WO2020138320A1

WO2020138320A1 - Transparent heat-shielding/heat-insulating member and method for producing same

Info

Publication number: WO2020138320A1
Application number: PCT/JP2019/051200
Authority: WO
Inventors: 宮田照久; 水谷拓雄; 光橋文枝
Original assignee: マクセルホールディングス株式会社
Priority date: 2018-12-27
Filing date: 2019-12-26
Publication date: 2020-07-02
Also published as: JP7344906B2; JPWO2020138320A1

Abstract

A transparent heat-shielding/heat-insulating member disclosed by the present application comprises a transparent substrate and a functional layer formed thereon. The functional layer comprises an infrared reflecting layer and a coating-type protective layer disposed in this sequence from the transparent substrate side. The infrared reflecting layer comprises, disposed in the indicated sequence from the transparent substrate side, at least a metal layer and a metal suboxide layer or metal oxide layer. The protective layer is constituted by a plurality of layers wherein at least one layer of the layers other than the layer disposed on the outermost surface side thereof is constituted by a hydroxy group-bearing (meth)acrylic copolymer and a polyisocyanate-type crosslinking agent that reacts with the hydroxy group. The (meth)acrylic copolymer contains, as copolymer units, a hydroxy group-bearing monomer and an alkyl (meth)acrylate ester monomer having a C4-10 alkyl group, the alkyl (meth)acrylate ester monomer being capable of forming a homopolymer having a glass transition temperature of 20°C-155°C. The layer disposed on the outermost surface side of the protective layer is constituted by an active energy radiation-curable resin.

Description

Transparent heat shield and heat insulating member and method for manufacturing the same

The present invention mainly relates to a transparent heat insulating and heat insulating member such as a film for adjusting solar radiation for energy saving, which is used by being attached to the indoor side such as window glass. In particular, the present invention relates to a transparent heat insulating and heat insulating member such as a solar radiation adjusting film for year-round energy saving, which is excellent in heat insulating property and suppresses corrosion deterioration due to dew condensation water or adhesion of human skin oil, and a manufacturing method thereof.

From the perspective of preventing global warming and saving energy, a heat shield film can be attached to the windows of buildings, show windows, automobile windows, etc. to cut the heat rays (infrared rays) of sunlight and reduce the internal temperature. It is widely practiced. In addition, in recent years, from the viewpoint of further energy saving, not only the heat shield property that cuts the heat rays that cause the temperature rise in summer, but also the heat insulation function that suppresses the heating heat outflow from the room in winter and reduces the heating load. With the development of a heat-insulating and heat-insulating material that is suitable for energy saving throughout the year and has been put on the market, its recognition is gradually increasing.

With the diversification of solar control films introduced into the market in this way, in view of the active commercialization of films with excellent heat insulation properties, the Japanese Industrial Standard (JIS) A5759 of architectural window glass films has been adopted. In 2016, the standard was revised, and in order to make the definition of heat insulation more clear, a new application and performance category was added as "low radiation film".

In JIS A5759-2016, low-emission films are classified into the following four types A to D depending on the combination of visible light transmittance and heat transmission coefficient which is an index of heat insulation performance.
Category A: Visible light transmittance of less than 60%, thermal transmittance of 4.2 W/(m ² ·K) or less Category B: Visible light transmittance of less than 60%, thermal transmittance of more than 4.2, 4.8 W/(m ²・K) or less Category C: visible light transmittance of 60% or more, heat transmission coefficient of 4.2 W/(m ² ·K) or less Category D: visible light transmittance of 60% or more, heat transmission coefficient of more than 4.2 4 0.8 W/(m ² ·K) or less

Among the low-emission films classified into the above 4 types, the low-emission films corresponding to the categories A and C having a heat transmission coefficient of 4.2 W/(m ² ·K) or less are particularly excellent in heat insulation. It is expected that low-emission films falling into these categories will gradually penetrate the market in the future.

Further, recently, in order to further improve the heat insulating property and the energy saving effect in winter, the heat transmission coefficient is 4.0 W/(m ² ·K) or less, more specifically, in the category A and the category C. Products in the 3.6 to 3.8 W/(m ² ·K) class are also targets for the development of next-generation low-emission films.

As the structure of the low-emission film, generally, a structure of an infrared reflection film in which a metal oxide layer, a metal layer, a metal oxide layer, and a transparent protective layer (hard coat layer) are provided in this order on a transparent substrate. Are listed. The laminated portion of the metal oxide layer, the metal layer, and the metal oxide layer is a relatively highly transparent infrared reflection layer, and the metal oxide layer is visible due to the interference effect at the interface with the metal layer that reflects infrared rays. The light reflectance is adjusted to control the balance between the visible light transmittance and the infrared reflectance of the entire infrared reflective layer, and at the same time, it has the role of suppressing the corrosion deterioration of the metal layer. However, the infrared reflective layer does not have sufficient scratch resistance as it is, and protection by only the metal oxide layer does not work under an environment where external environmental factors such as oxygen, water, and chloride ions act synergistically. Since the metal layer is apt to be corroded and deteriorated, a transparent protective layer is further provided thereon for the purpose of improving the scratch resistance of the infrared reflecting layer and suppressing the influence of the above external factors.

However, the thermal transmittance of the low emissivity film as described above 4.2W / (m ² · K) or less, and still more, in order to further improve the thermal insulation properties and 4.0W / (m ² · K) or less It is necessary to reflect far infrared rays to the indoor side more efficiently (to reduce the vertical emissivity), and it is necessary to make the thickness of the transparent protective layer as thin as possible. This is because in order to improve the scratch resistance of the protective layer, for example, a material that easily absorbs far infrared rays such as a radiation-curable acrylic hard coat material (the molecular skeleton has a C═O group, a C—O group, an aromatic group). As the thickness of the protective layer becomes thicker, the absorption of far infrared rays increases, and the solar radiation adjustment film itself absorbs far infrared rays. This is because the adjustment film cannot efficiently reflect far infrared rays to the indoor side.

The thickness of the transparent protective layer cannot be generally stated because it depends on the constituent material of the transparent protective layer, but a specific example will be explained. As a base infrared reflecting layer, the heat transmission coefficient is 3.7 W/( m ² ·K), for example, in order to set the heat transmission coefficient of the low radiation film to 4.2/(m ² ·K) or less, the thickness of the transparent protective layer is about It should be 1.0 μm or less. Similarly, in order to reduce the heat transmission coefficient of the low radiation film to 4.0 W/(m ² ·K) or less, the thickness of the transparent protective layer needs to be about 0.7 μm or less. In order to set the heat transmission coefficient of the radiation film to 3.8 W/(m ² ·K) or less, the thickness of the transparent protective layer needs to be about 0.5 μm or less.

As a conventional technique, in order to provide an infrared reflective film having both excellent heat insulation and practical durability, Patent Document 1 discloses that a first metal oxide layer and silver are mainly formed on a transparent film substrate. A second metal oxide layer comprising a metal layer as a component and a composite metal oxide layer containing zinc oxide and tin oxide, wherein the second metal oxide layer has a thickness of 30 nm to 150 nm and is polymerizable with an acidic group. Disclosed is an infrared reflective film characterized in that a transparent protective layer having a crosslinked structure derived from an ester compound having a functional group in the same molecule is in direct contact therewith.

Further, in addition to being excellent in heat shield property, Patent Document 2 discloses an infrared reflective film capable of effectively preventing the face of a resident or the like from being reflected in a window provided with an infrared reflective film. An infrared reflecting film comprising a transparent film substrate, a first metal oxide layer, an infrared reflecting layer, a second metal oxide layer, and a transparent protective layer, which are laminated in this order on the transparent film substrate. The thickness of the first metal oxide layer is 30 nm or less, the thickness of the first metal oxide layer is smaller than the thickness of the second metal oxide layer, and the thickness of the first metal oxide layer and the second metal oxide are Disclosed is an infrared reflective film characterized in that the difference from the thickness of the object layer is 2 nm or more.

Further, similarly, for the purpose of providing a transparent heat insulating and heat insulating member having excellent heat insulating properties and appearance (suppression of iris phenomenon and reflection color change depending on viewing angle), Patent Document 3 discloses a transparent substrate. An infrared reflective layer including at least a metal layer and a metal suboxide layer in which the metal is partially oxidized, and a protective layer in this order, and the protective layer has a total thickness of 200 to 980 nm. Disclosed is a transparent heat insulating and heat insulating member including at least a high refractive index layer and a low refractive index layer in this order from the side.

JP, 2014-167617, A JP, 2017-68118, A Japanese Patent Laid-Open No. 2017-053967

As described in the exemplified prior art documents, by making the thickness of the transparent protective layer thinner, it becomes possible to further reduce the heat transmission coefficient as a low radiation film, but on the other hand, As described above, making the thickness of the transparent protective layer thinner is generally a direction in which the function of protecting the infrared reflective layer from external environmental factors such as oxygen, moisture, and chloride ions is decreased, that is, oxygen, Since the diffusion and penetration time of moisture and chloride ions in the depth direction of the protective layer is shortened, there is a problem that corrosion deterioration of the metal layer is more likely to occur. Corrosion deterioration of the metal layer causes deterioration of the heat-insulating and heat-insulating function of the low-emission film and appearance defects such as discoloration. Further, making the thickness of the transparent protective layer thinner also tends to reduce physical properties such as scratch resistance, so that the film surface (transparent protective layer during film application or when the film is used for a long period of time). ) Is apt to be damaged, and there is a concern that the appearance may be deteriorated due to the damage and the metal layer may be corroded and deteriorated.

Regarding the problem of corrosion deterioration of the metal layer, in Patent Document 1, the metal oxide layer provided on the transparent protective layer side of the infrared reflective layer has chemical stability (durability against acids, alkalis, chloride ions, etc.). The problem is solved by using a composite metal oxide (ZTO) containing excellent zinc oxide and tin oxide.

However, the infrared reflective film disclosed in Patent Document 1 uses a ZTO layer having excellent chemical stability as the metal oxide layer provided on the transparent protective layer side of the infrared reflective layer, Since the thickness is extremely thin, from 30 nm to 150 nm, there is room for improvement in terms of scratch resistance, and the chloride contained in human sebum adheres to the infrared reflective film surface when the human hand or finger touches it. When used for a long period of time in a harsh environment where condensation is extremely likely to occur, the above-mentioned external environmental factors such as oxygen, moisture, and chloride ions act synergistically and strongly, resulting in corrosion deterioration of the metal layer. There is still concern about the fact that the heat insulation and heat insulation function may be deteriorated and the appearance may be deteriorated. In addition, since the thicknesses of the ZTO layers used as the first metal oxide layer and the second metal oxide layer are both about 30 nm, the visible light transmittance is relatively high and the visible light reflectance is relatively low. It is estimated that the solar radiation absorption rate is relatively high (about 25% to 30%), and when the infrared reflective film is attached to the window glass, the type of window glass, the orientation of the window glass, and the condition of the shadow of the window glass. In some cases, the temperature near the center of the window glass becomes high, which may cause thermal cracking of the window glass.

Further, also in Patent Document 2, as a metal oxide layer provided on the transparent protective layer side of the infrared reflective layer, zinc oxide and oxide excellent in chemical stability (durability against acids, alkalis, chloride ions, etc.) By using a mixed metal oxide (ZTO) containing tin, the problem of corrosion deterioration of the metal layer is solved.

However, the infrared reflective film disclosed in Patent Document 2 also uses the ZTO layer having excellent chemical stability as the metal oxide layer provided on the transparent protective layer side of the infrared reflective layer, but the transparent protective layer Since the thickness is extremely thin as 50 nm to 70 nm (in the range of Examples), there is room for improvement in terms of scratch resistance, and the chloride contained in human sebum by touching the infrared reflective film surface with human hands or fingers. If the product is used for a long period of time in a harsh environment where dew condensation is extremely likely to occur with substances attached, corrosion and deterioration of the metal layer may be accelerated, which may lead to deterioration of the heat insulation and heat insulation function and poor appearance. There is still concern about that. The thickness of the first metal oxide layer (ZTO layer) is 4 to 15 nm, the thickness of the second metal oxide layer (ZTO layer) is 10 to 25 nm, which is still large, and the solar radiation absorption rate is 22 to 35%. When the infrared reflection film is attached to the window glass, the temperature near the center of the window glass may become high depending on the type of the window glass, the orientation of the window glass, the shadow condition of the window glass, etc. There is also concern that it may cause thermal cracking.

Further, in Patent Document 3, a metal suboxide layer in which the metal is partially oxidized is provided on the metal layer, so that the metal is subjected to a corrosion resistance test in which the metal suboxide layer is left in an environment of a temperature of 50° C. and a relative humidity of 90% for 168 hours. We are trying to solve the problem of layer corrosion deterioration. In the transparent heat insulating and heat insulating member disclosed in Patent Document 3, since the thickness of the TiO _X layer used as the metal suboxide layer is set as thin as 2 to 6 nm, the visible light reflectance is relatively high. It is presumed that the solar radiation absorption rate is high and the solar radiation absorption rate is relatively low, and it is considered that the risk of thermal cracking of the window glass when the transparent heat insulating/insulating member is attached to the window glass is reduced. Further, since the thickness of the TiO _x layer is thin, the cost and manufacturing efficiency at the time of sputtering film formation are improved.

However, in the transparent thermal insulation member disclosed in Patent Document 3, the TiO _X layer used as the metal suboxide layer has a thin thickness of 2 to 6 nm, and the protective layer formed thereon. Since its thickness is relatively thin at 210 to 930 nm, there is no problem in the corrosion resistance test of leaving it in an environment of temperature 50°C and relative humidity 90% for 168 hours. If the product is used for a long period of time in a harsh environment where chloride contained in human sebum adheres to it when touched or touched with a finger, and it is extremely liable to cause dew condensation, corrosion deterioration of the metal layer is promoted and shielding occurs. There is concern that the thermal insulation function may be deteriorated and the appearance may be deteriorated.

As described above, in the low radiation film having the thermal conductivity of 4.2 W/(m ² ·K) or less, and further 4.0 W/(m ² ·K) or less, the low radiation film with improved heat insulation has oxygen, Excellent corrosion resistance deterioration when used for a long period of time in an extremely harsh environment where external environmental factors such as moisture and chloride ions synergistically affect, and also has practical scratch resistance. What has been obtained is not currently available. Further, there is still room for improvement in reducing the risk of thermal cracking of the glass when the film is attached to the window glass, that is, reducing the solar radiation absorption rate.

The present invention is incompatible with the above-mentioned problem, that is, in the transparent heat insulating and heat insulating member, it is not possible to meet the mutually opposing requirements of improving the heat insulating performance and suppressing the corrosion deterioration when used for a long period of time in a harsh environment. It is a solution to the problem, and in particular, it has excellent heat insulation properties and suppresses corrosion and deterioration caused by condensation water and the adhesion of human skin oil. A thermal insulation member is provided. In addition, the present invention provides a transparent heat insulating/insulating member which has a reduced solar absorptance and an improved appearance.

In order to solve the above-mentioned problems, the inventors of the present application firstly assumed a harsh environment for use of the heat insulating and heat insulating member disclosed in Patent Document 3 at a temperature of 50° C. and a concentration of 5 mass% sodium chloride. A salt water resistance test was carried out by immersing in an aqueous solution for 10 days, and the transmission spectrum in the wavelength range of 300 to 1500 nm was measured before and after the immersion. The transmission spectrum changed after the immersion, and the near-infrared reflection function tended to deteriorate. I knew it was. In this case, the function of reflecting far infrared rays having a wavelength of 5.5 to 25.2 μm is also deteriorated. Further, when the heat insulating and heat insulating member was taken out during the test and the surface thereof was observed, it was found that in the initial state of corrosion deterioration, the corrosion deteriorated portion mainly existed in the form of dots. This heat insulating and heat insulating member has a structure in which a thin metal suboxide layer and a protective layer are formed on a metal layer, but nevertheless, the metal layer when used in a harsh environment In view of the above situation, it was presumed that the cause was as follows as to the corrosion deterioration resistance of No. 1 was more than expected.

In the heat insulating and heat insulating member, when the first metal suboxide layer, the metal layer, and the second metal suboxide layer are formed as the infrared reflective layer on the transparent substrate by sputtering in this order, the metal suboxide is used. From the viewpoint of imparting corrosion resistance in the environment of a temperature of 50° C. and a relative humidity of 90% as the thickness of the layer, and suppressing the reduction of the visible light transmittance of the infrared reflective layer due to the effect of light absorption of metal suboxide. From the viewpoint of the above, and from the viewpoint of the processing speed of sputtering, that is, the viewpoint of improving productivity, the thickness of the metal suboxide layer is made extremely thin to several nm. It is presumed that this is due to SEM/EDX analysis of the surface of the infrared reflective layer, and it was found that minute protrusions on the transparent substrate (spike filler in the substrate, slippery filler in the easily adhesive layer of the substrate, Foreign matter, etc.), (1) a very small part where the metal layer is not completely covered by the second metal suboxide layer, or (2) the infrared reflection layer itself is partially torn and peeled off. It was found that a very small portion (a metal layer was exposed at the end surface of the torn layer) was present. Moreover, although the clear reason is not clear, it is surprising that (3) it seems to be an extremely minute aggregate or an extremely minute bump of the metal derived from the metal layer that seems to have penetrated the second metal suboxide layer. There are also (4) fine metal agglomerates presumed to be generated by arc during sputtering, and (5) flaky metal flakes estimated to be caused by falling contaminants in the sputtering chamber. I noticed that

In any case, “the metal layer is not completely covered by the second metal suboxide layer and the metal derived from the metal layer is exposed on the surface of the infrared reflective layer as described in (1) to (5) above. It is found that there are extremely minute parts (including minute metal aggregates, minute bump-like objects and metal flakes) that are present in the It was considered to be the main cause of corrosion and deterioration of the metal layer of the heat insulating and heat insulating member when used in the environment. That is, although a protective layer containing an organic substance and an inorganic oxide is formed on the infrared reflective layer, the thickness of the protective layer is as thin as 210 to 930 nm in order to reduce the heat transmission coefficient, and the protective layer contains oxygen and oxygen. It is difficult to completely suppress the diffusion and permeation of water and chloride ions, and when used in a harsh environment, oxygen, water and chloride ions gradually diffuse through the minute gaps in the protective layer, When it penetrates and reaches the above-mentioned “very minute area where the metal layer is not completely covered by the second metal suboxide layer and the metal derived from the metal layer is exposed,” Phenomenon in which corrosion deterioration of metal starts from a small part, and in some cases the start of corrosion deterioration of metal also triggers peeling of the protective layer, and corrosion deterioration gradually spreads over the entire metal layer. Presumed to be caused.

