preferably 20 to 70 ° C., although it depends on the type of the cured resin. .

  The glass transition point is a value measured according to JIS K 7121. Specifically, it is a value measured using a differential scanning calorimeter after providing a water-absorbing film as a specimen on a substrate and leaving it in an environment of 20 ° C. and a relative humidity of 50% for 1 hour. However, the heating rate at the time of measurement shall be 10 degrees C / min.

  The main component of the curable resin is not particularly limited as long as it becomes a cured resin by reacting with a combination of a compound having two or more reactive groups and a curing agent. This reaction is initiated or promoted by light such as heat or ultraviolet rays. Examples of the reactive group include a group having a polymerizable unsaturated group such as a vinyl group, an acryloyloxy group, a methacryloyloxy group, and a styryl group, and an epoxy group, an amino group, a hydroxyl group, a carboxyl group, an acid anhydride group, Examples include reactive groups such as isocyanate groups, methylol groups, ureido groups, mercapto groups, and sulfide groups. Among these, an epoxy group, a carboxyl group, and a hydroxyl group are preferable, and an epoxy group is more preferable. Moreover, only 1 type may be used for a main ingredient and it may use 2 or more types together.

  When the main agent is a low molecular compound or oligomer having a reactive group, the number of reactive groups contained in one molecule is preferably 2 or more, and more preferably 2 to 10. In some cases, it may contain a component having only one reactive group, in which case the average number of reactive groups per molecule in the curable component is 1.5 or more. It is preferable to do this.

  Examples of such a curable resin include a curable acrylic resin composed of a combination of a main agent composed of a low molecular compound (monomer) or oligomer having two or more acryloyloxy groups and a curing agent that is a radical generator, An epoxy resin comprising a combination of a main agent such as a low molecular compound or oligomer having at least one epoxy group and a curing agent that is a compound having at least two reactive groups reactive with an epoxy group such as an amino group, two or more An epoxy resin comprising a combination of a main component such as a low molecular compound or oligomer having an epoxy group and a curing agent which is a curing catalyst (Lewis acid or base), a polyol such as a low molecular compound or oligomer having two or more hydroxyl groups And a combination of polyisocyanate (curing agent) which is a compound having two or more isocyanate groups There is such that curable urethane resin. A photo-curing acrylic resin can be obtained by using a photopolymerization initiator as a curing agent for a curable acrylic resin, and a photo-curing agent (for example, a compound that generates a Lewis acid or the like by light irradiation) as a curing agent for an epoxy resin. Can be used as a photocurable epoxy resin.

  When the main agent is a polymer having a reactive group, the combination of a polymer having a reactive group (also referred to as a crosslinkable group) and a curing agent is usually referred to as a crosslinkable resin. If it reacts with a hardening | curing agent and becomes a crosslinked resin, there will be no restriction | limiting in particular. The polymer having a crosslinkable group is preferably a linear polymer. Examples of the crosslinkable group include the same groups as the reactive group, and an epoxy group, a carboxyl group, and a hydroxyl group are preferable. The number of crosslinkable groups possessed by the polymer as the main agent may be any as long as it is 2 or more per molecule, and it is usually preferably 1 to 20 per molecule. Moreover, it is preferable that the molecular weight of a polymer is 500-50000 in a number average molecular weight. The number average molecular weight is a value measured by gel permeation chromatography using polystyrene as a standard substance. Hereinafter, the number average molecular weight described in the present specification is a value measured by the same measuring method as described above.

  As the polymer having a crosslinkable group which is a main component of the crosslinkable resin, a vinyl polymer having a crosslinkable group as described above (hereinafter referred to as a crosslinkable vinyl polymer) is preferable. In the present invention, the crosslinkable vinyl polymer means a monomer having a polymerizable site containing a carbon-carbon double bond, such as an olefin monomer, an aromatic vinyl monomer, a vinyl halide monomer, a vinyl cyanide monomer, A polymer having a main chain formed by polymerization of a saturated carboxylic acid ester monomer, a vinyl ester monomer, a vinyl ether monomer or the like. The crosslinkable vinyl polymer is preferably a linear polymer. Moreover, it is preferable that the crosslinkable vinyl polymer has a hydrophilic group or a hydrophilic polymer chain in that a crosslinked resin having high water absorption can be obtained. In some cases, the curing agent may impart water absorption to the crosslinked resin. The crosslinkable vinyl polymer is preferably a crosslinkable vinyl polymer having a cationic group and a crosslinkable group.

  As the cationic group, a group having a quaternary ammonium structure is preferable. The crosslinkable group is not particularly limited as long as it is a group that can react with the reactive group of the curing agent to form a three-dimensional network structure. Examples of the crosslinkable group include the crosslinkable groups described above. A carboxyl group, an epoxy group, a hydroxyl group, and the like are preferable, and a carboxyl group is particularly preferable.

The molecular weight of the crosslinkable vinyl polymer is not particularly limited, but the number average molecular weight is preferably 500 to 50,000, and particularly preferably 1,000 to 20,000. If the molecular weight is less than 500, water absorption performance may be reduced. Moreover, when molecular weight exceeds 50000, there exists a possibility that the adhesiveness of the said heat ray reflective film and crosslinked resin may fall.
The proportion of the cationic group contained in the crosslinkable vinyl polymer is preferably 0.1 to 2.0 mmol, more preferably 0.4 to 2.0 mmol, and particularly 0.5 to 1.5 mmol, per 1 g of the polymer. A millimolar is preferred. Furthermore, the ratio of the crosslinkable group is preferably 1.0 to 3.0 mmol, and particularly preferably 1.5 to 2.5 mmol, per 1 g of the polymer.

  As a combination of the polymer having a crosslinkable group and a curing agent for obtaining a curable resin (crosslinkable resin), a polymer obtained by polymerizing various monomers, preferably a polymerizable containing a carbon-carbon double bond. Monomer having a site, for example, a linear crosslinkable vinyl polymer obtained by polymerizing acrylate or methacrylate, and a reactive group (crosslinkable group: for example, epoxy group, hydroxyl group, carboxyl group, etc.) on the side chain The combination of the polymer which has and the hardening | curing agent which is a compound which has a reactive group of the polymer side chain and two or more reactive reactive groups can be mentioned. More specifically, a combination of a linear polymer having an epoxy group in the side chain and a compound (curing agent) having two or more amino groups, a combination of a polyester polymer having a hydroxyl group and a polyisocyanate (curing agent), a hydroxyl group. A combination of a polyacrylate polymer having a methylol group and a curing agent having a methylol group (such as a methylolmelamine curing agent), a combination of a polyacrylate polymer having a carboxyl group and a compound having two or more amino groups (a curing agent), etc. Can be a curable resin.

  Among these, as the water-absorbing resin used in the present invention, a linear polyacrylate having a hydrophilic group, for example, a cationic group (such as an alkyl group having a quaternary ammonium ion) and a carboxyl group in the side chain. It is preferable to use a crosslinkable resin composed of a combination of a polymer and a curing agent. As the polymer crosslinking agent, polyamines and polyepoxides described below can be used. Specific examples of the polyacrylate polymer include Jurimer SPO-602 and Jurimer SPO-601 (trade names, manufactured by Toa Gosei Co., Ltd.) obtained by polymerizing ethyl trimethyl ammonium chloride, methoxyethyl acrylate, methyl methacrylate, and acrylic acid. ), Poliment NK350 (trade name, manufactured by Nippon Shokubai Co., Ltd.) and the like.

Furthermore, in the present invention, a cured product of an epoxy resin is also preferably used as the water absorbent resin. In the present invention, the epoxy resin refers to a curable resin containing the following curable components.
(I) A combination of a low molecular compound or oligomer having two or more epoxy groups and a curing agent.
(II) A combination of a polymer having two or more epoxy groups and a curing agent.
The number of epoxy groups per molecule in the low molecular weight compound or oligomer that is the main component of the epoxy resin (I) is preferably 2 to 10. As the curing agent, a low molecular compound having two or more reactive groups such as an amino group, a curing catalyst, or the like can be used, and both can be used in combination. The curing agent may be an oligomer or a polymer. For example, a polyamide oligomer, a polyamide polymer, an oligomer or polymer having an amino group or a carboxyl group in the side chain, and the like can be used as the curing agent. Furthermore, a photo-curing agent can be used as a curing agent to make a photo-curing epoxy resin.

  As the polymer which is the main component of the epoxy resin (II), a copolymer of an acrylic monomer such as acrylate or methacrylate or a copolymer of an acrylic monomer and another monomer is preferable. By using an acrylic monomer having an epoxy group as a part of the acrylic monomer, a polymer having an epoxy group can be obtained. Even when a monomer having an epoxy group other than an acrylic monomer is used, a polymer having the same epoxy group can be obtained. The number of epoxy groups per molecule in the polymer having an epoxy group is preferably 1 to 20. The curing agent is preferably a low molecular compound or oligomer having two or more reactive groups such as amino groups.

  The epoxy resin of type (I), which is usually called an epoxy resin, depends on the type of the low-molecular compound or oligomer (hereinafter referred to as polyepoxide) having two or more epoxy groups, which is the main agent. They are classified into epoxy resins, glycidyl ester epoxy resins, glycidyl amine epoxy resins, cycloaliphatic epoxy resins, and the like.

  The main component of the glycidyl ether epoxy resin is usually a polyepoxide (or an oligomer of the polyepoxide) having a structure in which a phenolic hydroxyl group of a polyphenol having two or more phenolic hydroxyl groups is substituted with a glycidyloxy group.

  Similarly, the main component of the glycidyl ester epoxy resin is a polyepoxide having a structure in which the carboxyl group of a polycarboxylic acid having two or more carboxyl groups is substituted with a glycidyloxycarbonyl group, and the main component of the glycidyl amine epoxy resin is a nitrogen atom. It consists of a polyepoxide having a structure in which a hydrogen atom bonded to a nitrogen atom of an amine having two or more bonded hydrogen atoms is substituted with a glycidyl group. Further, the main component of the cycloaliphatic epoxy resin is composed of a polyepoxide having an alicyclic hydrocarbon group (such as 2,3-epoxycyclohexyl group) in which an oxygen atom is bonded between adjacent carbon atoms of the ring. Moreover, as a main ingredient of a glycidyl ether type epoxy resin, there is also a polyepoxide having a structure in which an alcoholic hydroxyl group of a polyol having two or more alcoholic hydroxyl groups is substituted with a glycidyloxy group. This glycidyl ether-based polyepoxide derived from polyols is also called a reactive diluent or reactive flexibility imparting agent for epoxy resins, and is often used in combination with a glycidyl ether-based polyepoxide derived from polyphenols.

  The water-absorbing resin as the main component of the water-absorbing film in the present invention is preferably a cured product of an epoxy resin mainly composed of a polyepoxide having no aromatic nuclei from the viewpoint of obtaining high water absorption, specifically Is preferably a cured product of an epoxy resin mainly composed of a glycidyl ether polyepoxide derived from polyols. In contrast, a cured product of an epoxy resin mainly containing a glycidyl ether-based polyepoxide derived from polyphenols has a relatively low water absorption. This is considered that the cured product of the latter epoxy resin has an aromatic nucleus such as a benzene ring, and this aromatic nucleus is hard and imparts a property of low water absorption to the resin.

  Glycidyl ester-based polyepoxides, glycidylamine-based polyepoxides, and cycloaliphatic polyepoxides are also suitable as the main component of the epoxy-based resin that is a raw material of the water-absorbent resin, as long as the compound does not have an aromatic nucleus. An aromatic polyol is also known as a raw material polyol for polyepoxide, but the glycidyl ether-based polyepoxide derived from the above-mentioned polyol refers to a glycidyl ether-based polyepoxide derived from a polyol having no aromatic nucleus.

  For the same reason as described above, as the epoxy resin that is a raw material of the water-absorbent resin, the curing agent is also preferably a compound having no aromatic nucleus. However, when a hardening | curing agent is a reaction catalyst, the compound which has an aromatic nucleus may be sufficient from the usage-amount being small. When the curing agent is a reactive compound having a reactive group that reacts with the main agent, the cured product obtained from the combination with the curing agent, even if the polyepoxide does not have an aromatic nucleus, has a relatively large amount of fragrance. A cured resin having a nucleus may result in insufficient water absorption.

  The water-absorbing resin used in the present invention is particularly preferably a combination epoxy resin composed of a main compound composed of a polyepoxide having no aromatic nucleus and a reactive compound having no aromatic nucleus. As the polyepoxide having no aromatic nucleus, a glycidyl ether polyepoxide is preferable. Similarly, glycidyl ester polyepoxides, glycidyl amine polyepoxides, cycloaliphatic polyepoxides, and the like obtained from polyols having no aromatic nuclei and amines having no aromatic nuclei are epoxy resins for obtaining a superabsorbent resin. It is preferable as the main component of the resin. The most preferred polyepoxide having no aromatic nucleus is a glycidyl ether-based polyepoxide.

  As the raw material polyol of the glycidyl ether polyepoxide derived from polyols, there are polyols having no aromatic nucleus such as aliphatic polyols and alicyclic polyols, and the number of hydroxyl groups per molecule is preferably 2-8. ~ 4 are more preferred. Hereinafter, such polyols having no aromatic nucleus are referred to as aliphatic polyols. Examples of aliphatic polyols include alkane polyols, etheric oxygen atom-containing polyols, sugar alcohols, polyoxyalkylene polyols, and polyester polyols. The polyoxyalkylene polyol can be obtained by ring-opening addition polymerization of a monoepoxide such as propylene oxide or ethylene oxide to a relatively low molecular weight polyol such as an alkane polyol, an etheric oxygen atom-containing polyol or a sugar alcohol. The polyester polyol includes a compound having a structure in which an aliphatic diol and an aliphatic dicarboxylic acid are condensed, a compound having a structure in which a cyclic ester is ring-opening polymerized, and the like.