As a result of intensive studies to solve the above problems, the present inventors have made a transparent base material and at least a metal layer and a metal suboxide layer or a metal oxide layer formed on the transparent base material in this order. For the infrared reflection layer including the above, a coating type protective layer composed of a plurality of layers is provided on the infrared reflection layer, and at least one layer other than the layer positioned on the outermost surface side of the coating type protective layer is provided. An alkyl (meth)acrylate having 4 to 10 carbon atoms in the alkyl group capable of forming a homopolymer having a glass transition temperature of 20° C. to 155° C. with a monomer having a hydroxyl group as a pre-curing resin component. A (meth)acrylic copolymer containing an ester monomer as a copolymer unit and a layer containing a polyisocyanate crosslinking agent that reacts with the hydroxyl group, If the layer located on the outermost surface side is formed of a layer containing an active energy ray-curable resin as a pre-curing resin component, the total thickness of the protective layer is less than 1 μm in order to reduce the heat reflux rate. Even when set to the above, the layer containing the specific acrylic copolymer after being cured by the cross-linking agent is, for example, the layer of the above (1) to (5) present on the surface of the infrared reflecting layer. Oxygen, water, and chloride ions for "a minute portion where the metal layer is not completely covered by the second metal suboxide layer and the metal derived from the metal layer is exposed" It is possible to function as a layer that protects against external environmental factors such as barrier layer, that is, diffusion and penetration of oxygen, moisture, chloride ions, etc. in the depth direction of the protective layer are significantly suppressed, and as a result, metal The present invention has been completed by finding that the progress of corrosion deterioration of the layer is remarkably suppressed and that the protective layer of the coating type comprising the above-mentioned plurality of layers after curing has practical scratch resistance.

Further, in addition to the constitution of the coating type protective layer, in the heat insulating and heat insulating member, the infrared reflecting layer is provided from the transparent base material side to a first metal suboxide layer or a metal oxide layer, a metal. Layer, the second metal suboxide layer or the metal oxide layer in this order, and the total thickness of the infrared reflection layer is 7 to 25 nm or less, the second metal suboxide layer or the metal oxide. It has been found that when the layer thickness is 25% or less of the total thickness of the infrared reflective layer, the corrosion resistance of the metal layer is excellent and the solar radiation absorptivity of the transparent heat insulating/insulating member can be reduced, and the present invention is made. Came to.

The transparent heat insulating heat insulating member of the present invention is a transparent heat insulating heat insulating member including a transparent substrate and a functional layer formed on the transparent substrate, wherein the functional layer is from the transparent substrate side. Including an infrared reflection layer and a coating type protective layer in this order, the infrared reflection layer, from the transparent substrate side, at least a metal layer, and includes a metal suboxide layer or a metal oxide layer in this order, the coating The protective layer of the mold is composed of a plurality of layers, and at least one of the layers other than the layer located on the outermost surface side of the protective layer of the coating type has a hydroxyl group as a pre-curing resin component (meth). The (meth)acrylic copolymer is composed of a layer containing an acrylic copolymer and a polyisocyanate crosslinking agent that reacts with the hydroxyl group, and the (meth)acrylic copolymer contains a monomer having a hydroxyl group and a glass transition temperature of 20° C. or higher. A (meth)acrylic acid alkyl ester monomer having an alkyl group having a carbon number of 4 or more and 10 or less capable of forming a homopolymer at 155° C. or less is included as a copolymer unit, The layer located on the outer surface side is characterized by being a layer containing an active energy ray-curable resin as a pre-curing resin component.

In the above aspect, the hydroxyl value of the (meth)acrylic copolymer is preferably 30 mgKOH/g or more and 200 mgKOH/g or less.

Further, the coating type protective layer, from the infrared reflection layer side, includes a medium refractive index layer, a high refractive index layer and a low refractive index layer in this order, the middle refractive index layer, as a pre-curing resin component, It is preferable to include a (meth)acrylic copolymer having a hydroxyl group and a polyisocyanate crosslinking agent that reacts with the hydroxyl group.

Further, the coating type protective layer further includes an optical adjustment layer, a medium refractive index layer, a high refractive index layer and a low refractive index layer in this order from the infrared reflecting layer side, and the medium refractive index layer is a cured layer. More preferably, the (meth)acrylic copolymer having a hydroxyl group and a polyisocyanate crosslinking agent that reacts with the hydroxyl group are included as the pre-resin component.

Furthermore, it is more preferable that the (meth)acrylic acid alkyl ester monomer is at least one selected from the group consisting of t-butyl methacrylate and t-butyl acrylate.

The total thickness of the coating type protective layer is preferably 200 nm or more and 980 nm or less.

In addition, it is preferable that at least a layer of the coating type protective layer that is in direct contact with the metal suboxide layer or the metal oxide layer contains a corrosion inhibitor for metal.

Furthermore, it is more preferable that the corrosion inhibitor for the metal contains at least one compound selected from a compound having a nitrogen-containing group and a compound having a sulfur-containing group.

Further, the infrared reflective layer, from the transparent substrate side, includes a first metal suboxide layer or metal oxide layer, a metal layer, a second metal suboxide layer or metal oxide layer in this order, The total thickness of the infrared reflective layer is 7 nm or more and 25 nm or less, and the thickness of the second metal suboxide layer or the metal oxide layer is 25% or less of the total thickness of the infrared reflective layer. It is preferable.

Furthermore, it is more preferable that the metal layer of the infrared reflective layer contains silver, and the thickness of the metal layer is 5 nm or more and 20 nm or less.

Furthermore, it is more preferable that the metal suboxide or the metal oxide contained in the second metal suboxide layer or the metal oxide layer of the infrared reflective layer contains a titanium component.

The transparent heat insulating and heat insulating member has a visible light transmittance of 60% or more, a shielding coefficient of 0.69 or less, a heat transmission coefficient of 4.0 W/(m ² ·K) or less, and a solar absorptivity. Is preferably 20% or less.

Further, in the case where a salt water resistance test in which the transparent heat insulation heat insulating member is immersed in an aqueous sodium chloride solution having a temperature of 50° C. and a concentration of 5 mass% for 30 days is performed, the transparent heat insulation heat insulation member measured before the salt water resistance test. The transmittance of light having a wavelength of 1100 nm in the transmission spectrum in the wavelength range of 300 to 1500 nm of the member is T _B %, and the wavelength of the transmission spectrum is 1100 nm in the wavelength range of 300 to 1500 nm of the transparent heat insulating and heat insulating member measured after the salt water resistance test. It is more preferable that the value of T _A -T _B is less than 10 points, where T _A % is the light transmittance of.

Further, in the reflection spectrum measured according to JIS R3106-1998, it corresponds to the wavelength 535 nm on the virtual line a indicating the average value of the maximum reflectance and the minimum reflectance in the wavelength range of 500 to 570 nm of the reflection spectrum. The point is point A, the point corresponding to the wavelength 700 nm on the virtual line b indicating the average value of the maximum reflectance and the minimum reflectance in the wavelength range of 620 to 780 nm of the reflection spectrum is point B, and the points A and A straight line passing through the point B is extended in the wavelength range of 500 to 780 nm to form a reference straight line AB, and the reflectance value of the reflection spectrum and the reflectance value of the reference straight line AB in the wavelength range of 500 to 570 nm are compared. In this case, when the absolute value of the difference between the reflectance values at the wavelength where the difference between the respective reflectance values is the maximum is defined as the maximum variation difference ΔA, the value of the maximum variation difference ΔA is the% unit of the reflectance. Is 7% or less, and when the reflectance value of the reflectance spectrum in the wavelength range of 620 to 780 nm and the reflectance value of the reference line AB are compared, the difference between the reflectance values becomes maximum. When the absolute value of the difference in the reflectance values at the wavelength is defined as the maximum variation difference ΔB, the value of the maximum variation difference ΔB is more preferably 9% or less in% of the reflectance.

Further, the method for producing a transparent heat insulating and heat insulating member of the present invention comprises a step of forming an infrared reflective layer on a transparent substrate by a dry coating method, and a wet protective layer composed of a plurality of layers on the infrared reflective layer. And a step of forming by a coating method.

According to the present invention, a transparent heat shield having a high visible light transmittance, excellent heat insulation properties, and substantially suppressed corrosion deterioration due to dew condensation water or human skin oil adhesion, and practical scratch resistance. A heat insulating member can be provided. Further, it is possible to provide a transparent heat-insulating and heat-insulating member having a reduced solar radiation absorption rate. That is, the transparent heat insulating and heat insulating member of the present invention is attached to a window glass and used for a long period of time in an extremely harsh environment in which external environmental factors such as oxygen, water and chloride ions synergistically affect. Even so, the heat shield and heat insulating function and the good appearance can be maintained. Moreover, the risk of thermal cracking of the glass when it is attached to the window glass can be reduced.

FIG. 1 is a schematic cross-sectional view showing an example of a transparent heat insulating/insulating member according to an embodiment of the present invention. FIG. 2 is a diagram showing an example of a transmission spectrum of the transparent heat insulating/insulating member before and after the salt water resistance test of the present invention. FIG. 3 is a diagram for explaining how to obtain the “reference straight line AB”, the “maximum variation difference ΔA”, and the “maximum variation difference ΔB” of the reflectance of the transparent heat insulating and heat insulating member of the present invention with respect to the visible light reflection spectrum. FIG. 4 is a reflection spectrum in the visible light region when light is measured from the glass surface side in Example 1 of the present invention.

(Transparent heat insulating and heat insulating member)
First, an embodiment of the transparent heat insulating/insulating member of the present invention will be described. One embodiment of the transparent heat insulating and heat insulating member of the present invention includes a transparent base material and a functional layer formed on the transparent base material, wherein the functional layer is an infrared reflective layer and an infrared reflective layer from the transparent base material side. Includes a coating type protective layer in this order, the infrared reflective layer, from the transparent substrate side, at least a metal layer, and, containing a metal suboxide layer or a metal oxide layer in this order, the coating type protective layer Is composed of a plurality of layers, and at least one of the layers other than the layer located on the outermost surface side of the above-mentioned coating type protective layer has a (meth)acrylic copolymer copolymer having a hydroxyl group as a pre-curing resin component. The (meth)acrylic copolymer is composed of a layer containing a polymer and a polyisocyanate cross-linking agent that reacts with the hydroxyl group, and the (meth)acrylic copolymer has a monomer having a hydroxyl group and a glass transition temperature of 20° C. or higher and 155° C. or lower. A (meth)acrylic acid alkyl ester monomer having a carbon number of an alkyl group capable of forming a homopolymer of 4 or more and 10 or less is included as a copolymer unit, and the outermost surface side of the coating type protective layer is provided. The layer located is a layer containing an active energy ray-curable resin as a resin component before curing.

With the above-mentioned configuration, in order to reduce the heat transmission coefficient and further improve the heat insulating property, even if the protective layer composed of the plurality of coating type layers of the infrared reflective layer is thinly formed, the polyisocyanate-based material is also used. The layer containing the specific (meth)acrylic copolymer cured by the cross-linking agent becomes the above-mentioned "extremely minute portion where the metal derived from the metal layer is in a bare state" present on the infrared reflective layer surface. On the other hand, it can function as a layer that protects against external environmental factors such as oxygen, water, and chloride ions, that is, as a barrier layer, and diffuses and permeates oxygen, water, chloride ions, and other protective layers in the depth direction. Is significantly suppressed, and as a result, the progress of corrosion deterioration of the metal layer is significantly suppressed. In addition, the layer containing the specific (meth)acrylic copolymer cured by the polyisocyanate crosslinking agent naturally functions as a barrier layer for the infrared reflective layer including the metal layer. As a result, the transparent heat-insulating heat insulating member of the present embodiment has a large visible light transmittance and can reduce the heat transmission coefficient, and significantly suppresses the corrosion deterioration due to dew condensation water or the adhesion of human skin oil. You can Furthermore, since the layer located on the outermost surface side of the coating type protective layer is cured by irradiation with active energy rays, practical scratch resistance can be imparted.

Furthermore, one embodiment of the transparent heat insulating and heat insulating member of the present invention includes a transparent base material and a functional layer formed on the transparent base material, and the functional layer is provided from the transparent base material side. An infrared reflection layer and a coating type protective layer are included in this order, and the infrared reflection layer is formed from the transparent substrate side from the first metal suboxide layer or the metal oxide layer, the metal layer, the second metal suboxide. Object layer or a metal oxide layer in this order, the total thickness of the infrared reflective layer is 7 nm or more and 25 nm or less, the thickness of the second metal suboxide layer or the metal oxide layer is the infrared It is 25% or less of the total thickness of the reflective layer, and the coating type protective layer is composed of a plurality of layers, and at least one layer of the coating type protective layers other than the layer located on the outermost surface side. The layer is an alkyl (meth)acrylate having 4 to 10 carbon atoms in the alkyl group capable of forming a homopolymer having a glass transition temperature of 20° C. to 155° C. with a monomer having a hydroxyl group as a resin component before curing. A (meth)acrylic copolymer containing an ester monomer as a copolymer unit, and a layer containing a polyisocyanate crosslinking agent that reacts with the hydroxyl group, and among the coating-type protective layers, The layer located on the outermost surface side is a layer containing an active energy ray-curable resin as a resin component before curing.

By setting it as the said structure, in order to reduce a solar radiation absorptivity, the said 2nd metal suboxide layer or a metal oxide layer is formed thinly, and a heat transmission coefficient is reduced and heat insulation is improved more. Therefore, even if a thin protective layer consisting of the coating-type plurality of layers of the infrared reflecting layer is formed, a layer containing a specific (meth)acrylic copolymer cured by the polyisocyanate crosslinking agent is formed. As described above, “the metal layer present on the surface of the infrared reflective layer (1) to (5) is not completely covered by the second metal suboxide layer and the metal derived from the metal layer is exposed. It can function as a barrier layer, that is, a layer that protects the "microscopic part" and the infrared reflection layer from external environmental factors such as oxygen, water, and chloride ions. It is considered that diffusion and penetration of ions and the like in the depth direction of the protective layer are significantly suppressed, and as a result, the progress of corrosion deterioration of the metal layer is significantly suppressed. As a result, the transparent heat insulating and heat insulating member of the present embodiment has a large visible light transmittance, can reduce the heat transmission coefficient and the solar radiation absorptivity, and significantly corrodes and deteriorates due to dew condensation water or human skin oil adhesion. Can be suppressed.

Each component of the transparent heat insulating/insulating member of the present embodiment will be described below.

<Transparent substrate>
The transparent base material forming the transparent heat insulating and heat insulating member of the present embodiment is not particularly limited as long as it is made of a material having a light transmitting property. Examples of the transparent substrate include polyester-based resins (eg, polyethylene terephthalate, polyethylene naphthalate, etc.), polycarbonate-based resins, polyacrylic acid ester-based resins (eg, polymethylmethacrylate, etc.), alicyclic polyolefin-based resins, Polystyrene resin (for example, polystyrene, acrylonitrile-styrene copolymer, etc.), polyvinyl chloride resin, polyvinyl acetate resin, polyether sulfone resin, cellulose resin (for example, diacetyl cellulose, triacetyl cellulose, etc.), A resin such as a norbornene-based resin processed into a film shape or a sheet shape can be used. Examples of the method for processing the above resin into a film or sheet include an extrusion molding method, a calendar molding method, a compression molding method, an injection molding method, a method of dissolving the above resin in a solvent and casting. You may add additives, such as an antioxidant, a flame retardant, a heat stabilizer, an ultraviolet absorber, a slip agent, and an antistatic agent, to the said resin. The transparent substrate has a thickness of, for example, 10 μm or more and 500 μm or less, and preferably 25 μm or more and 125 μm or less in view of workability and cost.

<Infrared reflective layer>
The infrared reflective layer that constitutes the transparent heat insulating and heat insulating member of the present embodiment is particularly limited as long as it has a configuration including at least a metal layer and a metal suboxide layer or a metal oxide layer in this order from the transparent substrate side. Although not a thing, it is provided with a first metal suboxide layer or metal oxide layer, a metal layer, a second metal suboxide layer or metal oxide layer in this order from the transparent substrate side, and the infrared reflection The total thickness of the layers is 7 nm or more and 25 nm or less, and the thickness of the second metal suboxide layer or the metal oxide layer is set to 25% or less of the total thickness of the infrared reflective layer. Is preferred. The lower limit of the total thickness of the infrared reflective layer is preferably 7 nm or more in order to exhibit the functions (heat shielding performance and heat insulating performance) of the infrared reflective layer. When the total thickness of the infrared reflective layer is less than 7 nm, the reflectance of infrared rays decreases, the shielding coefficient and the heat transmission coefficient increase, and the heat shielding performance and the heat insulating performance may deteriorate.

The transparent heat insulating/insulating member can have a heat insulating function and a heat insulating function by including the infrared reflective layer. Further, in the transparent heat insulating/insulating member, when the total thickness of the infrared reflective layer is set to 25 nm or less, it becomes easy to design the visible light transmittance to be 60% or more. When the total thickness of the infrared reflective layer is more than 25 nm, the visible light transmittance becomes low and the transparency may be deteriorated.

Further, when the thickness of the second metal suboxide layer or the metal oxide layer is set to 25% or less of the total thickness of the infrared reflection layer, the thickness of the metal layer that greatly contributes to the infrared reflection function. The thickness can be relatively increased within the range of the total thickness of the infrared reflective layer. As a result, the reflectance of infrared rays can be increased, and the shielding coefficient and the heat transmission coefficient can be reduced.

Further, by increasing the thickness of the metal layer, the thickness of the first metal suboxide layer or metal oxide layer, and the second metal suboxide layer or metal oxide layer of the infrared reflection layer It can be made relatively thin within the range of 25% or less of the total thickness. In this case, the solar radiation characteristics (solar radiation transmittance, solar radiation reflectance, solar radiation absorption rate) of the infrared reflective layer formed on the transparent substrate are different depending on the type of metal, metal suboxide, or metal oxide used. Although it cannot be said, the thickness of the metal layer is the same, and the thickness of the first metal suboxide layer or metal oxide layer and the thickness of the second metal suboxide layer or metal oxide layer are the same as those of the present embodiment. Compared with the infrared reflection layer thicker than the range, it has the following features.

That is, in the infrared reflective layer of the present embodiment, the metal layers have the same thickness, and the first metal suboxide layer or the metal oxide layer and the second metal suboxide layer or the metal oxide layer have the same thickness. However, the solar radiation transmittance (A) tends to be lower in the wavelength range of 380 to 780 nm and higher in the wavelength range of 790 to 2500 nm as compared with the infrared reflective layer having a thickness larger than that of the present embodiment. Yes, (B) solar reflectance tends to be high in the wavelength range of 380 to 780 nm and low in the wavelength range of 790 to 2500 nm. Further, (C) solar reflectance and solar reflectance The added value tends to be higher. In other words, the solar radiation absorption rate, which is a value obtained by subtracting the solar radiation transmittance and the solar radiation reflectance from 100%, tends to be low. By providing a protective layer, which will be described later, on the infrared reflective layer having such a solar radiation property, the balance between the solar radiation transmittance and the solar radiation reflectance is controlled at a high level, and the thermal insulation has a relatively low solar radiation absorption rate. It can be a heat insulating member. As a result, when the infrared reflection film is attached to the window glass, the temperature rise near the central portion of the window glass can be suppressed and the window glass causes thermal cracking, as compared with the conventional infrared reflection film having heat insulation properties. The risk can be reduced.

On the other hand, when the thickness of the second metal suboxide layer or the metal oxide layer is set to be 25% or less of the total thickness of the infrared reflective layer, the heat insulation performance is improved and the solar radiation absorption rate is reduced. However, since it becomes difficult for the second metal suboxide layer or the metal oxide layer to completely cover the metal layer, it is difficult to completely cover the metal layer. There is a case where "a minute portion in which the metal derived from the metal layer is not completely covered by the second metal suboxide layer or the metal oxide layer and is in a bare state" is generated, and generally, The original protective function of the second metal suboxide layer or the metal oxide layer against the metal layer is deteriorated, and in a harsh environment of use, corrosion deterioration of the metal layer, which greatly contributes to the infrared reflection function, easily occurs. Become. However, in the transparent heat-insulating and heat-insulating member of the present embodiment, as described above, at least one of the layers other than the layer located on the outermost surface side of the protective layer composed of the plurality of coating-type layers is a Since the layer containing the specific (meth)acrylic copolymer hardened by the isocyanate crosslinking agent is included, the layer containing the specific (meth)acrylic copolymer is present on the surface of the infrared reflective layer. Oxygen, water, chloride for "a minute portion where the layer is not completely covered by the second metal suboxide layer or the metal oxide layer and the metal derived from the metal layer is exposed" It can function as a layer that protects from external environmental factors such as ions, that is, as a barrier layer, and can significantly suppress the progress of corrosion deterioration of the metal layer.

As a more specific preferred embodiment of the infrared reflective layer, for example, (A) transparent substrate/first metal suboxide layer/metal layer/second metal suboxide layer, (B) transparent substrate/first 1 metal oxide layer/metal layer/second metal suboxide layer, (C) transparent substrate/first metal suboxide layer/metal layer/second metal oxide layer, (D) transparent substrate/second Examples of the constitution include 1 metal oxide layer/metal layer/second metal oxide layer, (E) transparent substrate/metal layer/metal suboxide layer, and the like. Depending on the main purpose, it suffices to select one of the configurations, for example, from the viewpoint of further improving the corrosion resistance deterioration resistance of the metal layer of the infrared reflective layer and the effect of reducing the solar radiation absorptivity, among these, It is preferable to have a configuration of (A) to (C) including at least the metal suboxide layer, and (A) and (B) in which the second metal suboxide layer is laminated on the metal layer. The configuration is more preferable. Further, when it is desired to increase the visible light transmittance as much as possible, among these, it is preferable to have the configuration of (B) to (D) including at least the above metal oxide layer.

A hard coat layer or an adhesion improving layer (easy adhesion layer) may be provided between the infrared reflecting layer and the transparent substrate. When the hard coat layer is provided, an ordinary hard coat material can be used, and among them, an ultraviolet curable hard coat material composed of an acrylic oligomer or polymer having low shrinkage and bending resistance is used. Preference is given to using. By using such a hard coat material, for example, during the construction work of attaching the heat insulating and heat insulating film to the window glass, even if the heat insulating and heat insulating film is accidentally bent or bent, and a dent is generated, the hard coat layer is formed. Since microcracks are less likely to occur, microcracks in the infrared reflective layer formed on the hard coat layer are also less likely to occur, and the risk of impairing the function of the infrared reflective layer or the corrosion resistance deterioration of the metal layer. Can be reduced. The thickness of the hard coat layer is preferably 0.3 μm or more and 2.0 μm or less, more preferably 0.5 μm or more and 1.0 μm or less.

The metal layer contains a metal as a main component, and among general metals, silver (refractive index n=0.12), copper (n=n) having high electric conductivity and excellent far-infrared reflection performance. 0.95), gold (n=0.35), aluminum (n=0.96), and other metal materials can be used as appropriate, among which silver that absorbs visible light is relatively small and has the highest electrical conductivity. Is preferably used. Specifically, those containing 90% by mass or more of silver are preferable. Further, for the purpose of improving corrosion resistance, it may be used as an alloy containing at least one kind or two kinds or more of palladium, gold, copper, aluminum, bismuth, nickel, niobium, magnesium, zinc and the like. The metal layer can be formed by forming a film of any of these materials by a dry coating method such as a sputtering method, a vapor deposition method or a plasma CVD method. The thickness of each metal layer is preferably 5 nm or more and 20 nm or less, more preferably 8 nm or more and 16 nm or less, from the viewpoint of the balance between visible light transmittance and infrared reflectance. If the thickness of the metal layer is less than 5 nm, the reflectance of infrared rays is reduced, the shielding coefficient and the heat transmission coefficient are increased, and thus the heat shielding performance and the heat insulating performance may be deteriorated. On the other hand, when the thickness of the metal layer exceeds 20 nm, the visible light transmittance is reduced, and thus the transparency may be deteriorated.

The first metal suboxide layer or metal oxide layer and the second metal suboxide layer or metal oxide layer are provided above and below the metal layer as an optical compensation layer and a protective layer of the metal layer. To be In the first metal suboxide layer or metal oxide layer and the second metal suboxide layer or metal oxide layer, “metal suboxide” means oxidation according to the stoichiometric composition of the metal. It means a partial oxide (incomplete oxide) having a smaller oxygen element content than that of a substance, and the "metal oxide" means an oxide having a stoichiometric composition of a metal. Further, the metal suboxide layer does not necessarily have to be a layer of only partial oxides having a smaller oxygen element content than oxides according to the stoichiometric composition of the metal, and is formed by, for example, oxidation. It may be composed of an oxide layer according to the stoichiometric composition and an unoxidized layer left unoxidized. Specifically, the surface side directly in contact with the metal layer may be an unoxidized layer (as it is in the metal layer), and the surface opposite to the surface in direct contact with the metal layer may be oxidized.

The metal suboxide layer is provided above or below or above or below the metal layer with a predetermined thickness to be described later to improve the corrosion resistance deterioration of the metal layer of the infrared reflection layer and the solar absorptivity. The reduction can be compatible at a higher level. As the metal suboxide, partial oxides of metals such as titanium, nickel, chromium, cobalt, indium, tin, niobium, zirconium, zinc, tantalum, aluminum, cerium, magnesium, silicon, and mixtures thereof are appropriately used. It is possible. Among these, from the viewpoint of a dielectric that is relatively transparent to visible light and has a high refractive index, the metal suboxide is a partial oxide of titanium metal or a metal portion containing titanium as a main component. It is preferably an oxide. That is, the metal suboxide preferably contains a titanium component.

The method for forming the metal suboxide layer is not particularly limited, but it can be formed by, for example, a reactive sputtering method. That is, when a film is formed by the sputtering method using the above metal target, an oxidizing gas such as oxygen is added to an inert gas such as an argon gas at an appropriate concentration (oxidation when forming a metal oxide film). It is possible to form a partial (incomplete) oxide layer of a metal containing an oxygen element according to the oxidizing gas concentration, that is, a metal suboxide layer, in addition to a concentration lower than that of the oxidizing gas. It is also possible to form a metal suboxide layer by a sputtering method in an inert gas atmosphere using a reducing oxide composed of an oxide deficient in oxygen with respect to the stoichiometric composition of the metal as a target. Alternatively, the metal suboxide layer may be formed by once forming a metal thin film or a partially oxidized metal thin film by a sputtering method or the like, and then post-oxidizing it by heat treatment or exposure to the atmosphere. When forming the metal suboxide layer on the metal layer, from the viewpoint of suppressing the oxidation of the metal layer by an oxidizing gas and from the viewpoint of productivity, the atmosphere gas is an inert gas only, the target As once by a sputtering method using only the metal contained in the metal suboxide, after forming a metal thin film form, the metal thin film surface is post-oxidized by exposure to the atmosphere to form the metal suboxide layer. preferable.

As a preferable mode of the method for forming the metal suboxide layer in the present embodiment, specifically, on the transparent substrate under an inert gas atmosphere, first, a first metal suboxide layer as a target is first prepared. The first metal thin film corresponding to the precursor of the first metal suboxide layer is formed by the sputtering method using only the metal contained in the first metal, and then the first metal thin film is continuously formed without breaking the vacuum. The metal layer is formed on the thin film by a sputtering method using a metal such as silver as a target, and finally, continuously without breaking the vacuum, on the metal layer such as silver or the like as a target. The second metal thin film corresponding to the precursor of the second metal suboxide layer is formed by the sputtering method using only the metal contained in the second metal suboxide layer, and is wound as a roll. There is a method in which the surface of the second metal thin film is gradually oxidized while the roll is rewound in the atmosphere to transform the second metal suboxide layer into the second metal suboxide layer. In this case, when the first metal thin film is formed on the transparent substrate by the sputtering method, the surface side in contact with the transparent substrate is gradually oxidized by a small amount of outgas generated from the transparent substrate. It is considered that it is transformed into the first metal suboxide layer. Further, in this case, the surface side of the first metal suboxide layer and the second metal suboxide layer which is in direct contact with the metal layer such as silver is an unoxidized layer (metal layer, for example, titanium metal layer). It is considered that the unoxidized layer (metal layer, for example, titanium metal layer) can improve the function of protecting the metal layer such as silver from external environmental factors such as oxygen, water, chloride ions, etc. It is also suitable from the viewpoint of being able to.

Further, the metal oxide layer is provided above or below or above or below the metal layer with a predetermined thickness to be described later, thereby improving the visible light transmittance and reducing the solar absorptivity of the infrared reflective layer. be able to. Examples of the metal oxide include indium tin oxide (refractive index n=1.92), indium oxide zinc oxide (n=2.00), indium oxide (n=2.00), titanium oxide (n=2.50). ), tin oxide (n=2.00), zinc oxide (n=2.03), niobium oxide (n=2.30), aluminum oxide (n=1.77), tin oxide-zinc oxide (n= 2.00) and the like can be appropriately used, and the above metal oxide layer can be formed by forming a film of these materials by a dry coating method such as a sputtering method, a vapor deposition method, an ion plating method. Can be formed. Alternatively, the metal of the metal oxide may be used as a target and may be formed by a reactive sputtering method in an atmosphere gas in which the concentration of an oxidizing gas is sufficiently increased.

If the metal suboxide layer is formed of titanium (Ti) metal partial oxide of (TiO _X) layer, x in TiO _X in the layer, corrosion degradation of the metal layer of the infrared reflective layer From the viewpoint of further improving the effect of reducing the solar absorptance and improving the balance with the visible light transmittance, the range of 0.5 or more and less than 2.0 is preferable. When x in the above TiO _X is below 0.5, the visible light transmittance of the infrared reflective layer of the metal layer effects of corrosion degradation resistance and solar absorptance reduction of the infrared reflective layer is intended to improve is lowered, The transparency may be poor. When x in the above TiO _X is 2.0 or more, a possibility that the effect of the corrosion deterioration and solar absorptance reduction of the metal layer of the infrared reflection layer of which becomes high visible light transmittance of the infrared reflecting layer is lowered There is. The _x in TiO x can be analyzed and calculated using energy dispersive X-ray fluorescence analysis (EDX) or the like.

The thickness of the metal suboxide layer is preferably 1 nm or more and 6 nm or less, and when the thickness is in this range, the corrosion resistance deterioration effect of the metal layer of the infrared reflection layer and the solar radiation absorptivity reducing effect are further improved. At the same time, it can be balanced with the visible light transmittance. Further, the thickness of the metal oxide layer is preferably 1 nm or more and 6 nm or less, and when the thickness is in this range, the effect of reducing the solar absorptance of the infrared reflective layer and the visible light transmittance are balanced. You can When the thickness of the metal suboxide layer or the metal oxide layer is less than 1 nm, not only the protective function of the metal layer is inferior, but also the above-mentioned “the metal layer is the second metal suboxide layer or the metal oxide”. The risk of increasing ``microscopic parts where the metal derived from the metal layer is not completely covered by the layer and is in a bare state'' increases, and it may not be possible to secure sufficient corrosion deterioration resistance, and the visible light transmittance is It may become low and the transparency may be poor. Further, if the thickness of the metal suboxide layer or the metal oxide layer exceeds 6 nm, the solar absorptivity may be high especially in the case of the metal oxide layer.

<Coating type protective layer>
The coating-type protective layer that constitutes the transparent heat-insulating and heat-insulating member of the present embodiment includes a plurality of layers, and at least one layer of the coating-type protective layers other than the layer located on the outermost surface side is As a pre-curing resin component, a (meth)acrylic acid alkyl ester unit having 4 to 10 carbon atoms in the alkyl group capable of forming a monomer having a hydroxyl group and a homopolymer having a glass transition temperature of 20 to 155° C. A (meth)acrylic copolymer containing a monomer as a copolymer unit, and a layer containing a polyisocyanate crosslinking agent that reacts with the hydroxyl group, and the outermost layer of the coating type protective layer. The layer located on the surface side is a layer containing an active energy ray-curable resin as a resin component before curing. With the above structure, the heat reflux rate is reduced, and even if the protective layer composed of a plurality of the coating type layers is formed thin for the purpose of further improving the heat insulating property, the solar radiation absorption rate is further increased. For the purpose of reducing the above, even if the second metal suboxide layer or the metal oxide layer is thinly formed, as described above, the specific (meth) cured by the polyisocyanate-based crosslinking agent is used. The layer containing the acrylic copolymer protects the "extreme minute part where the metal derived from the metal layer is exposed" and the infrared reflective layer from external environmental factors such as oxygen, water, and chloride ions. Functioning as a barrier layer, that is, as a barrier layer, the diffusion and penetration of oxygen, moisture, chloride ions, etc. in the depth direction of the protective layer are significantly suppressed, and as a result, the progress of corrosion deterioration of the metal layer is prevented. It can be significantly suppressed. Further, since the layer located on the outermost surface side of the coating type protective layer is cured by the active energy ray-curable resin, practical scratch resistance can be imparted. Here, the “coating type protective layer” means a protective layer formed by a wet coating method described later.

Among the above-mentioned coating type protective layers, at least one layer other than the layer located on the outermost surface side has a monomer having a hydroxyl group as a pre-curing resin component and a glass transition temperature of 20° C. or higher and 155° C. or lower. A (meth)acrylic copolymer containing, as a copolymer unit, a (meth)acrylic acid alkyl ester monomer having an alkyl group capable of forming a homopolymer and having 4 to 10 carbon atoms is reacted with the hydroxyl group. A layer containing a polyisocyanate cross-linking agent is applied, and, in the coating type protective layer, the layer located on the outermost surface side is a layer containing an active energy ray-curable resin as a pre-curing resin component. It is applied for the following reasons.

Copolymerization of the above-mentioned monomer having a hydroxyl group with a (meth)acrylic acid alkyl ester monomer having a carbon number of 4 or more and 10 or less of an alkyl group capable of forming a homopolymer having a glass transition temperature of 20 to 155°C. A layer containing a (meth)acrylic copolymer contained as a united unit and a polyisocyanate crosslinking agent which reacts with the hydroxyl group is, after curing, "the metal derived from the metal layer is in a bare state in the infrared reflective layer. It was found that it has a high function (barrier function) to protect external minute factors such as oxygen, water, and chloride ions from "extremely minute parts" and the infrared reflection layer, but on the other hand, it seems to have scratch resistance. The physical properties tend to be inadequate, and when the layer is arranged on the outermost surface side of the coating type protective layer, the film surface (transparent The protective layer) is apt to be scratched, and there are problems of poor appearance and corrosion deterioration of the metal layer due to the effect of the scratch. That is, it was not possible to achieve both the function of protecting from external environmental factors such as oxygen, water, and chloride ions and the physical characteristics such as scratch resistance.

Therefore, in the present invention, the coating type protective layer is composed of a plurality of layers, and a barrier function is imparted to at least one layer of the coating type protective layers other than the layer located on the outermost surface side. For the purpose, as a pre-curing resin component, an alkyl (meth)acrylate having a carbon number of 4 or more and 10 or less in an alkyl group capable of forming a monomer having a hydroxyl group and a homopolymer having a glass transition temperature of 20° C. or more and 155° C. or less A layer containing a (meth)acrylic copolymer containing an ester monomer as a copolymer unit and a polyisocyanate cross-linking agent that reacts with the hydroxyl group is arranged, and in the coating type protective layer, , The layer located on the outermost surface side, for the purpose of imparting scratch resistance, by disposing a layer containing an active energy ray curable resin as a pre-curing resin component, the above problems are solved, and the plurality of layers As a whole, the coating-type protective layer made of (1) has both a function of protecting from external environmental factors such as oxygen, moisture, and chloride ions and physical properties such as scratch resistance.

A monomer having a hydroxyl group and a (meth)acrylic acid alkyl ester monomer having an alkyl group capable of forming a homopolymer having a glass transition temperature of 20° C. or higher and 155° C. or lower and having 4 to 10 carbon atoms are used. The (meth)acrylic copolymer contained as a polymer unit is not particularly limited in kind as long as it is soluble in a solvent and can be applied as a resin solution, and at least the above-mentioned monomer is used. It is possible to use a copolymer containing as a copolymerization unit. As the solvent, known solvents can be used, and specifically, aromatic hydrocarbons (benzene, toluene, xylene, etc.), aliphatic hydrocarbons (hexane, cyclohexane, etc.), ketones (acetone, methyl ethyl ketone, methyl). Isobutyl ketone, cyclohexanone, dimethyl sulfoxide and the like) and amide (dimethylformamide, N-methylpyrrolidone) and the like.