  Specific examples of glycidyl ether-based polyepoxides derived from polyols include ethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, dipropylene glycol diglycidyl ether, neopentyl glycol diglycidyl ether, 1,4-butanediol diglycidyl. Ether, 1,6-hexanediol diglycidyl ether, glycerin polyglycidyl ether, diglycerin polyglycidyl ether, trimethylolpropane polyglycidyl ether, sorbitol polyglycidyl ether, pentaerythritol polyglycidyl ether, polyethylene glycol diglycidyl ether, polyoxypropylene Diol diglycidyl ether, polyoxypropylene triol triglycidyl Ether, poly (oxypropylene-oxyethylene) triol triglycidyl ether and the like.

More preferred glycidyl ether-based polyepoxides derived from polyols are polyepoxides having an average number of glycidyloxy groups of more than 2 and 4 or less per molecule. For example, triol triglycidyl ether, tetraol tetraglycidyl ether, triol triglycidyl ether and the same triol diglycidyl ether, tetraol tetraglycidyl ether, mixture of triglycidyl ether and diglycidyl ether, triol Examples thereof include a mixture of triglycidyl ether and diglycidyl ether of diol. Specifically, the average number of glycidyloxy groups per molecule is more than 2 and 4 or less, glycerin polyglycidyl ether, diglycerin polyglycidyl ether, polyglycerin polyglycidyl ether, trimethylolpropane polyglycidyl ether, penta Examples include erythritol polyglycidyl ether and sorbitol polyglycidyl ether.
Among these, glycerin polyglycidyl ether, diglycerin polyglycidyl ether, polyglycerin polyglycidyl ether, and sorbitol polyglycidyl ether are particularly preferable.

  Examples of polyepoxides other than glycidyl ether-based polyepoxides include hexahydrophthalic acid diglycidyl ester, tetrahydrophthalic acid diglycidyl ester, 3,4-epoxycyclohexylmethyl-3 ′, 4′-epoxycyclohexanecarboxylate, and bis (3,3 4-epoxycyclohexylmethyl) adipate and the like.

  Examples of the curing agent in the epoxy resin include compounds having two or more reactive groups reactive with epoxy groups such as polyamines, polycarboxylic acid anhydrides, polyamides, polythiols, tertiary amines, imidazoles, Examples of the curing catalyst include Lewis acids, onium salts, dicyandiamides, organic acid dihydrazides, and phosphines. As the compound having two or more reactive groups, polyamines and polycarboxylic anhydrides having no aromatic nucleus are preferable, and as the curing catalyst, tertiary amines, imidazoles, phosphines, and allylsulfonium salts are preferable. Moreover, the photocurable catalyst which comprises photocurable epoxy resin as a curing catalyst is also preferable. Furthermore, a compound having two or more reactive groups and a curing catalyst can be used in combination, and a combination of polyamines and a curing catalyst is particularly preferable. Hereinafter, a compound having two or more reactive groups is referred to as a curing agent (α), and a curing catalyst is referred to as a curing agent (β).

  As the curing agent (α), polyamines, polycarboxylic acid anhydrides, polyamides, and the like can be used, and in order to obtain a highly water-absorbent resin, it is a reactive compound that does not have an aromatic nucleus like polyepoxide. preferable. As the curing agent (α), polyamines having no aromatic nucleus and polycarboxylic acid anhydrides having no aromatic nucleus are preferable, and polyamines having no aromatic nucleus are particularly preferable. Polyamines having 2 to 4 amino groups are preferred as polyamines, and dicarboxylic acid anhydrides, tricarboxylic acid anhydrides, and tetracarboxylic acid anhydrides are preferred as polycarboxylic acid anhydrides.

As polyamines having no aromatic nucleus, aliphatic polyamine compounds and alicyclic polyamine compounds are preferred. Specific examples of these polyamines include ethylenediamine, triethylenetetramine, tetraethylenepentamine, hexamethylenediamine, polyoxyalkylenepolyamine, isophoronediamine, mensendiamine, 3,9-bis (3-aminopropyl)- 2,4,8,10-tetraoxaspiro (5,5) undecane and the like. The polyoxyalkylene polyamine is a polyamine having a structure in which the hydroxyl group of the polyoxyalkylene polyol is substituted with an amino group, for example, a structure in which the hydroxyl group of a polyoxypropylene polyol having 2 to 4 hydroxyl groups is substituted with an amino group There are compounds having 2 to 4 amino groups having The molecular weight per amino group is preferably 1000 or less, and particularly preferably 500 or less.
Examples of the polycarboxylic acid anhydride having no aromatic nucleus include succinic anhydride, methyltetrahydrophthalic anhydride, hexahydrophthalic anhydride, 4-methylhexahydrophthalic anhydride, and the like.

  Examples of the curing agent (β) include 2-methylimidazole, 2-ethyl-4-methylimidazole, triethylenediamine, tris (dimethylaminomethyl) phenol, boron trifluoride-amine complex, dicyandiamide, and the like. Examples of the curing agent (β) that gives a photo-curable epoxy resin include onium salts that decompose by light such as ultraviolet light such as diphenyliodonium hexafluorophosphate and triphenylsulfonium hexafluorophosphate to generate a Lewis acid catalyst. Can be mentioned.

  The combination ratio of the polyepoxide and the curing agent is such that when the curing agent is a curing agent (α), the equivalent ratio of the reactive group of the curing agent (α) to the epoxy group is about 0.8 to 1.2. Is preferred. However, when using together with a hardening | curing agent ((beta)), it may be less than this ratio. Moreover, since the physical property of hardened | cured material will become inadequate when a mass ratio increases too much, it is preferable that it is 40 mass% or less with respect to a polyepoxide. It is preferable that the usage-amount of a hardening | curing agent ((beta)) is 2-20 mass% with respect to polyepoxide. When the amount of the curing agent (β) used is 2% by mass or more, the reaction proceeds sufficiently and sufficient water absorption and durability can be realized. Moreover, if the usage-amount of a hardening | curing agent ((beta)) is 20 mass% or less, it will be easy to prevent generation | occurrence | production problems, such as yellowing of hardened | cured material, which a hardening | curing agent residue remains in the obtained hardened | cured material.

  Other reactive additives and non-reactive additives may be added to the epoxy resin comprising a combination of polyepoxide and a curing agent. Examples of the reactive additive include a compound having one reactive group reactive with an epoxy group such as alkyl monoamine, and the coupling agent having an epoxy group or an amino group. In an epoxy resin comprising a combination of a polyepoxide, a curing agent and an optional additive, the content of the polyepoxide with respect to the epoxy resin is preferably 40 to 80% by mass. Moreover, it is preferable that the total amount of a hardening | curing agent is 40 mass% or less.