The hydroxyl group is usually introduced into the (meth)acrylic copolymer by copolymerizing a monomer having a hydroxyl group with a (meth)acrylic acid alkyl ester monomer described later. Examples of the monomer having a hydroxyl group include 2-hydroxyethyl vinyl ether, 3-hydroxypropyl vinyl ether, 2-hydroxypropyl vinyl ether, 2-hydroxy-2-methylpropyl vinyl ether, 4-hydroxybutyl vinyl ether, 4-hydroxy- Hydroxyl group-containing vinyl ethers such as 2-methylbutyl vinyl ether, 5-hydroxypentyl vinyl ether, 6-hydroxyhexyl vinyl ether; hydroxyl group-containing allyl ethers such as 2-hydroxyethyl allyl ether, 4-hydroxybutyl allyl ether, glycerol monoallyl ether; 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl acrylate, 2-hydroxybutyl acrylate, 2-hydroxy-3-phenoxypropyl acrylate, 4-hydroxybutyl acrylate, etc. Examples thereof include (meth)acrylic acid alkyl esters, which can be used alone or in combination.

The polymer unit based on the monomer having a hydroxyl group is preferably 5% by mass or more and 30% by mass or less, and 10% by mass or more 20% by mass, based on all the polymerized units constituting the (meth)acrylic copolymer. It is more preferable that the content is not more than mass %. When the polymerized units based on the monomer having a hydroxyl group is less than 5% by mass based on all polymerized units constituting the (meth)acrylic copolymer, the hardness and salt resistance of the resulting coating film after curing are cured. Water (barrier property) may be insufficient, or interlayer adhesion may be poor. When the polymerized units based on the monomer having a hydroxyl group exceeds 30 mass% with respect to the total polymerized units constituting the (meth)acrylic copolymer, the viscosity of the coating composition becomes high and the coatability is high. Since the coating film obtained is inferior, the appearance of the obtained coating film may deteriorate, and the flexibility after curing of the obtained coating film may deteriorate, so that minute cracks may occur in the coating film when the thermal insulation member is excessively bent. However, the salt water resistance (barrier property) may decrease.

The hydroxyl group-containing (meth)acrylic copolymer preferably has a hydroxyl value of 30 mgKOH/g or more and 200 mgKOH/g or less. When the hydroxyl value is less than 30 mgKOH/g, the hardness, salt water resistance (barrier property) and interlayer adhesion of the obtained coating film after curing may be deteriorated. When the hydroxyl value is more than 200 mgKOH/g, the solvent solubility and coatability are poor, so that the appearance of the obtained coating film may be deteriorated, or the flexibility after curing of the obtained coating film may be deteriorated. When the heat insulating/insulating member is bent excessively, minute cracks may occur in the coating film, and the salt water resistance (barrier property) may deteriorate. The above hydroxyl value is a value obtained by measurement according to JIS K0070, and is the amount (mg) of potassium hydroxide (KOH) required to acetylate the OH groups contained in 1 g of the object. Is.

The (meth)acrylic copolymer having a hydroxyl group is an alkyl (meth)acrylate in which the number of carbon atoms of the alkyl group capable of forming a homopolymer having the following glass transition temperature of 20° C. or higher and 155° C. or lower is 4 or more and 10 or less. It includes an ester monomer as a copolymer unit.

Examples of the (meth)acrylic acid alkyl ester monomer having an alkyl group having 4 to 10 carbon atoms capable of forming a homopolymer having a glass transition temperature (Tg) of 20° C. to 155° C. include acrylic acid. t-Butyl (Tg of homopolymer: 43° C., carbon number of alkyl group C: 4, alkyl group: branched, same below), n-butyl methacrylate (Tg: 20° C., C: 4, linear) , Isobutyl methacrylate (Tg: 48° C., C: 4, branched), t-butyl methacrylate (Tg: 107° C., C: 4, branched), cyclohexyl methacrylate (Tg: 83° C., C: 6, Alicyclic), isobornyl acrylate (Tg: 94° C., C:10, alicyclic), isobornyl methacrylate (Tg: 155° C., C:10, alicyclic), and the like, and these may be used alone or in combination. You can Among these, as a (meth)acrylic acid alkyl ester monomer having an alkyl group having a carbon number of 4 or more and 10 or less capable of forming a homopolymer having a glass transition temperature (Tg) of 20° C. or more and 155° C. or less, salt water resistance is preferable. From the viewpoints of (barrier property) and versatility, t-butyl methacrylate, t-butyl acrylate, cyclohexyl methacrylate, isobornyl acrylate, and isobornyl methacrylate are preferable. Further, instead of the (meth)acrylic acid alkyl ester monomer having a carbon number of the alkyl group capable of forming a homopolymer having a glass transition temperature (Tg) of 20° C. or more and 155° C. or less and 4 or more and 10 or less, acrylic acid is used. The glass transition temperature (Tg) of phenyl (Tg: 57° C., C: 6), phenyl methacrylate (Tg: 110° C., C: 6), benzyl methacrylate (Tg: 54° C., C: 7), etc. is 50° C. It is also possible to use a (meth)acrylic acid ester having an aromatic group having 6 or more and 10 or less carbon atoms capable of forming a homopolymer at 120° C. or higher.

When a glass transition temperature (Tg) of the above homopolymer is less than 20° C., a (meth)acrylic acid alkyl ester monomer is used, and the obtained coating film is blocked after curing in the raw material wound after coating. May occur. When the glass transition temperature (Tg) of the above homopolymer is higher than 155° C. (meth)acrylic acid alkyl ester monomer is used, the flexibility of the obtained coating film after curing is lowered, and the heat insulating and heat insulating member is obtained. When the film is extremely bent, minute cracks may occur in the coating film, resulting in a decrease in salt water resistance (barrier property).

When a (meth)acrylic acid alkyl ester monomer having an alkyl group having a carbon number of less than 4 is used, the alkyl chain is short, and thus the salt water resistance (barrier property) of the obtained coating film after curing may be poor. There is. When a (meth)acrylic acid alkyl ester monomer in which the number of carbon atoms of the alkyl group exceeds 10 is used, the glass transition temperature (Tg) of the obtained polymer tends to be low (less than 20° C.), and thus coating After that, in the wound web, the obtained coating film may cause blocking after curing.

The polymer unit based on the (meth)acrylic acid alkyl ester monomer having 4 to 10 carbon atoms of the alkyl group capable of forming a homopolymer having a glass transition temperature (Tg) of 20 to 155° C. is as described above. The content is preferably 50% by mass or more and 95% by mass or less, more preferably 70% by mass or more and 90% by mass or less, based on all the polymerized units constituting the (meth)acrylic copolymer. When these (meth)acrylic acid alkyl ester monomers are contained within the above range, an excellent effect is exhibited in the salt water resistance (barrier property) after curing of the obtained coating film.

The (meth)acrylic copolymer having a hydroxyl group is at least one polymer unit selected from the group consisting of a carboxyl group-containing monomer, an amino group-containing monomer, and a silyl group-containing monomer. May be included. The amount of the polymer units based on these functional group-containing monomers is preferably 1% by mass or more and 20% by mass or less based on all the polymer units forming the (meth)acrylic copolymer having a hydroxyl group. It is more preferable that the content is not less than 10% by mass. When the functional group-containing monomer is contained within the above range, the dispersibility of the pigment such as the inorganic fine particles and the interlayer adhesion are excellent.

As the carboxyl group-containing monomer, for example, acrylic acid, methacrylic acid, vinyl acetic acid, crotonic acid, pentenoic acid, hexenoic acid, heptenoic acid, octenoic acid, nonenic acid, decenoic acid, undecylenic acid, dodecenoic acid, tridecenoic acid. , Tetradecenoic acid, pentadecenoic acid, hexadecenoic acid, heptadecenoic acid, octadecenoic acid, nonadecenoic acid, eicosenoic acid, 22-tricosenoic acid, cinnamic acid, itaconic acid, itaconic acid monoester, maleic acid, maleic acid monoester, maleic anhydride , Fumaric acid, fumaric acid monoester, vinyl phthalate, vinyl pyromellitic acid, 3-allyloxypropionic acid, 3-(2-allyloxyethoxycarbonyl)propionic acid, 3-(2-allyloxybutoxycarbonyl)propionic acid , 3-(2-vinyloxyethoxycarbonyl)propionic acid, 3-(2-vinyloxybutoxycarbonyl)propionic acid and the like. Among these, as the above-mentioned carboxyl group-containing monomer, homopolymerization is difficult to form a low homopolymer, crotonic acid, undecylenic acid, itaconic acid, maleic acid, maleic acid monoester, fumaric acid, fumaric acid. At least one acid selected from the group consisting of acid monoester, 3-allyloxypropionic acid, and 3-(2-allyloxyethoxycarbonyl)propionic acid is preferable.

Examples of the amino group-containing monomer include amino vinyl ethers, allyl amines, amino methyl styrene, vinyl amine, acrylamide, vinyl acetamide, vinyl formamide and the like.

Examples of the silyl group-containing monomer include silicone vinyl monomers. Examples of the silicone vinyl monomer include (meth)acrylic acid esters such as (meth)acrylic acid 3-trimethoxysilylpropyl and (meth)acrylic acid 3-triethoxysilylpropyl; vinyltrimethoxysilane, vinyl Vinylsilanes such as triethoxysilane, vinyltrichlorosilane or partial hydrolysates thereof; trimethoxysilylethyl vinyl ether, triethoxysilylethyl vinyl ether, trimethoxysilylbutyl vinyl ether, methyldimethoxysilylethyl vinyl ether, trimethoxysilylpropyl vinyl ether, trimethoxysilylethyl vinyl ether Examples thereof include vinyl ethers such as ethoxysilylpropyl vinyl ether.

The (meth)acrylic copolymer having a hydroxyl group may include a polymer unit based on at least one non-fluorine-containing vinyl monomer selected from the group consisting of carboxylic acid vinyl ester, alkyl vinyl ether and non-fluorinated olefin. good.

The vinyl ester of carboxylic acid has a function of improving compatibility. Examples of the vinyl carboxylate include vinyl acetate, vinyl propionate, vinyl butyrate, vinyl isobutyrate, vinyl pivalate, vinyl caproate, vinyl versatate, vinyl laurate, vinyl stearate, vinyl cyclohexylcarboxylate, vinyl benzoate. , Vinyl para-t-butyl benzoate and the like.

Examples of the alkyl vinyl ether include methyl vinyl ether, ethyl vinyl ether, butyl vinyl ether, cyclohexyl vinyl ether and the like.

Examples of the above non-fluorinated olefin include ethylene, propylene, n-butene, isobutene and the like.

Specific examples of the (meth)acrylic copolymer having a hydroxyl group include a copolymer of t-butyl (meth)acrylate/isobutene/4-hydroxybutyl vinyl ether/other monomer, (meth ) Copolymer of t-butyl acrylate/vinyl versatic/4-hydroxybutyl vinyl ether/other monomer, t-butyl (meth)acrylate/4-hydroxybutyl acrylate/other monomer Polymer, t-butyl (meth)acrylate/2-hydroxyethyl acrylate/other monomer copolymer, cyclohexyl methacrylate/isobutene/hydroxybutyl vinyl ether/other monomer copolymer, methacryl Acid cyclohexyl/vinyl versatate/hydroxybutyl vinyl ether/other monomer copolymer, cyclohexyl methacrylate/4-hydroxybutyl acrylate/other monomer copolymer, cyclohexyl methacrylate/acrylic acid 2- Examples thereof include copolymers of hydroxyethyl/other monomers. The above-mentioned other monomer may or may not be contained.

The (meth)acrylic copolymer having a hydroxyl group is an acrylic resin having a hydroxyl group, if necessary, such as blocking, coating property, interlayer adhesion, and improvement of hardness, as long as the effect of the present invention is not impaired. It may be used as a mixture with another resin compatible with the copolymer. That is, the layer containing the (meth)acrylic copolymer having a hydroxyl group may contain another resin compatible with the (meth)acrylic copolymer having a hydroxyl group. Here, being compatible with the (meth)acrylic copolymer having a hydroxyl group means that when the respective resins are mixed, the transparency of the obtained coating film is not significantly impaired without separating the layers. To do.

The other resin is not particularly limited as long as it is a resin compatible with the (meth)acrylic copolymer having a hydroxyl group, but is not limited to thermoplastic (meth)acrylic resin, acrylic silicone resin, polyester resin. , A polyurethane resin, etc., but a thermoplastic acrylic resin is preferable from the viewpoint of versatility.

Examples of the thermoplastic (meth)acrylic resin include homopolymers of (meth)acrylic acid esters such as methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, and butyl (meth)acrylate. Examples thereof include copolymers thereof or copolymers with monomers copolymerizable therewith. Examples of the copolymerizable monomer include aromatic vinyl compounds such as styrene, acrylonitrile, various vinyl ethers, allyl ethers, vinyl compounds such as various vinyl esters, unsaturated compounds having a functional group such as a carboxyl group, an amino group and an epoxy group. Examples thereof include monomers.

As a cross-linking agent that reacts with the hydroxyl group of the (meth)acrylic copolymer, a polyisocyanate cross-linking agent composed of a polyisocyanate compound can be used. By this reaction, the (meth)acrylic copolymer can be three-dimensionally crosslinked and cured. As a result, a barrier function is imparted to the layer containing the (meth)acrylic copolymer and the polyisocyanate crosslinking agent.

Examples of the polyisocyanate compound include 2,4-tolylene diisocyanate, diphenylmethane-4,4′-diisocyanate, xylylene diisocyanate, isophorone diisocyanate, lysine methyl ester diisocyanate, methylcyclohexyl diisocyanate, trimethylhexamethylene diisocyanate, hexamethylene diisocyanate, n. -Pentane-1,4-diisocyanate, trimers of these, adducts thereof, burettes and isocyanurates, polymers of these polymers having two or more isocyanate groups, blocked isocyanates, etc. However, the present invention is not limited to these. Among these, as the polyisocyanate compound, from the viewpoint of weather resistance, an isocyanurate prepolymer which is a trimer of hexamethylene diisocyanate and an isocyanurate prepolymer which is a trimer of isophorone diisocyanate are preferable. Examples of such a polyisocyanate compound include Coronate (registered trademark) HX manufactured by Tosoh Corporation, Destannate T1890 (trade name) manufactured by Evonik Degussa, and Desmodur (registered trademark) Z4470 manufactured by Sumika Covestrourethane. Can be illustrated.

The content of the cross-linking agent is such that the isocyanate group (-NCO) of the cross-linking agent is 0.3 molar equivalent or more and 2.0 or more with respect to 1 equivalent of the hydroxyl group (-OH) of the (meth)acrylic copolymer. It is preferable to add it so as to be a molar equivalent or less, more preferably 0.5 molar equivalent or more and 1.5 molar equivalent or less, and further preferably 0.8 molar equivalent or more and 1.2 molar equivalent or less. When the content of the cross-linking agent is less than 0.3 molar equivalent, the obtained coating film may be insufficiently cross-linked and the hardness and the barrier property may be deteriorated. When the content of the cross-linking agent exceeds 2.0 molar equivalents, when the coated raw material is wound up, the coating film and the opposite surface of the coated film adhere to each other due to the influence of the low-molecular weight crosslinking agent, and the coated raw material Blocking may occur when unwinding.

In addition, when the other resin has a curable functional group, if the curable functional group is a hydroxyl group, a crosslinking agent that reacts with the hydroxyl group is also a crosslinking agent used for the (meth)acrylic copolymer having the hydroxyl group. The same as the agent can be used. If the curable functional group is other than the hydroxyl group, a crosslinking agent is appropriately selected and used according to the curable functional group.

The coating type protective layer constituting the transparent heat insulating and heat insulating member of the present embodiment comprises a plurality of layers, among the coating type protective layer, the layer located on the outermost surface side is a pre-curing resin component, It is composed of a layer containing an active energy ray-curable resin. This protects the layer containing the (meth)acrylic copolymer having a hydroxyl group and the polyisocyanate crosslinking agent that reacts with the hydroxyl group after irradiation with active energy rays, and improves salt water resistance (barrier property). While assisting, the scratch resistance of the entire coating type protective layer can be secured. As the active energy ray, far-ultraviolet rays, ultraviolet rays, near-ultraviolet rays, infrared rays, etc., X-rays, γ-rays, etc. may be used as long as they can generate radicals, cations, anions, etc. that can trigger polymerization reactions. In addition to the electromagnetic waves described above, any of electron beams, proton beams, neutron beams and the like can be used, but from the viewpoints of curing speed, availability of irradiation equipment, cost, etc., curing by ultraviolet irradiation is preferable. The active energy ray is preferably light in the wavelength band of 200 to 450 nm, and more preferably light in the wavelength band of 250 to 430 nm. The light source is not particularly limited, and examples thereof include a high pressure mercury lamp, a metal halide lamp, a low pressure mercury lamp, an ultrahigh pressure mercury lamp, an ultraviolet laser, sunlight, and an LED lamp. A layer containing an active energy ray-curable resin can be instantly cured by using these light sources and irradiating with active energy rays so that the integrated light amount is preferably 300 mJ/cm ² or more.

As the active energy ray-curable resin, for example, a polyfunctional (meth)acrylate monomer or a polyfunctional (meth)acrylate oligomer (prepolymer) can be preferably used, and these can be used alone or in combination. it can. Specifically, ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, 1,4-cyclohexane diacrylate, pentaerythritol tetra(meth)acrylate, pentaerythritol tri(meth)acrylate. ) Acrylate, trimethylolpropane tri(meth)acrylate, trimethylolethane tri(meth)acrylate, dipentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, 1, Acrylate such as 2,3-cyclohexanetrimethacrylate; vinylbenzene such as 1,4-divinylbenzene, 4-vinylbenzoic acid-2-acryloylethyl ester and 1,4-divinylcyclohexanone and its derivatives; pentaerythritol triacrylate hexamethylene Urethane-based polyfunctional acrylate oligomers such as diisocyanate urethane prepolymers; Ester-based polyfunctional acrylate oligomers formed from polyhydric alcohol and (meth)acrylic acid; Epoxy-based polyfunctional acrylate oligomers and their inclusion Examples thereof include a fluorine compound and a silicone-containing compound. If necessary, a photopolymerization initiator may be added and an active energy ray may be irradiated to form the outermost surface layer of the coating type protective layer.