  Commercially available products can be used as the polyepoxide, the curing agent, and the combination thereof (epoxy resin). As such a commercial product, specifically, as an aliphatic glycidyl ether polyepoxide, all trade names manufactured by Nagase Chemtex Co., Ltd., Denacol EX-1610, Denacol EX-313, Denacol EX-314, etc. are sorbitol. Examples of the polyglycidyl ether include Denacol EX614B (trade name, manufactured by Nagase ChemteX), and examples of the curing agent include Jeffamine T403 (trade name, manufactured by Huntsman) as a polyoxyalkylene triamine. Examples of the triarylsulfonium salt that is a photocuring catalyst include Adekaoptomer SP152 (trade name, manufactured by Adeka).

(Optional component)
The water-absorbent coating in the heat ray reflective glass of the present invention is composed mainly of the water-absorbent resin, but contains optional components having various functions as necessary. As optional components, an inorganic filler for increasing the mechanical strength of the water-absorbing coating, a coupling agent for increasing the adhesion to the layer in contact with the water-absorbing coating, and a leveling agent used for improving the film-forming property , Antifoaming agents, viscosity modifiers, light stabilizers and the like.

(Inorganic filler)
An inorganic filler is a component which can provide high mechanical strength and heat resistance by adding a water-absorbing coating. In addition, when a cured resin is used as the water-absorbing resin, the curing shrinkage of the resin during the curing reaction can be reduced. As such an inorganic filler, a filler made of a metal oxide is preferable. Examples of the metal oxide include silica, alumina, titania, and zirconia. Among these, silica is preferable.

  In addition to the filler made of the metal oxide, a filler made of ITO (Indium Tin Oxide) can also be used. Since ITO has infrared absorptivity, heat absorption can be imparted to the water-absorbent coating. Therefore, if a filler made of ITO is used, an antifogging effect due to heat ray absorption can be expected in addition to water absorption.

  These inorganic fillers contained in the water-absorbent coating are preferably in the form of particles. Moreover, the average particle diameter is preferably 0.01 to 0.3 μm, and more preferably 0.01 to 0.1 μm. Moreover, about the compounding quantity of an inorganic filler, when using cured resin as a water absorbing resin, it is preferable that it is 1-20 mass% with respect to the total mass of a main ingredient and a hardening | curing agent, and 1-10 mass%. More preferred. When using a linear polymer as a water absorbing resin, it is preferable that it is 0.5 to 5.3% with respect to the mass of a water absorbing resin. When the blending amount of the inorganic filler with respect to the mass of the water absorbent resin is set to the above lower limit value or more, mechanical strength can be imparted to the water absorbent coating. Moreover, when using cured resin, it is easy to suppress the fall of the cure shrinkage reduction effect. Moreover, if the compounding quantity of an inorganic filler shall be below the said upper limit, the space for water absorption can fully be ensured, and it will be easy to make water absorption and antifogging property high.

  The silica preferably used as the inorganic filler, more preferably, silica fine particles are described later as water or colloidal silica dispersed in an organic solvent such as methanol, ethanol, isobutanol, propylene glycol monomethyl ether, butyl acetate or the like. It can mix | blend with the liquid composition for water-absorbing film formation. Examples of colloidal silica include silica hydrosols dispersed in water and organosilica sols in which water is replaced with an organic solvent. When blended in a liquid composition for forming a water-absorbing film, a solvent preferably used for the composition In accordance with the above, silica hydrosol or organosilica sol is used. For example, when the solvent used in the liquid absorbent film-forming liquid composition is an organic solvent, it is preferable to use an organosilica sol using the same organic solvent as a dispersion medium.

As such an organosilica sol, a commercially available product can be used. As a commercially available product, for example, silica fine particles having a particle diameter of 10 to 15 nm are in isopropanol, and the SiO ₂ content is 30% by mass with respect to the total amount of the organosilica sol. Organosilica sol IPA-ST (trade name, manufactured by Nissan Chemical Industries, Ltd.) dispersed in a proportion, silica fine particles having a particle diameter of 10 to 15 nm were dispersed in butyl acetate at a rate of 30% by mass as SiO ₂ content with respect to the total amount of organosilica sol. And organosilica sol NBAC-ST (trade name, manufactured by Nissan Chemical Industries, Ltd.). In addition, when colloidal silica is used as the silica fine particles, the amount of the solvent to be blended in the liquid composition for forming a water-absorbent coating is appropriately adjusted in consideration of the amount of solvent contained in the colloidal silica.

  The inorganic filler is blended in the liquid composition for forming a water-absorbing film, for example, as a silica precursor such as tetraethoxysilane, and is present in the film as silica when the water-absorbing film is formed. It may be. As such a silica precursor, silicate compounds such as tetramethoxysilane, monomethyltriethoxysilane, monomethyltrimethoxysilane, dimethyldimethoxysilane, and dimethyldiethoxysilane can be used in addition to the tetraethoxysilane.

  As alumina, titania, zirconia, etc., exemplified as inorganic fillers other than the above silica, alkoxides and acetylacetonates can be used as precursors, and in particular, zirconium chloride can also be used as zirconium. .

(Coupling agent)
A coupling agent is added to the liquid composition for forming a water-absorbing film, and forms a water-absorbing film, a layer in contact with the water-absorbing film, specifically, between the silver-based heat ray reflective film. It is a component that acts to increase adhesion. In the case where the coupling agent has a reactive group, the reactive group reacts with other components constituting the water-absorbing film to improve the adhesion, so that the liquid composition for forming a water-absorbing film The coupling agent blended in is present in a slightly different shape after the formation of the water-absorbing film. Below, the coupling agent added to the liquid composition for water-absorbing film formation is demonstrated.

  In addition, when the coupling agent blended as an optional component using a curable resin as the water-absorbing resin has a functional group reactive with the main agent or the curing agent, the coupling agent is adhesive. In addition to the purpose of improving the film, it can also be used for the purpose of adjusting the physical properties of the water-absorbent coating.

  Here, even when the curable resin contains an epoxy resin, the liquid composition for forming a water-absorbent film preferably contains a coupling agent. As such a coupling agent, an organometallic coupling agent is used. Or it is preferable that it is a polyfunctional organic compound.

  Examples of the organometallic coupling agent include silane coupling agents, titanium coupling agents, and aluminum coupling agents, with silane coupling agents being preferred. When these coupling agents are used together with a curable resin, it preferably has a reactive group capable of reacting with a reactive group of the main agent or the curing agent. Here, the coupling agent is preferably a compound having one or more (preferably one or two) bonds between a metal atom and a carbon atom. As the organometallic coupling agent, a silane coupling agent is particularly preferable.

A silane coupling agent is a compound in which one or more hydrolyzable groups and one or more monovalent organic groups (however, the terminal bonded to the silicon atom is a carbon atom) are bonded to the silicon atom. Yes, one of the monovalent organic groups is a functional organic group (an organic group having a reactive group or an organic group exhibiting characteristics such as hydrophobicity). As the organic group other than the functional organic group, an alkyl group having 4 or less carbon atoms is preferable. The number of hydrolyzable groups bonded to the silicon atom is preferably 2 or 3. The silane coupling agent is preferably a compound represented by the following formula (1).
R ³ R ⁴ _c SiX ² _3-c (1)
In the above formula (1), R ³ represents a monovalent functional organic group, R ⁴ represents an alkyl group having 4 or less carbon atoms, and c represents an integer of 0 or 1. R ⁴ is preferably a methyl group or an ethyl group, and particularly preferably a methyl group. X ² is a hydrolyzable group such as a chlorine atom, an alkoxy group, an acyl group, or an amino group, and an alkoxy group having 4 or less carbon atoms is particularly preferable.