The coating type protective layer is formed of a plurality of layers on the infrared reflective layer in order to achieve both salt water resistance (barrier property) and scratch resistance of the transparent heat insulating and heat insulating member as described above. From the viewpoint of productivity, the coating type protective layer is formed of, for example, 2 to 4 layers. When the coating-type protective layer has a two-layer structure, a medium refractive index layer or a high refractive index layer, and a medium refractive index layer or a low refractive index layer are formed on the infrared reflecting layer from the infrared reflecting layer side. Just prepare for it in order. In this case, the medium refractive index layer or high refractive index layer in contact with the infrared reflective layer contains the (meth)acrylic copolymer having a hydroxyl group and a polyisocyanate crosslinking agent that reacts with the hydroxyl group, and further The active energy ray-curable resin may be contained in the medium refractive index layer or the low refractive index layer (outermost surface layer) formed in 1. When the coating type protective layer has a three-layer structure, a medium refractive index layer, a high refractive index layer, and a low refractive index layer may be provided in this order on the infrared reflecting layer from the infrared reflecting layer side. Good. In this case, at least one of the medium refractive index layer and the high refractive index layer, the (meth) acrylic copolymer having a hydroxyl group, and a polyisocyanate crosslinking agent that reacts with the hydroxyl group, at least It is sufficient that the low refractive index layer contains the active energy ray-curable resin. When the coating type protective layer has a four-layer structure, an optical adjustment layer, a medium refractive index layer, a high refractive index layer, and a low refractive index layer are provided in this order on the infrared reflecting layer from the infrared reflecting layer side. All you have to do is prepare. In this case, at least one of the optical adjustment layer, the medium refractive index layer, and the high refractive index layer has a (meth)acrylic copolymer having a hydroxyl group and a polyisocyanate crosslinking agent that reacts with the hydroxyl group. And at least the low energy layer contains the active energy ray-curable resin.

The coating-type protective layer is, in the multilayer structure exemplified above, from the viewpoint of the optical characteristics of the transparent heat-insulating and heat-insulating member, the appearance (iris phenomenon, reflection color change depending on the viewing angle), from the viewpoint of the infrared rays. It is preferable to have a two-layer structure in which a high refractive index layer and a low refractive index layer are provided in this order from the reflective layer side. In addition to the above-mentioned balance, from the viewpoint of improving the visible light transmittance, from the infrared reflection layer side, a three-layer structure including a medium refractive index layer, a high refractive index layer, and a low refractive index layer in this order. More preferably, it is most preferably composed of a four-layer structure including an optical adjustment layer, a medium refractive index layer, a high refractive index layer and a low refractive index layer in this order from the infrared reflecting layer side. That is, when a protective layer (usually having a refractive index of about 1.50) made of a normal acrylic ultraviolet (UV) curable hard coat resin is provided on the infrared reflective layer as a layer composed of one layer, In the visible light reflectance spectrum, the visible light reflectance tends to fluctuate up and down as the wavelength increases, especially in the wavelength range of 500 nm to 780 nm, and the fluctuation in the thickness of the protective layer is also taken into consideration to generate an iris pattern. Or the reflected color changes greatly depending on the viewing angle. In particular, in order to reduce the heat transmission coefficient and improve the heat insulation performance, when the thickness of the protective layer is set to be thin within the range of 380 to 780 nm which is the wavelength range of visible light, interference of multiple reflections may occur. , This phenomenon becomes remarkable. However, when the coating type protective layer is composed of a plurality of layers having different refractive indexes as described above, the total thickness of the protective layer is thin in the range overlapping with 380 to 780 nm which is the wavelength range of visible light. Even if it is set, it is possible to reduce the vertical fluctuation of the visible light reflectance linked with the wavelength in the visible light reflection spectrum, and it is possible to suppress the occurrence of the iris pattern and the change of the reflected color depending on the viewing angle.

The total thickness of the coating type protective layer is preferably 980 nm or less from the viewpoint of reducing the heat transmission coefficient, which is an index of the heat insulating performance of the transparent heat insulating heat insulating member. Further, in consideration of scratch resistance and corrosion deterioration resistance, the total thickness of the coating type protective layer is more preferably 200 nm or more and 980 nm or less. If the total thickness is less than 200 nm, physical properties such as scratch resistance and corrosion resistance may deteriorate, and if the total thickness exceeds 980 nm, the optical adjustment layer, the medium refractive index layer, and the high refractive index. Of C=O groups, CO groups and aromatic groups contained in the molecular skeleton of the resin used for the layer and the low refractive index layer, and inorganic oxide fine particles used for adjusting the refractive index of each layer As a result, absorption of far infrared rays having a wavelength of 5.5 μm to 25.2 μm in the coating type protective layer is increased, and the vertical emissivity is increased. As a result, the heat insulating performance may be deteriorated. When the total thickness is in the range of 200 nm or more and 980 nm or less, the heat transmission coefficient can be 4.2 W/(m ² ·K) or less, and the heat insulating performance can be sufficiently exhibited. In addition, the total thickness is set to 300 nm or more from the viewpoint of further improving scratch resistance and corrosion deterioration resistance, and is set to 700 nm or less from the viewpoint of further reducing the heat transmission coefficient to a range of 300 nm to 700 nm. It is most preferable to set. If the total thickness is in the range of 300 nm or more and 700 nm or less, the heat transmission coefficient can be set to 4.0 W/(m ² ·K) or less, and the physical properties such as heat insulation performance, scratch resistance, and corrosion deterioration resistance can be obtained. The characteristics can be compatible at an even higher level.

Each layer constituting the above-mentioned coating type protective layer will be described below.

[Optical adjustment layer]
The optical adjustment layer is a layer for adjusting the optical characteristics of the infrared reflective layer of the transparent heat insulating and heat insulating member of the present embodiment, and the refractive index of light having a wavelength of 550 nm is in the range of 1.60 to 2.00. Is preferable, and more preferably 1.65 or more and 1.90 or less. Further, when the coating type protective layer is formed of a plurality of layers, for example, when it is formed of four layers in a preferred embodiment, the thickness of the optical adjustment layer is in order on the optical adjustment layer. Since the appropriate range varies depending on the refractive index and thickness of each layer of the medium refractive index layer, the high refractive index layer, and the low refractive index layer to be laminated, it cannot be said unconditionally, but with the configuration of the other layers described above. In view of the above, it is preferable to set in the range of 30 nm or more and 80 nm or less, and more preferably set in the range of 35 nm or more and 70 nm or less. By setting the thickness of the optical adjustment layer in the range of 30 nm or more and 80 nm or less, the visible light transmittance and the near infrared reflectance of the transparent heat insulating/insulating member of the present embodiment can be compatible with each other in a high balance. When the thickness of the optical adjustment layer is less than 30 nm, the coating itself becomes difficult, and for example, "the metal layer is not completely covered by the second metal suboxide layer or the metal oxide layer, the metal layer The coating liquid may be easily repelled at the "very small area where the metal from which it is exposed," and coverage may not be achieved. In addition, the visible light transmittance may be lowered, the transparency may be deteriorated, and the reddish color of the reflected color may be increased. On the other hand, when the thickness of the optical adjustment layer exceeds 80 nm, the near-infrared reflectance is lowered and the heat shield performance may be deteriorated. Further, when the optical adjustment layer contains a large amount of inorganic fine particles, the absorption of light in the far infrared region increases, and the heat insulating performance may deteriorate.

Further, the material forming the optical adjusting layer may include the same kind of material as the material forming the second metal suboxide layer or the metal oxide layer of the infrared reflecting layer, It is preferable from the viewpoint of ensuring adhesion with the second metal suboxide layer or the metal oxide layer that is in direct contact, and for example, as the second metal suboxide layer or the metal oxide layer, partial oxidation of titanium metal is performed. When a material layer or an oxide layer or a partial oxide layer or an oxide layer of a metal containing titanium as a main component is selected, the constituent material of the optical adjustment layer is preferably a material containing titanium oxide fine particles. Since the constituent material of the optical adjusting layer contains fine particles of titanium oxide, the refractive index of the optical adjusting layer can be appropriately controlled to a high refractive index within the range of 1.60 to 2.00. Without, it is possible to improve the adhesion with the metal suboxide layer or metal oxide layer consisting of the titanium metal partial oxide layer or oxide layer or the titanium partial metal oxide layer or oxide layer. ..

The constituent material of the optical adjustment layer containing inorganic fine particles typified by the titanium oxide fine particles is not particularly limited as long as the refractive index of the optical adjustment layer can be designed within the above range, and examples thereof include a thermoplastic resin and a thermosetting resin. A material containing a resin, a resin such as an active energy ray-curable resin, and inorganic fine particles dispersed in the resin is preferably used. Among the constituent materials of the optical adjustment layer, in terms of optical properties such as transparency, physical properties such as scratch resistance, active energy ray-curable resin from the viewpoint of productivity, and in the active energy ray-curable resin A material containing dispersed inorganic fine particles is preferable. Further, the material containing inorganic fine particles in the active energy ray-curable resin is generally an active material such as an ultraviolet ray after being applied on the second metal suboxide layer or the metal oxide layer of the infrared reflective layer. The film is cured by irradiation with energy rays to form the optical adjustment layer. However, since the film contains inorganic fine particles, shrinkage of the film during curing is suppressed. Therefore, the optical adjustment layer and the second metal suboxide are suppressed. The adhesiveness with the material layer or the metal oxide layer can be improved.

The thermoplastic resin, for example, modified polyolefin resin, vinyl chloride resin, acrylonitrile resin, polyamide resin, polyimide resin, polyacetal resin, polycarbonate resin, polyvinyl butyral resin, acrylic resin, polyacetic acid Examples of the thermosetting resin include a vinyl resin, a polyvinyl alcohol resin, and a cellulose resin, and examples of the thermosetting resin include a phenol resin, a melamine resin, a urea resin, an unsaturated polyester resin, an epoxy resin, and a polyurethane. Examples of the resin include a resin, a silicone resin, and an alkyd resin, which can be used alone or in combination, and the optical adjustment layer can be formed by adding a crosslinking agent as necessary and thermosetting.

Examples of the active energy ray-curable resin include polyfunctional (meth)acrylate monomers having two or more unsaturated groups, polyfunctional (meth)acrylate oligomers (prepolymers), and the like, which may be used alone or in combination. Can be used. Specifically, ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, 1,4-cyclohexane diacrylate, pentaerythritol tetra(meth)acrylate, pentaerythritol tri(meth)acrylate. ) Acrylate, trimethylolpropane tri(meth)acrylate, trimethylolethane tri(meth)acrylate, dipentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, 1, Acrylate such as 2,3-cyclohexanetrimethacrylate; vinylbenzene such as 1,4-divinylbenzene, 4-vinylbenzoic acid-2-acryloylethyl ester and 1,4-divinylcyclohexanone and its derivatives; pentaerythritol triacrylate hexamethylene Urethane-based polyfunctional acrylate oligomers such as diisocyanate urethane prepolymers; ester-based polyfunctional acrylate oligomers produced from polyhydric alcohol and (meth)acrylic acid; epoxy-based polyfunctional acrylate oligomers and the like. The optical adjustment layer can be formed by adding a photopolymerization initiator as needed and irradiating it with an active energy ray to cure it.

In order to further improve the adhesion between the optical adjustment layer containing the active energy ray-curable resin and the second metal suboxide layer or the metal oxide layer of the infrared reflective layer, the active energy ray is added. Add a (meth)acrylic acid derivative having a polar group such as a phosphoric acid group, a sulfonic acid group or an amide group or a silane coupling agent having an unsaturated group such as a (meth)acrylic group or a vinyl group to the curable resin. You may use it.

The inorganic fine particles are dispersed and added in the resin in order to adjust the refractive index of the optical adjustment layer. Examples of the inorganic fine particles include titanium oxide (TiO ₂ ), zirconium oxide (ZrO ₂ ), zinc oxide (ZnO), indium tin oxide (ITO), niobium oxide (Nb ₂ O ₅ ), yttrium oxide (Y ₂ O ₃ ). Indium oxide (In ₂ O ₃ ), tin oxide (SnO ₂ ), antimony oxide (Sb ₂ O ₃ ), tantalum oxide (Ta ₂ O ₅ ), tungsten oxide (WO ₃ ), and the like can be used. The inorganic particles may be surface-treated with a dispersant, if necessary. Among the above-mentioned inorganic fine particles, titanium oxide and zirconium oxide capable of increasing the refractive index by adding a small amount as compared with other materials are preferable, and the metal suboxide layer and the metal suboxide layer having relatively low absorption of light in the far infrared region. Titanium oxide is more preferable from the viewpoint of securing the adhesion with the TiO _X layer which is suitable as

From the viewpoint of transparency of the optical adjustment layer, the average particle size of the inorganic fine particles is preferably in the range of 5 nm to 100 nm, more preferably in the range of 10 nm to 80 nm. If the average particle diameter exceeds 100 nm, the haze value may increase when the optical adjustment layer is formed, resulting in a decrease in transparency. If the average particle diameter is less than 5 nm, the optical adjustment layer may have a smaller thickness. It may be difficult to maintain the dispersion stability of the inorganic fine particles when used as a coating material for a vehicle.

When the optical adjustment layer is a layer containing a (meth)acrylic copolymer having a hydroxyl group and a polyisocyanate crosslinking agent that reacts with the hydroxyl group, the thermoplastic resin, thermosetting resin, active energy Instead of the line-curable resin, the above-mentioned (meth)acrylic copolymer having a hydroxyl group or a mixture of the (meth)acrylic copolymer having a hydroxyl group and another resin is used to adjust the refractive index. After dispersing the inorganic fine particles, a coating material for an optical adjustment layer containing a polyisocyanate crosslinking agent that reacts with the hydroxyl group is prepared, and a coating film may be formed and cured.

[Medium refractive index layer]
The medium refractive index layer preferably has a refractive index of light having a wavelength of 550 nm in the range of 1.45 to 1.55, and more preferably in the range of 1.47 to 1.53. preferable. When the coating type protective layer is formed of a plurality of layers, for example, when it is formed of 4 layers or 3 layers in a preferred embodiment, the thickness of the medium refractive index layer is smaller than that of the medium refractive index layer. The optical adjustment layer to be the lower layer, and the appropriate range varies depending on the refractive index and thickness of each of the high refractive index layer and the low refractive index layer, which are the upper layer in order with respect to the medium refractive index layer. Although it cannot be said, it is preferable that the thickness is set within the range of 35 nm or more and 200 nm or less, and the thickness is set within the range of 50 nm or more and 150 nm or less, in consideration of the configuration of the other layers. Is more preferable. When the thickness of the medium refractive index layer is less than 35 nm, it may lead to a decrease in the adhesion of the infrared reflective layer to the second metal suboxide layer or the metal oxide layer or the optical adjustment layer, for example, There is a possibility that the reddish color becomes stronger in the reflected color of the transparent heat insulating and heat insulating member, the greenish color becomes stronger in the transmitted color, and the total light transmittance is lowered. On the other hand, if the thickness of the medium refractive index layer exceeds 200 nm, the absorption of light in the infrared region increases, which may deteriorate the heat insulating property, which is not preferable. Further, the size of the ripple in the visible light reflection spectrum of the transparent heat insulating and heat insulating member, that is, the fluctuation of the reflectance with respect to the wavelength of the visible light region cannot be sufficiently reduced, and not only the iris pattern becomes conspicuous, The change in reflected color increases depending on the viewing angle, which may cause a problem in appearance, which is not preferable. For example, the reddish color of the reflection color of the transparent heat insulating/insulating member may become strong, or the visible light transmittance may decrease. In addition, the absorption of light in the infrared region becomes large, and the heat insulating property may deteriorate.

When the coating type protective layer is formed of a plurality of layers, the constituent material of the medium refractive index layer is not particularly limited as long as the refractive index of the medium refractive index layer can be set within the above range, for example, heat A plastic resin, a thermosetting resin, an active energy ray curable resin and the like are preferably used. As the resin such as the thermoplastic resin, the thermosetting resin or the active energy ray-curable resin, the same resin as that which can be used for the optical adjustment layer described above can be used, and the medium refraction with the same prescription is performed. A rate layer can be formed. In addition, in order to adjust the refractive index, inorganic fine particles may be dispersed and added to the resin as needed. Among the constituent materials of the medium refractive index layer, a material containing an active energy ray-curable resin is preferable in terms of optical characteristics such as transparency, physical characteristics such as scratch resistance, and productivity.

Among the above active energy ray-curable resins, resins containing urethane-, ester-, or epoxy-based polyfunctional (meth)acrylate oligomers (prepolymers), which have relatively little curing shrinkage when irradiated with active energy rays such as ultraviolet rays, A super polyfunctional acrylic polymer resin having a large number of acryloyl groups is more preferable. Thereby, the adhesion between the medium refractive index layer and the optical adjustment layer or the second metal suboxide layer or the metal oxide layer can be improved.

In order to further improve the adhesion between the medium refractive index layer containing the active energy ray-curable resin and the optical adjustment layer or the second metal suboxide layer or metal oxide layer, the active energy ray is used. Add a (meth)acrylic acid derivative having a polar group such as a phosphoric acid group, a sulfonic acid group or an amide group or a silane coupling agent having an unsaturated group such as a (meth)acrylic group or a vinyl group to the curable resin. You may use it.

When the medium refractive index layer is a layer containing a (meth)acrylic copolymer having a hydroxyl group and a polyisocyanate crosslinking agent that reacts with the hydroxyl group, the thermoplastic resin, thermosetting resin, active Instead of the energy ray curable resin, the above-mentioned hydroxyl group-containing (meth)acrylic copolymer or a mixture of the hydroxyl group-containing (meth)acrylic copolymer and another resin is used to react with the hydroxyl group. The coating for the medium refractive index layer to which the crosslinking agent is added is prepared, and the coating film is formed and cured. Inorganic fine particles for adjusting the refractive index may be dispersed if necessary.