  The functional organic group may be a hydrophobic organic group such as a polyfluoroalkyl group or a long-chain alkyl group having 6 to 22 carbon atoms. Preferably, it is an alkenyl group having an addition polymerizable unsaturated group or an alkyl group having a reactive group. The alkyl group having a reactive group may be an alkyl group substituted with an organic group having a reactive group. As for carbon number of such an alkyl group, 1-4 are preferable. Examples of reactive groups include epoxy groups, amino groups, mercapto groups, ureido groups, hydroxyl groups, carboxyl groups, acryloyloxy groups, methacryloyloxy groups, and isocyanate groups. Examples of the organic group having such a reactive group include a glycidyl group, an epoxycyclohexyl group, an alkylamino group, a dialkylamino group, an arylamino group, and an N-aminoalkyl-substituted amino group. When the curable resin is an epoxy resin, the reactive group is preferably an epoxy group, an amino group, a mercapto group, or a ureido group.

  Examples of such silane coupling agents include 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 3- Glycidoxypropylmethyldiethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-acryloxypropyltrimethoxysilane, 3-isocyanatopropyltrimethoxysilane, N- (2-amino Ethyl) -3-aminopropylmethyldimethoxysilane, N- (2-aminoethyl) -3-aminopropyltrimethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropylmethyldimethoxysilane, N-phenyl-3- Mino propyltrimethoxysilane, 3-ureidopropyltriethoxysilane, and 3-mercaptopropyltrimethoxysilane.

  Among these, 3-aminopropyltrimethoxysilane, 3-aminopropylmethyldimethoxysilane, N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane, N- (2-aminoethyl) -3-amino Propyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropyl Trimethoxysilane, 3-acryloxypropyltrimethoxysilane and the like are preferable.

  The polyfunctional organic compound means an organic compound having two or more functional groups, and preferably two or more reactive groups capable of reacting with the main component of the curable resin or the reactive group of the curing agent. It is what you have. Examples of the reactive group include a vinyl group, an epoxy group, a styryl group, an acryloyloxy group, a methacryloyloxy group, an amino group, a ureido group, a chloropropyl group, a mercapto group, a sulfide group, an isocyanate group, a hydroxyl group, and a carboxyl group. And acid anhydride groups. When a curable resin is used as the water absorbent resin and the curable resin is an epoxy resin, the reactive group of the polyfunctional organic compound is an isocyanate group, an amino group, an acid anhydride group, an epoxy group, and a hydroxyl group. Are preferable, and an isocyanate group and an epoxy group are more preferable. Specific examples of the polyfunctional organic compound include polyisocyanate and polyepoxide.

  When the coupling agent is a polyfunctional organic compound, the substance is not distinguished from the curing agent. However, the role of the coupling agent and the role of the curing agent are different. That is, the coupling agent serves to improve the adhesion between the silver-based heat ray reflective film and the water-absorbing film, and the curing agent serves to react with the main component of the curable resin to form a cured resin.

  The amount of the coupling agent used in the liquid composition for forming a water-absorbent film is not an essential component, so there is no lower limit. However, the mass ratio of the coupling agent to the total mass of the water-absorbing resin (main agent and curing agent in the case of a cured resin) and the coupling agent in order to fully exhibit the effect of the coupling agent formulation. Is preferably 0.1% by mass or more, and more preferably 0.5% by mass or more. The upper limit of the amount of coupling agent used is limited by the physical properties and functions of the coupling agent, but for the total mass of the water-absorbing resin (in the case of a curable resin, the main agent and the curing agent) and the coupling agent In general, the content is preferably 20% by mass or less, and more preferably 15% by mass or less.

(Other optional ingredients)
Examples of the leveling agent include polydimethylsiloxane-based surface conditioners, acrylic copolymer surface conditioners, fluorine-modified polymer-based surface conditioners, and antifoaming agents include silicone-based antifoaming agents, surfactants, Organic antifoaming agents such as ether and higher alcohols, acrylic copolymers, polycarboxylic acid amides, modified urea compounds, etc. as viscosity modifiers, hindered amines as light stabilizers; nickel bis (octylphenyl) Examples include nickel complexes such as sulfide, nickel complex-3,5-di-tert-butyl-4-hydroxybenzyl phosphate monoethylate, nickel dibutyldithiocarbamate. Each component may be used in combination of two or more of the exemplified compounds. The content of the various components in the liquid composition for forming a water-absorbent coating is 0.000 parts by mass with respect to 100 parts by mass of the water-absorbent resin (in the case of a cured resin, the total of the main agent and the curing agent). The amount can be 001 to 10 parts by mass.

(Formation of water-absorbing film)
The water-absorbing film contains a water-absorbing resin (in the case of a curable resin, a main agent and a curing agent) as essential components in the above-mentioned predetermined proportion, and further contains the optional components in the above-mentioned blending amounts as necessary. A film-forming liquid composition is prepared, and this water-absorbing film-forming liquid composition is applied on the silver-based heat ray reflective film and dried or, if necessary, cured (crosslinked). Formed.
Hereinafter, a method of forming a water-absorbing film when the linear polymer is used as the water-absorbing resin and when a cured resin is used will be described.

  When a linear polymer is used as the water-absorbent resin, it is particularly preferable to contain the inorganic filler in the water-absorbent coating in order to increase mechanical strength. As a liquid composition for forming a water-absorbing film used for forming such a water-absorbing film, a predetermined amount of a water-absorbing resin and an inorganic filler precursor are dissolved in an appropriate solvent, and further if necessary. And a composition to which an optional component such as the coupling agent is added.

  In order to contain the silica preferably used as the inorganic filler contained in the water-absorbent coating, when a silicate compound is used as a silica precursor in the liquid composition for forming a water-absorbent coating, a lower alcohol as the solvent, For example, a mixed solvent of methanol, ethanol, propanol, etc. and water can be mentioned.

  The composition may further contain water and an alcohol solvent as a dilution solvent. Specific examples of alcohol solvents include methanol, ethanol, propanol, ethylene glycol, propylene glycol, hexylene glycol, esters such as ethyl acetate, butyl acetate, and amyl acetate, and methyl cellosolve, ethyl cellosolve, and butyl cellosolve. And cellosolves such as These may be used alone or in combination of two or more.

  In order to form a water-absorbing film on a glass substrate, the method for applying the liquid composition for forming a water-absorbing resin obtained above to the coated surface of the silver-based heat ray reflective film is not particularly limited. , Known methods such as dip coating, spin coating, spray coating, flexographic printing, screen printing, gravure printing, roll coating, meniscus coating, die coating, and wiping.

The total solid content concentration in the liquid composition for forming a water-absorbent resin when coating is formed by these coating methods is preferably about 1 to 5% by mass, and the coating solution viscosity is 0.002 to 0.01 N · s. / M ² is preferable.

  As a treatment after the application, a water-absorbing coating is formed on the silver-based heat ray reflective film by performing a drying treatment. As the drying treatment, a drying temperature of about 90 to 150 ° C. and a drying time of about 10 to 120 minutes are preferable, and more preferably, the drying temperature is about 110 to 130 ° C. and a drying time of about 20 to 80 minutes. . Below the drying temperature, evaporation of the solvent is insufficient, water resistance, mechanical strength and chemical durability may be insufficient, and no change in performance is observed even at higher temperatures. Because.

  When a cured resin is used as the water-absorbent resin, the liquid composition for forming a water-absorbent coating contains the main agent and the curing agent as essential components in the above-mentioned predetermined proportion, and further, if necessary, the above optional components in the above blending amounts. A liquid composition for forming a water-absorbing film is prepared, and this liquid composition for forming a water-absorbing film is coated on the above-mentioned silver-based heat ray reflective film, dried as necessary, and cured (crosslinked) to form. Is done.

  The liquid composition for forming a water-absorbent coating preferably contains a solvent in order to improve the coating workability when a solid or high viscosity liquid curable resin is used. In general, the reaction between the main component of the curable resin and the curing agent is carried out after being applied to the surface of the silver-based heat ray reflective film as a liquid composition for forming a water-absorbing film, but the composition contains a solvent. Alternatively, these components may be reacted in advance in the composition before being applied to the surface of the silver-based heat ray reflective film, then applied to the surface of the silver-based heat ray reflective film, dried, and further reacted. Thus, when the main agent and the curing agent are reacted to some extent in a solvent as a liquid composition for forming a water-absorbent film, the curing reaction can be ensured by setting the reaction temperature to 40 ° C. or higher in advance. This is preferable because it proceeds.

  The solvent used in the liquid composition for forming a water-absorbent film is not particularly limited as long as it is a solvent having good solubility of components such as a main agent and a curing agent and is inert to these components. Specifically, alcohols, acetate esters, ethers, ketones, water and the like can be mentioned.

  When an epoxy group-containing compound is used as the main agent or curing agent, if a protic solvent is used as the solvent, the solvent and the epoxy group may react with each other depending on the type, and a cured resin may not be formed easily. Therefore, when a protic solvent is used, it is preferable to select a solvent that does not easily react with the epoxy compound. Examples of protic solvents that can be used include ethanol and isopropanol. As other solvents, methyl ethyl ketone, butyl acetate, propylene carbonate, diethylene glycol dimethyl ether and the like are preferable.

  These solvents may be used alone or in combination of two or more. In addition, components such as a main agent and a curing agent may be prepared as a mixture with a solvent. In this case, the solvent contained in the mixture may be used as it is as the solvent in the liquid composition for forming a water-absorbent coating, and the same or other solvents may be added to the composition. Good.

  Moreover, when the liquid composition for water-absorbing film formation contains an epoxy group-containing compound, the amount of the solvent is 1 to 5 times the total mass of the epoxy group-containing compound, the curing agent, and the following coupling agent. It is preferable that

  In order to form a water-absorbing film on the substrate, the liquid absorbent resin-forming liquid composition obtained as described above is applied to the coated surface of the substrate by using a linear polymer as the water-absorbing resin. A similar method can be mentioned. After applying the liquid composition for forming a water-absorbing film on the substrate, the solvent is removed by drying as necessary, and a curing treatment is performed under conditions suitable for the curable resin to be used to form a cured resin layer.

Specific examples of the curing treatment include heat treatment at 50 to 120 ° C. for about 10 to 60 minutes. In the case of a room temperature curable resin, room temperature curing can also be performed. In the case of using a photocurable resin, a treatment such as performing UV irradiation of 50 to 1000 mJ / cm ² for 5 to 10 seconds with a UV curing device or the like can be mentioned.

  In the case where a linear polymer is used as the water-absorbent resin, the film thickness of the water-absorbent coating is preferably 5 μm or more, more preferably 10 μm or more, regardless of whether the cured resin is used. This makes it possible to secure the necessary saturated water absorption amount without degrading or altering the silver-based heat ray reflective film and sufficiently protecting from mechanical factors. On the other hand, from the viewpoint of preventing the durability of the water-absorbent coating from being lowered, the film thickness of the water-absorbent coating is preferably 50 μm or less, and more preferably 30 μm or less. The water-absorbing film may be composed of a single layer, for example, a water-absorbing layer formed using different types of water-absorbing resins, or a water-absorbing layer containing the same water-absorbing resin but having different contents. A laminated structure such as

The heat ray reflective glass of the present invention may have other functional films as long as the effects of the present invention are not impaired in addition to the silver heat ray reflective film and the water absorbing film.
For example, when a linear polymer is used as the water absorbent resin, it is preferable to further provide the following water repellent coating on the surface of the water absorbent coating. By providing the water-repellent coating, properties such as oil repellency and antifouling properties can be simultaneously imparted.
As the water-repellent film further provided on the water-absorbent film, a silicon compound: a compound in which at least one of functional groups is a methyl group (—CH ₃ ) and another functional group is an isocyanate group (—NCO) ( For example, a water-repellent coating composed of silyl isocyanate), fluoroalkyltrimethoxysilane, fluoroalkyltrimethoxysilane and the like is preferable.

  For the water-repellent coating, a liquid composition for forming a water-repellent coating is prepared in the same manner as in the case of using a linear polymer as the water-absorbent resin, and after applying this to the surface of the water-absorbent coating, preferably a drying temperature of 70 It is formed by holding at a temperature of about 130 ° C. for about 5 to 120 minutes, more preferably at a temperature of 100 to 120 ° C. for 15 to 60 minutes. The film thickness of the water repellent coating is preferably 10 nm or less. If it is thicker than 10 nm, it is difficult to adsorb and desorb moisture that occurs through the water-repellent coating, the function of the underlying water-absorbing coating is not fully exhibited, and it becomes difficult to exhibit water absorption and antifogging properties.

  In the heat ray reflective glass having the water-absorbent coating of the present invention obtained in this way, by having the above-described configuration, it has excellent wear resistance. Specifically, for the surface of the water-absorbent coating, Even in a 70-rotation wear test using a CS-10F wear wheel having a load of 500 g based on JIS-R3212 (1998), the silver-based heat ray reflective film does not peel off from the glass substrate.

  Further, in the heat ray reflective glass of the present invention, in the humidity resistance test in which the entire heat ray reflective glass is maintained for 500 hours under the conditions of a temperature of 80 ° C. and a relative humidity of 85%, white spots are generated in the silver-based heat ray reflective film. It can be said that the moisture resistance is very excellent.