The coating type protective layer of the present embodiment, in particular, the middle refractive index layer, as a pre-curing resin component, a (meth)acrylic copolymer having a hydroxyl group, and a polyisocyanate crosslinking agent that reacts with the hydroxyl group. Most preferably, it is a layer containing and. This is for the following reason. That is, the coating type protective layer is formed of a plurality of layers for the purpose of achieving a good balance of optical characteristics and appearance (iris phenomenon, reflection color change depending on viewing angle) of the transparent heat insulating and heat insulating member. In this case, the medium refractive index layer preferably has a refractive index of light having a wavelength of 550 nm in the range of 1.45 or more and 1.55 or less. In many cases, the refractive index in this range is resin alone. Alternatively, it is possible to obtain a resin in which a very small amount of inorganic fine particles for adjusting the refractive index is added, and such a medium refractive index layer has a refractive index adjustment like the optical adjustment layer or a high refractive index layer described later. As compared with a layer containing a large amount of inorganic fine particles for use in the present invention, it has a very small number of fine voids and becomes a denser layer. Therefore, when a layer containing the (meth)acrylic copolymer having a hydroxyl group and a polyisocyanate crosslinking agent that reacts with the hydroxyl group is applied to the medium refractive index layer, the inorganic fine particles for adjusting the refractive index are used. In comparison with the case where it is applied to an optical adjustment layer or a high refractive index layer containing a large amount of “the metal layer present on the surface of the infrared reflection layer is completely covered by the second metal suboxide layer. To further enhance the function (barrier function) to protect the ultra-small area where the metal from the metal layer is exposed" and the infrared reflection layer from external environmental factors such as oxygen, water, and chloride ions. You can

[High refractive index layer]
The high refractive index layer preferably has a refractive index of light having a wavelength of 550 nm in the range of 1.65 to 1.95, and more preferably in the range of 1.70 to 1.90. preferable. Further, when the coating type protective layer is formed of a plurality of layers, for example, when it is formed of four layers, three layers or two layers in a preferred embodiment, the high refractive index layer has a high refractive index. The appropriate range varies depending on the refractive index and thickness of each of the medium refractive index layer, the optical adjustment layer, which is the lower layer with respect to the refractive index layer, and the low refractive index layer, which is the upper layer with respect to the high refractive index layer. Therefore, although it cannot be generally stated, it is preferable to set the thickness in the range of 60 nm or more and 550 nm or less and the thickness in the range of 65 nm or more and 400 nm or less in consideration of the configuration of the other layers. More preferably. If the thickness of the high refractive index layer is less than 60 nm, physical properties such as scratch resistance as a protective layer may deteriorate, and if the thickness of the high refractive index layer exceeds 550 nm, the high refractive index layer is When a large amount of inorganic fine particles are contained, absorption of light in the infrared region becomes large, which may lead to deterioration of heat insulating property, which is not preferable.

The constituent material of the high refractive index layer is not particularly limited as long as the refractive index of the high refractive index layer can be set within the above range, and examples thereof include a thermoplastic resin, a thermosetting resin, and an active energy ray curable resin. A material containing a resin and inorganic fine particles dispersed in the resin is preferably used. As the thermoplastic resin, the thermosetting resin and the resin such as the active energy ray-curable resin and the inorganic fine particles, it is possible to use the same resin and inorganic fine particles that can be used for the optical adjustment layer described above, The high refractive index layer can be formed with the same formulation. Among the constituent materials of the high refractive index layer, the active energy ray-curable resin and the active energy ray-curable resin in terms of optical characteristics such as transparency, physical characteristics such as scratch resistance, and productivity. A material containing inorganic fine particles dispersed therein is preferable. The material containing inorganic fine particles in the active energy ray-curable resin is generally formed as the high refractive index layer by coating on the medium refractive index layer and then curing by irradiation with active energy ray such as ultraviolet rays. However, by containing the inorganic fine particles, the shrinkage of the film at the time of curing is suppressed, so that the adhesion between the high refractive index layer and the medium refractive index layer can be made good.

Further, the inorganic fine particles are added to adjust the refractive index of the high refractive index layer, but among the inorganic fine particles, titanium oxide capable of increasing the refractive index by adding a small amount compared to other materials. Further, zirconium oxide is preferable, and titanium oxide is more preferable because it absorbs relatively little light in the infrared region.

Further, in order to further improve the adhesion between the high refractive index layer containing the active energy ray-curable resin and the medium refractive index layer or the second metal suboxide layer or metal oxide layer, the active energy Addition of (meth)acrylic acid derivatives having polar groups such as phosphoric acid groups, sulfonic acid groups, amide groups, and silane coupling agents having unsaturated groups such as (meth)acrylic groups and vinyl groups to linear curing resins You may use it.

When the high refractive index layer is a layer containing a (meth)acrylic copolymer having a hydroxyl group and a polyisocyanate crosslinking agent that reacts with the hydroxyl group, the thermoplastic resin, thermosetting resin, active Instead of the energy ray-curable resin, the above-mentioned (meth)acrylic copolymer having a hydroxyl group or a mixture of the (meth)acrylic copolymer having a hydroxyl group and another resin is used for adjusting the refractive index. After dispersing the above-mentioned inorganic fine particles, the polyisocyanate crosslinking agent that reacts with the hydroxyl group is added to prepare a coating material for a high refractive index layer, and a coating film is formed and cured.

[Low refractive index layer]
The low refractive index layer preferably has a refractive index of light having a wavelength of 550 nm in the range of 1.30 or more and less than 1.45, and more preferably in the range of 1.35 or more and 1.43 or less. preferable. When the protective layer is formed of a plurality of layers, for example, when it is formed of four layers, three layers or two layers in a preferred embodiment, the thickness of the low refractive index layer is the same as that of the low refractive index layer. On the other hand, since the appropriate range varies depending on the refractive index and thickness of each layer of the high refractive index layer, the medium refractive index layer, and the optical adjustment layer, which are the lower layers in order, it cannot be said unconditionally. In consideration of the constitution, the thickness is preferably set in the range of 70 nm to 150 nm, and more preferably the thickness is set in the range of 80 nm to 130 nm. When the thickness of the low refractive index layer is out of the range of 70 nm or more and 150 nm or less, the size of the ripple of the reflection spectrum in the visible light region of the transparent heat insulating and heat insulating member of the present embodiment, that is, the reflectance with respect to the wavelength of the visible light region. Can not be sufficiently reduced, the iris pattern tends to be conspicuous, and the change in reflected color increases depending on the viewing angle, which may cause a problem in appearance. In addition, the visible light transmittance may decrease.

The constituent material of the low refractive index layer is not particularly limited as long as the refractive index of the low refractive index layer can be set within the above range, but it is preferable to include an active energy ray curable resin as a resin component before curing. As the active energy ray-curable resin, the same resin as the active energy ray-curable resin that can be used in the above-mentioned optical adjustment layer and a fluorine-containing compound or a silicone-containing compound thereof can be used, and if necessary. The outermost surface layer of the coating type protective layer can be formed by adding a photopolymerization initiator and irradiating with active energy rays. Further, in order to adjust the refractive index, inorganic fine particles may be dispersed and added into the active energy ray-curable resin, if necessary. For example, a material containing the active energy ray-curable resin and low refractive index inorganic fine particles dispersed in the active energy ray-curable resin, and the active energy ray curable resin and the low refractive index inorganic fine particles are chemically Materials containing organic-inorganic hybrid materials bound to are preferred.

The above-mentioned inorganic fine particles are dispersed and added to the above resin in order to adjust the refractive index of the above low refractive index layer. As the low-refractive-index inorganic fine particles, for example, silicon oxide, magnesium fluoride, aluminum fluoride or the like can be used, but from the viewpoint of physical properties such as scratch resistance of the low-refractive-index layer which is the outermost surface of the protective layer. From the above, a silicon oxide-based material is preferable, and a hollow type silicon oxide (hollow silica)-based material having voids inside for exhibiting a low refractive index is particularly preferable.

The material containing inorganic fine particles in the active energy ray-curable resin is generally formed as the low refractive index layer by coating on the high refractive index layer and then curing by irradiation with active energy rays such as ultraviolet rays. However, since the inorganic fine particles are contained, the shrinkage of the film at the time of curing is suppressed, so that the adhesion with the high refractive index layer can be made good.

In order to further improve the adhesion between the low refractive index layer containing the active energy ray-curable resin and the high refractive index layer or the second metal suboxide layer or the metal oxide layer, the active energy ray is added. Add a (meth)acrylic acid derivative having a polar group such as a phosphoric acid group, a sulfonic acid group or an amide group or a silane coupling agent having an unsaturated group such as a (meth)acrylic group or a vinyl group to the curable resin. You may use it.

As the constituent material of the low refractive index layer, in addition to the constituent materials described above, a leveling agent, a lubricant, an antistatic agent, an additive such as a haze imparting agent may be contained, and the content of these additives Are appropriately adjusted within a range that does not impair the purpose of the present embodiment.

As described above, as the coating type protective layer formed of multiple layers, (1) a laminated structure including a high refractive index layer and a low refractive index layer in this order from the infrared reflecting layer side, (2) A laminated structure including a medium refractive index layer, a high refractive index layer, and a low refractive index layer in this order from the infrared reflecting layer side, or (3) an optical adjustment layer, a medium refractive index layer, and a high refractive index from the infrared reflecting layer side. A laminated structure including a refractive index layer and a low refractive index layer in this order is a preferred embodiment of the present embodiment, but in any case, the total thickness of the coating type protective layer formed of each laminated layer is The refractive index of light having a wavelength of 550 nm is 1.60 or more and 2.00 or less so as to be in the range of 200 nm or more and 980 nm or less. The refractive index of light having a wavelength of 550 nm is 1.45 or more and 1.55 or less. The thickness of the medium refractive index layer is in the range of 40 nm or more and 200 nm or less, and the refractive index of light having a wavelength of 550 nm is 1.65 or more. The high refractive index layer having a thickness of 1.95 or less is selected from the range of 60 nm or more and 550 nm or less, and the refractive index of light having a wavelength of 550 nm is 1.30 or more and less than 1.45. The thickness of 70 nm or more and 150 nm or less, the heat resistance (4.2 W/(m ² ·K) or less as a heat transmission coefficient) is maintained and the scratch resistance is set by appropriately setting the thickness. It is possible to provide a transparent heat insulating and heat insulating member which has excellent physical properties such as corrosion resistance and deterioration, has a low solar absorptance, and suppresses the iris phenomenon and reflected color change depending on the viewing angle and has a good appearance. In particular, in order to lower the solar absorptance while keeping the visible light transmittance high, the above-mentioned plurality of wavelengths are generally set so as to increase the reflectance in the wavelength band 800-1500 nm where the weight coefficient of energy is large. It is preferable to set layers to form the above-mentioned coating type protective layer.

Further, as a more preferable range, if the total thickness of the coating type protective layer is set in the range of 300 nm or more and 700 nm or less, the value of the heat transmission coefficient becomes 4.0 W/(m ² ·K) or less, In addition, since the mechanical properties of the protective layer can be sufficiently ensured, the heat insulation performance and the physical characteristics such as scratch resistance and corrosion deterioration resistance can be compatible at a higher level.

When the coating type protective layer is composed of two layers including a medium refractive index layer (lower) and a medium refractive index layer (upper) in this order from the infrared reflecting layer side, when the medium refractive index layer is Each thickness does not need to be limited to the above-mentioned thickness, and is appropriately adjusted within a range of 200 nm or more and 980 nm or less, which is a preferable total thickness of the protective layer, as long as the effect of the present invention is not impaired. You can set it. However, in the case of the two-layer protective layer of this combination, the appearance of the transparent heat insulating/insulating member obtained may be poor depending on the refractive index of the medium refractive index layer.

In the transparent heat insulating and heat insulating member of the present embodiment, among the coating type protective layers, at least the layer which is in direct contact with the (second) metal suboxide layer or the metal oxide layer of the infrared reflecting layer is made of metal. It is preferable to include a corrosion inhibitor for. For the purpose of reducing the solar radiation absorptivity of the low-emissivity film by including a corrosion inhibitor for the metal in the layer which is in direct contact with the (second) metal suboxide layer or the metal oxide layer, Even if the (second) metal suboxide layer or the metal oxide layer is thinly formed, the corrosion inhibitor against the metal is "the metal layer is (second) Corrosion-preventive layer is formed by adsorbing to the microscopic part where the metal derived from the metal layer is not completely covered and is exposed, and the microscopic metal part is oxygen, water or chloride ions. In addition to the barrier effect of the layer containing the specific (meth)acrylic copolymer cured by the polyisocyanate-based crosslinking agent, it is possible to protect from corrosion deterioration of the metal layer. The progress can be further suppressed.

The type of the corrosion inhibitor for the above metals is not particularly limited, and any compound that can suppress the corrosion of the metals may be used. Of these, compounds capable of suppressing silver corrosion are preferable, and compounds having a functional group that easily adsorbs silver are preferable. For example, amines and their derivatives, compounds having a pyrrole ring, compounds having a triazole ring, compounds having a pyrazole ring, compounds having an imidazole ring, compounds having an indazole ring, guanidines and their derivatives, compounds having a thiazole ring, Examples thereof include thioureas, compounds having a mercapto group, thioethers, naphthalene compounds, copper chelate compounds, and silicone-modified resins. Of these, a compound having a nitrogen-containing group and a compound having a sulfur-containing group are particularly preferable, and it is preferable that they are selected from at least one kind or a mixture thereof.

Examples of the compound having a nitrogen-containing group include alkyl alcohol amine derivatives such as amino alcohol, methyl ethanol amine, dimethyl amino ethanol and N,N-dimethyl ethanol amine; phenyl amine derivatives such as diphenylamine, alkylated diphenylamine and phenylenediamine. Guanidine derivatives such as guanidine, 1-o-tolylbiguanide, 1-phenylguanidine and aminoguanidine; triazoles such as 1,2,3-triazole, 1,2,4-triazole, benzotriazole and 1-hydroxybenzotriazole And derivatives thereof; pyrrole derivatives such as N-butyl-2,5-dimethylpyrrole and N-phenyl-2,5-dimethylpyrrole; pyrazole, pyrazoline, pyrazolone, pyrazolidine, pyrazolidone, 3,5-dimethylpyrazole, 3-methyl -Pyrazoles such as 5-hydroxypyrazole and 4-aminopyrazole and derivatives thereof; imidazoles such as imidazole, histidine, 2-heptadecylimidazole and 2-methylimidazole and derivatives thereof; 4-chloroindazole, 4-nitroindazole, Examples thereof include indazoles such as 5-nitroindazole and 4-chloro-5-nitroindazole and derivatives thereof.

Examples of the compound having a sulfur-containing group include thiol derivatives such as alkanethiol and alkyl disulfide; thioglycerols such as 1-thioglycerol and derivatives thereof; thioglycols such as 2-hydroxyethanethiol and derivatives thereof. Thiobenzoic acids and their derivatives; pentaerythritol-tetrakis(3-mercaptobutyrate), 1,4-bis(3-mercaptobutyryloxy)butane, trimethylolpropane-tris(3-mercaptobutyrate), trimethylol Polyfunctional thiol monomers such as ethane-tris(3-mercaptobutyrate); thiophenol, glycol dimercaptoacetate, 3-mercaptopropyltrimethoxysilane and the like can be mentioned.

Furthermore, examples of the compound having both the nitrogen-containing group and the sulfur-containing group include mercaptotriazoles such as 3-mercapto-1,2,4-triazole and 1-methyl-3-mercapto-1,2,4-triazole. And derivatives thereof; mercaptothiazoles such as 2-mercaptobenzothiazole and derivatives thereof; mercaptoimidazoles such as 2-mercaptobenzimidazole and derivatives thereof; mercaptotriazines such as 2,4-dimercaptotriazine and derivatives thereof; thio Thioureas such as urea and guanylthiourea and their derivatives; aminothiophenols such as 2-aminothiophenol and 4-aminothiophenol and their derivatives; 2-mercapto-N-(2-naphthyl)acetamide and the like. ..

The content of the corrosion inhibitor for the metal is preferably 1% by mass or more and 20% by mass or less based on the total mass of the layer containing the corrosion inhibitor for the metal. If the content is less than 1% by mass, the effect as an additive is difficult to be exhibited, and if it exceeds 20% by mass, the protective layer in contact with the second metal suboxide layer or the metal oxide layer and There is a possibility that the strength of the layer containing the corrosion inhibitor with respect to the other metals may be lowered, or that the adhesion at the interface where they are in contact is lowered.

A corrosion inhibitor for the metal is contained in at least a layer of the infrared reflective layer that is in direct contact with the (second) metal suboxide layer or the metal oxide layer, of the coating type protective layer composed of a plurality of layers. What is caused is that, on the surface of the infrared reflective layer, "the metal layer is not completely covered by the (second) metal suboxide layer or the metal oxide layer and the metal derived from the metal layer is exposed. This is because it is possible to adsorb the corrosion inhibitor for the above metal and form the corrosion prevention layer most efficiently in the "extremely minute portion". As a result, when the (second) metal suboxide layer or the metal oxide layer is thinly formed for the purpose of reducing the solar radiation absorptivity of the low-emissivity film, the "metal layer (second)" Even if ``a minute portion where the metal derived from the metal layer is not completely covered by the metal suboxide layer or the metal oxide layer and is in a bare state'' occurs, the corrosion inhibitor for the metal, Corrosion preventive layer formed by adsorbing to minute metal parts acts as a barrier layer against external environmental factors such as oxygen, water and chloride ions that have diffused and permeated the protective layer. In order to protect the metal layer from the metal layer, the metal layer was not completely covered by the (second) metal suboxide layer or the metal oxide layer, and the metal derived from the metal layer was exposed. It is possible to remarkably suppress the progress of corrosion deterioration of the metal layer starting from "the extremely minute portion".