  In the past, when a silver-based heat ray reflective film was used in combination with a glass substrate, it was often used as a laminated glass. When using a silver-based heat ray reflective film in laminated glass, since there are glass plates on both sides of the silver-based heat ray reflective film, the emissivity is the same as that of normal glass on the reflective side where heat rays are incident and reflected. It becomes the same, and the radiant heat when the temperature of the laminate itself rises is no different from that of normal glass.

On the other hand, in the present invention, since a silver-based heat ray reflective film is provided on a glass substrate and a glass substrate is not provided on the opposite side, when heat rays are incident / reflected from the side without the glass substrate, the incidence of heat rays is caused. On the reflection side where reflection occurs, the emissivity is the emissivity of the heat ray reflective film, so that it is considered that the re-radiation of heat can be reduced.
Therefore, the case where the silver heat ray reflective film is used for the single plate glass as in the present invention can enhance the heat ray reflection effect of the silver heat ray reflective film more than the case where the silver heat ray reflective film is used for the laminated glass. It becomes possible.

  Hereinafter, the present invention will be described in more detail with reference to examples. However, the present invention is not limited to these examples. Examples 1 to 3 are examples, and example 4 is a comparative example. In addition, evaluation of the heat ray reflective glass obtained by the following example and the comparative example was performed by the following method about the following item.

[Evaluation items and methods]
1. Visible light transmittance (Tv) and solar reflectance (Re): a glass substrate on which a water-absorbing film and a silver-based heat ray reflective film are formed using a spectrophotometer (manufactured by Shimadzu Corporation, product name: UV-3150) With respect to incident light incident from the glass substrate side of (heat-reflecting glass having a water-absorbing coating), the transmittance and reflectance between wavelengths of 300 to 2500 nm are measured, and the visible light transmittance Tv (%) in accordance with the provisions of JIS R3211 The solar reflectance Re (%) was calculated according to JIS R3106.

2. Abrasion resistance: Using a Taber type abrasion resistance tester, CS-10F abrasion with a load of 500 g is applied to the surface of the water-absorbing film of the heat ray reflective glass having a water-absorbing film by the method described in JIS-R3212 (1998). A 70-turn wear test was performed with the wheel, and the film was evaluated by the presence or absence of film peeling after the test and the change in haze (haze value).

3. Moisture resistance: A silver-based heat ray reflective film of a heat ray reflective glass having a water-absorbing film by visual observation after holding the heat-ray reflecting glass having a water-absorbing film in a constant temperature and humidity chamber at 80 ° C. and a relative humidity of 85% for 500 hours. It was evaluated whether there was any alteration or deterioration such as white spots.

4). Anti-fogging performance: The surface of the water-absorbing coating of the heat ray reflective glass having a water-absorbing coating was subjected to breathing to evaluate whether it was clouded (x) or not clouded (O).

[Production Example 1] Production of glass substrate with silver-based heat ray reflective film Heat treatment having two silver (Ag) layers on a colorless transparent soda-lime silica glass substrate (manufactured by Asahi Glass Co., Ltd.) having a thickness of 300 mm x 300 mm and a thickness of 4 mm. A possible silver-based heat ray reflective film was formed by magnetron sputtering. In addition, sectional drawing of the obtained glass substrate with a silver type heat ray reflective film is the same as that shown in FIG. Table 1 shows layer constituent materials, film thicknesses, and compositions of each layer of the heat ray reflective film.

ZnAlO _{x in} Table 1 is a mixed oxide containing Zn and Al formed by a reactive direct current magnetron sputtering method in the presence of oxygen using a target of an alloy or mixture of Zn and Al. AlSi _x N _y is a mixed nitride containing Si and Al formed by a reactive DC magnetron sputtering method in the presence of nitrogen and argon using a target of a mixture of Al and Si. The Ag layer was formed by a direct current magnetron sputtering method in an argon atmosphere using an Ag target.

Any ZnAlO _y barrier layer can be used to form an alloy of Zn and Al in an argon atmosphere containing oxygen (an insufficient amount of oxygen to fully oxidize) so that a barrier layer that is not fully oxidized can be formed. A target of the mixture is a mixed oxide layer partially formed in an unoxidized state formed by a direct current magnetron sputtering method.
As another means, the mixed oxide ZnAlO _x layer contains a target of a mixture of zinc oxide and aluminum oxide in argon gas or oxygen (an insufficient amount of oxygen for complete oxidation). It can also be formed by sputtering in an argon atmosphere.

The glass substrate provided with the silver-based heat ray reflective film obtained above was subjected to a heat treatment at 645 ° C. for 14 minutes. The cross-sectional view of the glass substrate with a silver-based heat ray reflective film obtained after the heat treatment is the same as that shown in FIG.
Here, each upper barrier layer is oxidized by itself when the ZnAlO _x oxide layer on the upper barrier layer is formed by a direct current magnetron sputtering method and when the glass substrate is heat-treated after the heat ray reflective film is formed. It has a function of preventing the lower Ag layer from being oxidized. In addition, each lower barrier layer has an action of preventing oxidation of the Ag layer thereon by oxidizing itself when the glass substrate is heat-treated after the heat ray reflective film is formed.

[Example 1] Production of heat ray reflective glass having water-absorbing film Polyoxyalkylene triamine (trade name: Jeffamine T403, manufactured by Mitsui Chemicals Fine Co., Ltd.) (15.98 g) in a glass container in which a stirrer and a thermometer are set. And organosilica sol (manufactured by Nissan Chemical Industries, product number: NBAC-ST) (2.36 g) were charged and stirred for 10 minutes. Next, methyl ethyl ketone (38.37 g) was added thereto and stirred for 1 minute, and then glycerol polyglycidyl ether (manufactured by Nagase ChemteX Corporation, trade name: Denacol EX-313) (16.27 g) and aliphatic polyepoxide (Nagase Chem). Tex, trade name: Denacol EX-1610) (19.59 g) was added and stirred for 1 hour.

  Further, N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd., product number: KBM602) (7.36 g) was added thereto and stirred for 1 hour. Next, a polyoxyalkyleneamino-modified dimethylpolysiloxane copolymer (manufactured by Nippon Unicar Co., Ltd., product number: FZ-3789) (0.07 g) was added and stirred for 20 minutes, and the mixing ratio of tetrohydrofuran and dioxane was 1: The diluted solvent (100 g) 9 was added and stirred for 10 minutes to obtain a liquid composition 1 for forming a water-absorbent film. In addition, the number of epoxy functional groups of Denacol EX-1610 is 2 or more.

The glass substrate with the silver-based heat ray reflective film obtained above was set horizontally, 30 g of the liquid composition 1 for forming a water-absorbent coating was dropped, and then applied by rotating the substrate at 50 rpm for 20 seconds by spin coating. C. for 60 minutes to obtain heat ray reflective glass 1 having a water-absorbing film having an average film thickness of 22 .mu.m.
The saturated water absorption amount of the water absorbent resin obtained above was 24 mg / cm ³ .

  Table 2 shows the evaluation results of visible light transmittance (Tv), solar reflectance (Re), abrasion resistance, moisture resistance and antifogging performance. A photograph (optical microscope: 500 times) showing the appearance of the heat ray reflective glass 1 having a water-absorbing coating after the moisture resistance test is shown in FIG.