As described above, when the coating type protective layer is formed of a plurality of layers on the (second) metal suboxide layer or the metal oxide layer in the infrared reflective layer, among the plurality of layers, It is preferable that at least the layer in direct contact with the (second) metal suboxide layer or the metal oxide layer in the infrared reflective layer contains a corrosion inhibitor for the above metal, but in addition, another layer Also, a corrosion inhibitor for the above metals may be contained. The reason is that, for example, when the layer is formed by wet coating as the first layer of the above-mentioned coating type protective layer, the wet coating liquid should have the above-mentioned "metal layer (second) metal sub-layer". It is not completely covered by the oxide layer or the metal oxide layer and the metal derived from the metal layer is exposed. Even if the agent could not be adsorbed well on the very small metal part, if the next second protective layer contains a corrosion inhibitor for the above metal, the above-mentioned 2nd protective layer is formed on the first protective layer. When forming the protective layer of the second layer by wet coating, there is an opportunity to adsorb the corrosion inhibitor for the above-mentioned metal again to the minute metal portion where the above-mentioned coverage could not be adsorbed and the corrosion inhibitor for the above-mentioned metal could not be adsorbed. Because it can be given. As a result, the "metal layer is not completely covered by the (second) metal suboxide layer or the metal oxide layer, and the metal derived from the metal layer is exposed, in which the corrosion inhibitor for the metal is not adsorbed. It is possible to significantly reduce the remaining rate of "extremely minute parts".

<Adhesive layer>
In the transparent heat insulating and heat insulating member of the present embodiment, it is preferable that the pressure-sensitive adhesive layer is arranged on the surface of the transparent substrate opposite to the surface on which the coating type protective layer is formed. Thereby, the transparent heat insulating/insulating member of this embodiment can be easily attached to a transparent substrate such as a window glass. As a material for the pressure-sensitive adhesive layer, a material having a high visible light transmittance and a small difference in refractive index from a transparent substrate is preferably used. For example, acryl-based, polyester-based, urethane-based, rubber-based, silicone-based resin or the like can be used. Among them, acrylic resins are more preferably used because of their high optical transparency, good balance between wettability and adhesive strength, high reliability and many achievements, and relatively low price.

As the acrylic resin (adhesive), acrylic acid and its esters, methacrylic acid and its esters, homopolymers or copolymers of acrylic monomers such as acrylamide and acrylonitrile, and at least one of the above acrylic monomers. And a vinyl monomer such as vinyl acetate, maleic anhydride, or styrene. Particularly preferred acrylic adhesives are alkyl acrylate-based main monomers such as methyl acrylate, ethyl acrylate, butyl acrylate, and 2-ethylhexyl acrylate, which serve as components for expressing adhesiveness, and are used for improving cohesive strength. Monomers such as vinyl acetate, acrylamide, acrylonitrile, styrene, and methacrylate, which are the components, and acrylic acid, methacrylic acid, itaconic acid, crotonic acid, and anhydride, which are the components for further improving the adhesive force and imparting crosslinking points. Examples thereof include those obtained by appropriately copolymerizing monomers having a functional group such as maleic acid, hydroxylethyl methacrylate, hydroxylpropyl methacrylate, dimethylaminoethyl methacrylate, methylol acrylamide, and glycidyl methacrylate. The acrylic pressure-sensitive adhesive preferably has a Tg (glass transition temperature) in the range of −60° C. to −10° C., and a weight average molecular weight of 100,000 to 2,000,000, particularly preferably 500. Those in the range of 1,000 or more and 1,000,000 or less are more preferable. As the acrylic pressure-sensitive adhesive, one type or a mixture of two or more types of crosslinking agents such as isocyanate type, epoxy type and metal chelate type can be used, if necessary.

The thickness of the pressure-sensitive adhesive layer may be 10 μm or more and 100 μm or less, and more preferably 15 μm or more and 50 μm or less.

The adhesive layer preferably contains a benzophenone-based, benzotriazole-based, or triazine-based UV absorber in order to suppress the deterioration of the transparent heat-insulating and heat-insulating member due to UV rays such as sunlight. Further, it is preferable that the pressure-sensitive adhesive layer is provided with a release film on the pressure-sensitive adhesive layer until the transparent heat insulating/insulating member is attached to the transparent substrate for use.

<Transparent thermal insulation member>
Since the transparent heat-insulating heat insulating member of the present embodiment has the above-mentioned configuration, the visible light transmittance is 60% or more and the shielding coefficient is 0.69 by the combination of the proper design of the infrared reflective layer and the coating type protective layer. Hereinafter, the heat transmission coefficient can be set to 4.0 W/(m ² ·K) or less, and the solar radiation absorption rate can be set to 20% or less. That is, it is possible to provide a low-emission film having high transparency and excellent heat-shielding and heat-insulating properties, in which the risk of thermal cracking of the glass when the film is attached to a window glass is reduced.

Further, since the transparent heat insulating and heat insulating member has the above-mentioned constitution, it is immersed in a sodium chloride aqueous solution having a temperature of 50° C. and a concentration of 5% by mass for 30 days depending on the combination of an appropriate design of the infrared reflecting layer and the coating type protective layer. When the salt water resistance test is performed, the transmittance of light having a wavelength of 1100 nm in the transmission spectrum (initial) in the wavelength range of 300 to 1500 nm of the transparent heat insulating and heat insulating member measured before the salt water resistance test is T _B %, When the transmittance of light having a wavelength of 1100 nm in the transmission spectrum (after immersion for 30 days) in the wavelength range of 300 to 1500 nm of the transparent heat insulating and heat insulating member measured after the salt water resistance test is T _A %, the value of T _A -T _B Can be less than 10 points. That is, the above aspect means that the deterioration of the function of the infrared reflective layer under a severe test environment is significantly suppressed, and a low radiation film excellent in corrosion resistance deterioration can be provided.

Further, since the transparent heat insulating and heat insulating member has the above-mentioned structure, the reflection spectrum in the reflection spectrum measured according to JIS R3106-1998 by the combination of the proper design of the infrared reflection layer and the coating type protective layer. Point A is a point corresponding to a wavelength of 535 nm on the virtual line a indicating the average value of the maximum reflectance and the minimum reflectance in the wavelength range of 500 to 570 nm, and the maximum reflectance in the wavelength range of 620 to 780 nm of the reflection spectrum. And a point corresponding to a wavelength of 700 nm on an imaginary line b indicating the average value of the minimum reflectance is defined as a point B, and a straight line passing through the points A and B is extended in a wavelength range of 500 to 780 nm to form a reference straight line AB. Then, when the reflectance value of the reflectance spectrum in the wavelength range of 500 to 570 nm and the reflectance value of the reference line AB are compared, the reflectance at the wavelength at which the difference between the reflectance values becomes maximum. When the absolute value of the difference between the values is defined as the maximum fluctuation difference ΔA, the value of the maximum fluctuation difference ΔA is 7% or less in% of the reflectance, and the reflectance of the reflection spectrum in the wavelength range of 620 to 780 nm. The absolute value of the difference between the reflectance values at the wavelength where the difference between the reflectance values is the maximum when the value of the above is compared with the reflectance value of the reference straight line AB is defined as the maximum variation difference ΔB. At the same time, the value of the maximum variation difference ΔB can be 9% or less in% of the reflectance. That is, the above aspect means that the vertical fluctuation of the visible light reflectance linked with the wavelength in the reflection spectrum is reduced, and the appearance that suppresses the occurrence of the iris pattern and the reflected color change due to the viewing angle. It is also possible to provide an excellent low-emission film.

Next, an example of the transparent heat insulating/insulating member of the present embodiment will be described with reference to the drawings.

FIG. 1 is a schematic cross-sectional view showing an example of the transparent heat insulating/insulating member of the present embodiment. In FIG. 1, the transparent heat insulating/insulating member 10 includes a transparent substrate 11, a functional layer 23 including an infrared reflective layer 21 and a coating type protective layer 22, and an adhesive layer 19. The infrared reflection layer 21 is composed of a first metal suboxide layer or metal oxide layer 12, a metal layer 13, and a second metal suboxide layer or metal oxide layer 14 from the transparent substrate side. .. The coating type protective layer 22 includes an optical adjustment layer 15, a medium refractive index layer 16, a high refractive index layer 17, and a low refractive index layer 18. For example, a layer containing a specific (meth)acrylic copolymer having a hydroxyl group and a polyisocyanate cross-linking agent that reacts with the hydroxyl group, and the low refractive index layer 18 using the medium refractive index layer 16 as a pre-curing resin component. A layer containing an active energy ray-curable resin can be used as the pre-curing resin component.

FIG. 2 is a diagram showing an example of transmission spectra of the transparent heat insulating and heat insulating member of the present embodiment before and after the salt water resistance test. When the salt water resistance test in which the transparent heat insulation heat insulating member is immersed in a sodium chloride aqueous solution having a temperature of 50° C. and a concentration of 5 mass% for 30 days is performed, the wavelength of the transparent heat insulation heat insulating member measured before the salt water resistance test is 300. The transmittance of light having a wavelength of 1100 nm in the transmission spectrum (initial) in the range of up to 1500 nm is T _B %, and the transmission spectrum of the transparent heat insulating and heat insulating member measured after the salt water resistance test is in the range of 300 to 1500 nm (soaking for 30 days the transmittance of light of wavelength 1100nm after) When T _a%, the value of T _a -T _B may be less than 10 points.

FIG. 3 is a diagram illustrating how to obtain the “reference straight line AB”, the “maximum variation difference ΔA”, and the “maximum variation difference ΔB” with respect to the visible light reflection spectrum of the transparent heat insulating and heat insulating member of the present invention. In the reflection spectrum measured according to JIS R3106-1998, a point corresponding to a wavelength of 535 nm on the virtual line a indicating the average value of the maximum reflectance and the minimum reflectance in the wavelength range of 500 to 570 nm of the reflection spectrum is point A. The point corresponding to the wavelength 700 nm on the virtual line b indicating the average value of the maximum reflectance and the minimum reflectance in the wavelength range of 620 to 780 nm of the reflection spectrum is point B, and the points A and B are When the passing straight line is extended in the wavelength range of 500 to 780 nm as the reference straight line AB, and the reflectance value of the reflection spectrum in the wavelength range of 500 to 570 nm is compared with the reflectance value of the reference straight line AB, The absolute value of the difference in the reflectance values at the wavelength where the difference in the reflectance values is maximum is defined as the maximum variation difference ΔA. Similarly, when the reflectance value of the reflection spectrum in the wavelength range of 620 to 780 nm and the reflectance value of the reference straight line AB are compared, the reflectance at the wavelength at which the difference between the reflectance values becomes maximum. The absolute value of the difference between the rate values is defined as the maximum variation difference ΔB.

FIG. 4 is a diagram showing an example of a reflection spectrum in the visible light region when light is measured from the glass surface side in the transparent heat insulating/insulating member of Example 1 described later. The value of the maximum variation difference ΔA may be 7% or less in% of reflectance and the value of the maximum variation difference ΔB may be 9% or less in% of reflectance in the transparent heat insulating/insulating member. ..

Thus, the transparent heat insulating heat insulating member of the above embodiment, while lowering the solar radiation absorption rate by the infrared reflection layer, can exhibit a heat insulating function and a heat shielding function, also scratch resistance by the coating type protective layer, Corrosion resistance is improved and the heat insulation function can be maintained.

(Manufacturing method of transparent heat insulating and heat insulating member)
Next, an embodiment of the method for manufacturing the transparent heat insulating/insulating member of the present invention will be described. The embodiment of the method for producing a transparent heat insulating and heat insulating member of the present invention comprises a step of forming an infrared reflective layer on a transparent substrate by a dry coating method, and a protective layer composed of a plurality of layers on the infrared reflective layer. Is formed by a wet coating method.

Hereinafter, an example of a method of manufacturing the transparent heat insulating/insulating member of the present embodiment will be described with reference to FIG.

First, the infrared reflection layer 21 is formed on one surface of the transparent substrate 11. The infrared reflective layer 21 can be formed by a dry coating method such as a method of sputtering a conductive material or a transparent dielectric material, but may be formed by another method. The infrared reflective layer 21 has a three-layer structure including a first metal suboxide layer or metal oxide layer 12, a metal layer 13, and a second metal suboxide layer or metal oxide layer 14. It is preferable in terms of heat shielding/heat insulating function, corrosion resistance and productivity. In particular, when forming the first metal suboxide layer 12 and the second metal suboxide layer 14, it is preferable to form them by the various sputtering methods as described above. Thereby, the metal suboxide layer in which the metal is partially oxidized can be reliably formed.

Next, the optical adjustment layer 15 containing a corrosion inhibitor for metals is formed on the infrared reflection layer 21. Subsequently, a medium refractive index layer 16 containing a specific (meth)acrylic copolymer having a hydroxyl group and a polyisocyanate crosslinking agent that reacts with the hydroxyl group is formed on the optical adjustment layer 15, and the medium refractive index layer 16 is formed. A high refractive index layer 17 is formed on the refractive index layer 16, and a low refractive index layer 18 containing an active energy ray curable resin is formed on the high refractive index layer 17. Each of these layers can be formed by a wet coating method using a coater such as a die coater, a comma coater, a reverse coater, a dam coater, a doctor bar coater, a gravure coater, a micro gravure coater, and a roll coater. The coating-type protective layer 22 formed of a plurality of layers formed in this manner can prevent the infrared reflective layer 21 from being damaged by window wiping and the like even when the infrared reflective layer 21 is placed on the indoor side, and can be resistant to damage. It is excellent in corrosion deterioration and can suppress the angular dependence such as the iris phenomenon and the change of the reflected color depending on the viewing angle in appearance, and can further maintain the heat insulating function of the infrared reflective layer while lowering the solar radiation absorption rate. ..

Finally, the adhesive layer 19 is formed on the other surface of the transparent substrate 11. The method of forming the pressure-sensitive adhesive layer 19 is not particularly limited, and the pressure-sensitive adhesive may be directly applied to the outer surface of the transparent substrate 11, or a separately prepared pressure-sensitive adhesive sheet may be attached.

By the above steps, an example of the transparent heat insulating/insulating member of the present embodiment is obtained, and thereafter, it is used by being attached to a glass substrate or the like as needed.

The present invention will be described in detail below based on examples. However, the present invention is not limited to the following examples.

(Measurement of refractive index)
The refractive index of the optical adjustment layer, the medium refractive index layer, the high refractive index layer, and the low refractive index layer described in the following examples and comparative examples were measured by the methods described below.

First, the polyethylene terephthalate (PET) film "A4100" (trade name, thickness: 50 μm) manufactured by Toyobo Co., Ltd., which has been subjected to easy-adhesion treatment on one side, was coated with each layer-forming coating in a thickness of 500 nm on the surface not subjected to the easy-adhesion treatment. It is applied so as to be dried and dried to prepare a sample for measuring a refractive index. When a UV-curable coating material is used for each layer-forming coating material, the coating material is dried and then irradiated with ultraviolet light having a light amount of 300 mJ/cm ^{2 by} a high-pressure mercury lamp to be cured to prepare a refractive index measurement sample. ..

Next, a black tape was attached to the back side of the prepared sample for measuring refractive index, the reflection spectrum was measured with a reflection spectral film thickness meter "FE-3000" (trade name, manufactured by Otsuka Electronics Co., Ltd.), and the measured reflection was measured. Based on the spectrum, fitting was performed from the n-Cauchy equation to determine the refractive index of light having a wavelength of 550 nm in each layer.

(Measurement of film thickness)
Regarding the film thicknesses of the optical adjustment layer, the medium refractive index layer, the high refractive index layer, and the low refractive index layer described in the following Examples and Comparative Examples, the infrared reflective layer and the protective layer of the transparent substrate are not formed. A black tape is attached to the surface side, and a reflection spectrum is measured for each layer by an instant multi-photometry system "MCPD-3000" (trade name, manufactured by Otsuka Electronics Co., Ltd.), and the obtained reflection spectrum is used to measure the above-mentioned refractive index. Using the obtained refractive index, fitting by an optimization method was performed to obtain the film thickness of each layer.

(Example 1)
<Preparation of transparent substrate with infrared reflective layer>
First, as a transparent substrate, a polyethylene terephthalate (PET) film "A4100" (trade name, thickness: 50 μm) manufactured by Toyobo Co., Ltd. on one side of which is easily adhered is used, and the surface side of the PET film which is not easily adhered is used. Then, a first metal suboxide layer, a metal layer, and a second metal suboxide layer were formed from the PET film side as follows. First, using a titanium target, a 2 nm-thick first metal suboxide layer (TiO _x layer) was formed by a reactive sputtering method. As the sputtering gas in the reactive sputtering method, a mixed gas of Ar/O ₂ was used, and the gas flow volume ratio was Ar 97%/O ₂ 3%. Then, a 12 nm-thick metal layer (Ag layer) was formed on the first metal suboxide layer by a sputtering method using a silver target. Ar gas 100% was used as the sputtering gas in the sputtering method. Further, a second target metal suboxide layer (TiO _x layer) having a thickness of 2 nm was formed on the metal layer by a reactive sputtering method using a titanium target. As the sputtering gas in the reactive sputtering method, a mixed gas of Ar/O ₂ was used, and the gas flow volume ratio was Ar 97%/O ₂ 3%. Thereby, the infrared reflective layer having a three-layer structure of the first metal suboxide layer (TiO _x layer)/metal layer (Ag layer)/second metal suboxide layer (TiO _x layer) from the PET film side. An attached PET film was produced. The x of the TiO _x layer was 1.5.

The total thickness of the infrared reflective layer [first metal suboxide layer (TiO _x layer)+metal layer (Ag layer)+second metal suboxide layer (TiO _x layer)] obtained by the above method is It was 16 nm, and the ratio of the thickness of the second metal suboxide layer (TiO _x layer) to the total thickness was 12.5%.

<Formation of optical adjustment layer>
Toyo Ink Co., Ltd. titanium oxide hard coating agent "Rioduras TYT80-01" (trade name, solid content concentration 25 mass%, refractive index 1.80 [nominal value]) 96.00 parts by mass, and a corrosion inhibitor for metals As a diluting solvent, 1.20 parts by mass of 2-mercaptobenzothiazole having a sulfur-containing group (5.00 parts by mass with respect to the solid content of TYT80-01) and 902.80 parts by mass of methyl isobutyl ketone as a diluting solvent were used as a disperser. To prepare an optical control coating material A. Next, the optical adjustment coating A is applied on the infrared reflective layer using a micro gravure coater (manufactured by Inui Seiki Co., Ltd.) so that the thickness after drying becomes 50 nm, and after drying, high pressure is applied. An optical adjustment layer having a thickness of 50 nm was formed by irradiating with a mercury lamp an ultraviolet ray having a light amount of 300 mJ/cm ² to cure the ultraviolet ray. The refractive index of the manufactured optical adjustment layer was 1.79 when measured by the above-mentioned method.