[Example 2] Production of heat ray reflective glass having water-absorbing film Polyvinyl alcohol (reagent, degree of polymerization 2000, manufactured by Kishida Chemical Co.) and ethyl silicate (reagent, manufactured by Kishida Chemical Co., Ltd.) at a mass ratio of 99.5: 0.5 So that the solid content concentration becomes 3% by mass using a mixed solvent of Echinen F-1 (manufactured by Kishida Chemical) and water (by mass ratio, Echinen F-1: Water = 5: 5). Dilution was performed to prepare a liquid composition 2 for forming a water-absorbing film.

  Methyl triisocyanate (SIC-003, manufactured by Matsumoto Pharmaceutical Co., Ltd.) is diluted with ethyl acetate (reagent: manufactured by Kishida Chemical Co., Ltd.) so that the solid content concentration is 1% by mass, and a liquid composition for forming a water-repellent film is prepared. did.

  Next, the glass substrate with the silver-based heat ray reflective film obtained above was set smoothly, and the liquid composition 2 for forming a water-absorbent coating was applied on the substrate by dip coating, and then at 120 ° C. for 20 minutes. Allow to dry and cool to room temperature. Further, a water-repellent film-forming liquid composition is applied onto the formed water-absorbing film by a spin coating method, dried at 120 ° C. for 20 minutes, and then cooled to room temperature to have an average film thickness of 15 μm. The heat ray reflective glass 2 which has this was obtained.

The saturated water absorption amount of the water absorbent resin obtained above was 16 mg / cm ³ .
Table 2 shows the evaluation results of visible light transmittance (Tv), solar reflectance (Re), abrasion resistance, moisture resistance and antifogging performance.

[Example 3] Production of heat ray reflective glass having water-absorbing coating 36.0 g of acrylic acid polymer (trade name: Julimer SPO601, manufactured by Toa Gosei Co., Ltd.) and an aliphatic glycidyl ether compound (trade name: Denacol EX-314) 10.8 g of Nagase ChemteX Corp.) was added.

  Next, 2.76 parts by weight of isophorone diamine (manufactured by Nagase ChemteX Corp.) was added as a curing agent, and the mixture was stirred at room temperature for 1 hour. Furthermore, 2.0 g of aminosilane (trade name: KBM-602, manufactured by Shin-Etsu Chemical Co., Ltd.) was added thereto and stirred at room temperature for 30 minutes. Next, 0.4 g of tetraethoxysilane (manufactured by Junsei Chemical Co., Ltd.) was added, and 92.8 g of ethanol (manufactured by Wako Pure Chemical Industries, Ltd.) was added, followed by stirring at room temperature for 30 minutes. Next, 0.043 g of amino-modified silicone (product number: FZ3789, manufactured by Toray Dow Corning Silicone Co., Ltd.) was added thereto, and the mixture stirred at room temperature for 30 minutes was designated as Liquid Composition 3 for forming a water-absorbent coating.

The glass substrate with the silver-based heat ray reflective film obtained above was set horizontally, 30 g of the liquid composition 3 for forming a water-absorbent coating was dropped, and then applied by spin coating at 50 rpm for 20 seconds while rotating the substrate. The heat ray reflective glass 1 having a water-absorbing film with an average film thickness of 20 μm was obtained by drying at 60 ° C. for 60 minutes.

The saturated water absorption amount of the water absorbent resin obtained above was 17 mg / cm ³ .
Table 2 shows the evaluation results of visible light transmittance (Tv), solar reflectance (Re), abrasion resistance, moisture resistance and antifogging performance.

[Example 4] Production of heat ray reflective glass without water-absorbing coating The heat-reflecting glass 1 was obtained without attaching a water-absorbing coating to the glass substrate with a silver-based heat ray reflective layer obtained above.
Table 2 shows the evaluation results of visible light transmittance (Tv), solar reflectance (Re), abrasion resistance, moisture resistance and antifogging performance. In addition, the photograph (optical microscope: 500 times) showing the external appearance of the heat ray reflective glass 1 after a moisture resistance test is shown in FIG.4 (B).

  The heat ray reflective glass of the present invention is a heat ray reflective glass having a high wear resistance and moisture resistance, in which a silver-based heat ray reflective film and a water-absorbing film are formed on a single glass substrate. It can be used as a window glass for a vehicle attached to a building, or a window glass for a building material attached to a building such as a house or a building.

DESCRIPTION OF SYMBOLS 1 ... Glass substrate, 2 ... Silver type multilayer heat ray reflective film, 3 ... Water absorbing film, 10 ... Heat ray reflective glass 20 ... Glass substrate 110 with a silver type heat ray reflective film, 120 ... Heat ray reflective layer 210 ... Bottom dielectric layer, 220 ... center dielectric layer, 230 ... top dielectric layer 311, 312, 321, 322 ... barrier layer

Claims (11)

  A heat ray reflective glass having a heat ray reflective film having a layer mainly composed of silver on at least one surface of a glass substrate, and further having a water absorbent film mainly comprising a water absorbent resin on the surface thereof. The heat ray reflective glass according to claim 1, wherein the water absorption resin has a saturated water absorption amount of 5 to 150 mg / cm ³ .   The heat ray reflective glass according to claim 1 or 2, wherein the water-absorbent coating has a thickness of 5 to 50 µm.   The heat ray reflective glass according to any one of claims 1 to 3, wherein the water-absorbent resin is a crosslinked resin obtained by a reaction between a polyepoxide and a curing agent.   The heat ray reflective glass according to any one of claims 1 to 3, wherein the water-absorbent resin is a crosslinked resin obtained by a reaction between a crosslinkable vinyl polymer having a cationic group and a crosslinkable group and a crosslinking agent. . The heat ray reflective glass according to any one of claims 1 to 3, wherein the water absorbent resin is hydroxypropyl cellulose, polyvinyl alcohol, polyvinyl acetal, polyvinyl pyrrolidone, or polyvinyl acetate.   The heat ray reflective glass according to claim 4, wherein the polyepoxide is a glycidyl ether-based polyepoxide.   The heat ray reflective glass according to claim 7, wherein the glycidyl ether-based polyepoxide is at least one selected from the group consisting of glycerin polyglycidyl ether, diglycerin polyglycidyl ether, polyglycerin polyglycidyl ether, and sorbitol polyglycidyl ether. .   The heat ray reflective glass according to claim 6, further comprising a water repellent coating on the surface of the water absorbing coating.   In the 70-rotation wear test using a CS-10F wear wheel with a load of 500 g based on JIS-R3212 (1998) on the surface of the water-absorbent coating, the heat ray reflective film does not peel from the glass substrate. The heat ray reflective glass according to any one of claims 1 to 9, wherein   11. The white spot is not generated in the heat ray reflective film in a moisture resistance test in which the entire heat ray reflective glass is maintained for 500 hours under conditions of a temperature of 80 ° C. and a relative humidity of 85%. The heat ray reflective glass according to Item.

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