<Formation of medium refractive index layer>
Acrylic copolymer A (t-butyl methacrylate (Tg: 107° C.)/isobutene/4-hydroxybutyl acrylate/crotonic acid=84 parts by mass/5 parts by mass/10 parts by mass/1 part by mass, solid content concentration 35.28 parts by mass of a solution of 50% by mass, a hydroxyl value of 38 mgKOH/g, an acid value of 6 mgKOH/g) and an isocyanate cross-linking agent "Coronate HX" manufactured by Tosoh Corporation (trade name, solid content concentration 100% by mass) 2. 39 parts by mass (molar equivalent ratio of isocyanate group (—NCO) of cross-linking agent to hydroxyl group (—OH) of (meth)acrylic copolymer: NCO/OH=1.0) and methyl isobutyl as a diluting solvent 962.33 parts by mass of ketone was blended with a disper to prepare a medium refractive index coating material A. Next, the medium refractive index coating material A is applied on the optical adjustment layer using the microgravure coater so that the thickness after drying is 60 nm, and dried at 120° C. for 2 minutes to be heat-cured. As a result, a medium refractive index layer having a thickness of 60 nm was formed. The refractive index of the manufactured medium refractive index layer was 1.48 when measured by the above-mentioned method.

<Formation of high refractive index layer>
200.00 parts by mass of titanium oxide type hard coating agent "Riodurus TYT80-01" (trade name, solid content concentration 25% by mass, refractive index 1.80 [nominal value]) manufactured by Toyo Ink and methylisobutyl as a diluting solvent 800.00 parts by mass of ketone was mixed with a disper to prepare a high refractive index coating material A. Next, the high refractive index coating material A was applied on the medium refractive index layer using the microgravure coater so that the thickness after drying was 90 nm, and after drying, it was exposed to 300 mJ with a high pressure mercury lamp. A high-refractive-index layer having a thickness of 90 nm was formed by irradiating and curing with an ultraviolet ray having a light amount of /cm ² . The refractive index of the produced high refractive index layer was 1.80 when measured by the above-mentioned method.

<Formation of low refractive index layer>
Hollow silica-containing low-refractive-index paint "ELCOM P-5062" (trade name, solid content concentration 3% by mass, refractive index 1.38 [nominal value]) manufactured by JGC Catalysts & Chemicals Co., Ltd. was used as the low-refractive-index paint A. The low-refractive-index coating material A was applied on the high-refractive-index layer using the microgravure coater so that the thickness after drying was 100 nm, and after drying, it was dried with a high-pressure mercury lamp at 300 mJ/cm ² . A low-refractive-index layer having a thickness of 100 nm was formed by irradiating with a light amount of ultraviolet rays and curing. The refractive index of the manufactured low refractive index layer was 1.37 when measured by the above-mentioned method.

As described above, an infrared reflection film (transparent heat insulating/insulating member) having a protective layer including an optical adjustment layer, a medium refractive index layer, a high refractive index layer and a low refractive index layer was produced. The protective layer thus obtained had a thickness of 300 nm.

<Formation of adhesive layer>
First, a release PET film “NS-38+A” (trade name, thickness: 38 μm) manufactured by Nakamoto Pax Co., Ltd., one surface of which was treated with silicone, was prepared. Further, with respect to 1000.00 parts by mass of acrylic adhesive "SKDyne 2094" (trade name, solid content: 25% by mass) manufactured by Soken Chemical Co., Ltd., ultraviolet absorber (benzophenone) 12. manufactured by Wako Pure Chemical Industries, Ltd. 50 parts by mass and 2.70 parts by mass of a cross-linking agent "E-AX" (trade name, solid content: 5% by mass) manufactured by Soken Chemical Industry Co., Ltd. were added and mixed with a disper to prepare an adhesive coating composition.

Next, the pressure-sensitive adhesive coating was applied on the silicone-treated surface of the release PET film so that the thickness after drying was 25 μm, and the pressure-sensitive adhesive layer was formed after drying. Furthermore, the side of the infrared reflective film on which the infrared reflective layer is not formed is bonded to the upper surface of this adhesive layer, and the infrared reflective film with the adhesive layer is provided with a protective layer consisting of four layers (transparent heat insulating and heat insulating film). Member) was produced.

<Lamination with glass substrate>
First, as a glass substrate, a float glass (made by Nippon Sheet Glass Co., Ltd.) having a size of 5 cm×5 cm and a thickness of 3 mm was prepared. Next, the infrared reflective film with an adhesive layer provided with the protective layer is cut into a size of 3 cm×3 cm, the release PET film is peeled off, and the adhesive layer side of the infrared reflective film with an adhesive layer is attached. It was attached to the center of the float glass.

(Example 2)
Example 1 except that the amount of the isocyanate crosslinking agent "Coronate HX" (trade name, solid content concentration 100% by mass) manufactured by Tosoh Corporation was changed to 3.59 parts by mass (NCO/OH=2.0). A medium-refractive-index coating B was prepared in the same manner as the medium-refractive-index coating A, and the pressure-sensitive adhesive layer provided with a protective layer consisting of four layers was prepared in the same manner as in Example 1 except that this medium-refractive-index coating B was used. An infrared reflection film with a coating was prepared and attached to a glass substrate. The refractive index of the manufactured medium refractive index layer was 1.48 when measured by the above-mentioned method.

(Example 3)
Example 1 except that the amount of the isocyanate cross-linking agent "Coronate HX" (trade name, solid content concentration 100% by mass) manufactured by Tosoh Corporation was changed to 1.20 parts by mass (NCO/OH=0.5). A medium-refractive-index coating C was prepared in the same manner as the medium-refractive-index coating A, and the pressure-sensitive adhesive layer provided with a protective layer consisting of four layers was prepared in the same manner as in Example 1 except that this medium-refractive-index coating C was used. An infrared reflection film with a coating was prepared and attached to a glass substrate. The refractive index of the manufactured medium refractive index layer was 1.48 when measured by the above-mentioned method.

(Example 4)
<Preparation of medium refractive index paint>
First, acrylic copolymer B (t-butyl acrylate (Tg: 43° C.)/2-hydroxyethyl methacrylate/methacrylic acid=89 parts by mass/10 parts by mass/1 part by mass, solid content concentration 50% by mass, 34.87 parts by mass of a solution having a hydroxyl value of 42 mgKOH/g and an acid value of 6 mgKOH/g, and 2.58 parts by mass of an isocyanate-based crosslinking agent "Coronate HX" (trade name, solid content concentration 100% by mass) manufactured by Tosoh Corporation ( NCO/OH=1.0) and 962.55 parts by mass of methyl isobutyl ketone as a diluting solvent were mixed with a disper to prepare a medium refractive index coating D.

An infrared reflective film with a pressure-sensitive adhesive layer having a protective layer consisting of four layers was prepared in the same manner as in Example 1 except that the medium refractive index coating material D was used, and the infrared reflective film was attached to a glass substrate. The refractive index of the manufactured medium refractive index layer was 1.48 when measured by the above-mentioned method.

(Example 5)
<Preparation of medium refractive index paint>
First, acrylic copolymer C (cyclohexyl methacrylate (Tg: 83° C.)/4-hydroxybutyl acrylate=90 parts by mass/10 parts by mass, solid content concentration 50% by mass, hydroxyl value 38 mgKOH/g) 35.95 2.0 parts by mass (NCO/OH=1.0) of a solution of an isocyanate cross-linking agent "Coronate HX" (trade name, solid content concentration 100% by mass) manufactured by Tosoh Corporation, and methylisobutyl as a diluting solvent. 962.02 parts by mass of ketone was mixed with a disper to prepare a medium refractive index coating material E.

An infrared reflective film with a pressure-sensitive adhesive layer provided with a protective layer consisting of four layers was prepared in the same manner as in Example 1 except that the medium refractive index coating material E was used, and was bonded to a glass substrate. The refractive index of the manufactured medium refractive index layer was 1.50 when measured by the above-mentioned method.

(Example 6)
<Preparation of medium refractive index paint>
First, a solution 35 of acrylic copolymer D (isobornyl acrylate (Tg: 94° C.)/4-hydroxybutyl acrylate=90 parts by mass/10 parts by mass, solid concentration 50% by mass, hydroxyl value 38 mgKOH/g) .95 parts by mass, Tosoh's isocyanate cross-linking agent "Coronate HX" (trade name, solid content concentration 100% by mass) 2.03 parts by mass (NCO/OH=1.0), and methyl isobutyl as a diluting solvent. 962.02 parts by mass of ketone was blended with a disper to prepare a medium refractive index coating material F.

An infrared reflecting film with a pressure-sensitive adhesive layer having a protective layer consisting of four layers was prepared in the same manner as in Example 1 except that the medium refractive index coating material F was used, and was bonded to a glass substrate. The refractive index of the manufactured medium refractive index layer was 1.51 as measured by the above method.

(Example 7)
<Preparation of medium refractive index paint>
First, acrylic copolymer E (t-butyl methacrylate (Tg: 107° C.)/isobutene/4-hydroxybutyl vinyl ether=80 parts by mass/10 parts by mass/10 parts by mass, solid content concentration 50% by mass, hydroxyl value 34.42 parts by mass of a solution of 46 mg KOH/g) and 2.79 parts by mass (NCO/OH=1.0) of an isocyanate cross-linking agent "Coronate HX" (trade name, solid content concentration 100% by mass) manufactured by Tosoh Corporation. And, as a diluting solvent, methyl isobutyl ketone/toluene=866.51/96.28 parts by mass were mixed with a disper to prepare a medium refractive index coating material G.

An infrared reflective film with a pressure-sensitive adhesive layer provided with a protective layer consisting of four layers was produced in the same manner as in Example 1 except that the medium refractive index coating material G was used, and the infrared reflective film was attached to a glass substrate. The refractive index of the manufactured medium refractive index layer was 1.49 as measured by the above-mentioned method.

(Example 8)
<Preparation of medium refractive index paint>
First, acrylic copolymer F (t-butyl methacrylate (Tg: 107° C.)/versatitic acid (C9) vinyl ester/4-hydroxybutyl vinyl ether=70 parts by mass/20 parts by mass/10 parts by mass, solid content concentration 34.42 parts by mass of a solution of 50% by mass and a hydroxyl value of 46 mgKOH/g, and 2.79 parts by mass of NCO/isocyanate-based cross-linking agent "Coronate HX" (trade name, solid content concentration 100%) manufactured by Tosoh Corporation. OH=1.0) and 962.79 parts by mass of methyl isobutyl ketone as a diluting solvent were mixed with a disper to prepare a medium refractive index coating material H.

An infrared reflective film with a pressure-sensitive adhesive layer provided with a protective layer consisting of four layers was produced in the same manner as in Example 1 except that the above medium refractive index coating material H was used, and was bonded to a glass substrate. The refractive index of the manufactured medium refractive index layer was 1.48 when measured by the above-mentioned method.

(Example 9)
An infrared reflective film with a pressure-sensitive adhesive layer provided with a protective layer consisting of four layers was produced in the same manner as in Example 1 except that the formation of the optical adjustment layer and the medium refractive index layer was changed to the following, and the laminated film was attached to a glass substrate. It was

<Formation of optical adjustment layer>
First, 13.92 parts by mass of titanium oxide ultrafine particles "TTO-55(A)" (trade name) manufactured by Ishihara Sangyo Co., Ltd. and acrylic copolymer G (t-butyl methacrylate (Tg: 107°C)/acryl) Acid 4-hydroxybutyl/crotonic acid=84 parts by mass/15 parts by mass/1 part by mass, solid content concentration 50% by mass, hydroxyl value 58 mgKOH/g, acid value 6 mgKOH/g) solution 16.78 parts by mass, and methyl A mixed solution was prepared by mixing 43.67 parts by mass of isobutyl ketone. Zirconia beads having a diameter of 0.3 mm were added to this mixed solution and dispersed using a paint conditioner (manufactured by Toyo Seiki Co., Ltd.) to prepare a titanium oxide ultrafine particle dispersion. To this titanium oxide ultrafine particle dispersion, 1.71 parts by mass (NCO/OH=1.0) of isocyanate-based cross-linking agent "Coronate HX" (trade name, solid content concentration 100% by mass) manufactured by Tosoh Corporation and a diluting solvent Was mixed with 923.92 parts by mass of methyl isobutyl ketone by a disper to prepare an optical adjustment coating material B. Next, the above optical adjustment coating B was applied onto the infrared reflective layer used in Example 1 using a micro gravure coater (manufactured by Rensai Seiki Co., Ltd.) so that the thickness after drying would be 50 nm, An optical adjustment layer having a thickness of 50 nm was formed by drying at 120° C. for 2 minutes and thermosetting. The refractive index of the manufactured optical adjustment layer was 1.80 when measured by the above-mentioned method.

<Formation of medium refractive index layer>
UV-curable acrylic polymer "SMP-360A" (trade name, solid content concentration 50% by mass) manufactured by Kyoeisha Chemical Co., Ltd. 28.00 parts by mass, methyl ethyl ketone 389.80 parts by mass as a diluting solvent, and cyclohexanone 582.20 parts by mass. And 0.30 part by mass of a photopolymerization initiator "Irgacure 907" (trade name) manufactured by BASF Corp. were mixed with a disper to prepare a medium refractive index coating material I. Next, the medium refractive index coating material I was applied on the optical adjustment layer using the microgravure coater so that the thickness after drying was 60 nm, and after drying, it was 300 mJ/ with a high pressure mercury lamp. A medium-refractive-index layer having a thickness of 60 nm was formed by irradiating and curing the ultraviolet ray having a light amount of cm ² . The refractive index of the manufactured medium refractive index layer was 1.50 when measured by the above-mentioned method.

(Example 10)
The medium refractive index layer was formed in the same manner as in Example 1 except that the formation of the medium refractive index layer was changed to the following without providing the optical adjustment layer and the thickness of the high refractive index layer after drying was changed to 290 nm. An infrared reflective film with a pressure-sensitive adhesive layer provided with a protective layer consisting of three layers, a high refractive index layer and a low refractive index layer, was prepared and attached to a glass substrate. The protective layer thus obtained had a thickness of 540 nm.

<Formation of medium refractive index layer>
First, acrylic copolymer G (t-butyl methacrylate (Tg: 107° C.)/4-hydroxybutyl acrylate/crotonic acid=84 parts by mass/15 parts by mass/1 part by mass, solid content concentration 50% by mass, 33.21 parts by mass of a solution having a hydroxyl value of 58 mgKOH/g and an acid value of 6 mgKOH/g) and 3.39 parts by mass of an isocyanate cross-linking agent "Coronate HX" (trade name, solid content concentration 100% by mass) manufactured by Tosoh Corporation ( NCO/OH=1.0) and 963.40 parts by mass of methyl isobutyl ketone as a diluting solvent were mixed with a disper to prepare a medium refractive index coating material J. Next, the medium refractive index coating material J was coated on the optical adjustment layer using the microgravure coater so that the thickness after drying was 150 nm, and after drying, 300 mJ/ A medium-refractive index layer having a thickness of 150 nm was formed by irradiating and curing with ultraviolet rays of a light amount of cm ² . The refractive index of the manufactured medium refractive index layer was 1.48 when measured by the above-mentioned method.

(Example 11)
In the same manner as in Example 1 except that the formation of the high refractive index layer was changed to the following without providing the optical adjustment layer and the medium refractive index layer, and the thickness of the low refractive index layer after drying was changed to 95 nm. An infrared reflective film with a pressure-sensitive adhesive layer provided with a protective layer composed of two layers, a high refractive index layer and a low refractive index layer, was prepared and attached to a glass substrate. The thickness of the resulting protective layer was 240 nm.

<Formation of high refractive index layer>
First, 29.00 parts by mass of titanium oxide ultrafine particles “TTO-55(A)” (trade name) manufactured by Ishihara Sangyo Co., Ltd. and acrylic copolymer G (t-butyl methacrylate (Tg: 107° C.)/acryl) Acid 4-hydroxybutyl/crotonic acid=84 parts by mass/15 parts by mass/1 part by mass, solid content concentration 50% by mass, hydroxyl value 58 mgKOH/g, acid value 6 mgKOH/g) solution 34.88 parts by mass, and methyl A mixed solution was prepared by mixing 90.92 parts by mass of isobutyl ketone. Zirconia beads having a diameter of 0.3 mm were added to this mixed solution and dispersed using a paint conditioner (manufactured by Toyo Seiki Co., Ltd.) to prepare a titanium oxide ultrafine particle dispersion. To this titanium oxide ultrafine particle dispersion, 3.56 parts by mass (NCO/OH=1.0) of isocyanate-based cross-linking agent "Coronate HX" (trade name, solid content concentration 100% by mass) manufactured by Tosoh Corporation, and a diluting solvent Was mixed with 84.64 parts by mass of methyl isobutyl ketone by a disper to prepare a high refractive index coating material B. Next, the high refractive index coating material B was applied onto the infrared reflective layer used in Example 1 using a micro gravure coater (manufactured by Rensai Seiki Co., Ltd.) so that the thickness after drying was 145 nm. A high refractive index layer having a thickness of 145 nm was formed by drying at 120° C. for 2 minutes and thermosetting. The refractive index of the produced high refractive index layer was 1.80 when measured by the above-mentioned method.

(Example 12)
An optical adjustment paint similar to the optical adjustment paint A of Example 1 except that 2-mercaptobenzothiazole having a sulfur-containing group as a corrosion inhibitor for metals was changed to 1-o-tolylbiguanide having a nitrogen-containing group. Infrared reflective film with a pressure-sensitive adhesive layer provided with a protective layer consisting of four layers was produced in the same manner as in Example 1 except that C was produced and this optical adjustment coating C was used, and was laminated on a glass substrate. The refractive index of the manufactured optical adjustment layer was 1.79 when measured by the above-mentioned method.

(Example 13)
An optical adjustment coating D was prepared in the same manner as the optical adjustment coating A of Example 1 except that 2-mercaptobenzothiazole having a sulfur-containing group was not added as a corrosion inhibitor for metals. An infrared reflective film with a pressure-sensitive adhesive layer provided with a protective layer consisting of four layers was prepared in the same manner as in Example 1 except that it was used, and was bonded to a glass substrate. The refractive index of the manufactured optical adjustment layer was 1.80 when measured by the above-mentioned method.

(Example 14)
A pressure-sensitive adhesive layer provided with a protective layer consisting of four layers in the same manner as in Example 1 except that the thickness of the medium refractive index layer after drying was changed to 130 nm and the thickness of the high refractive index layer was changed to 500 nm. An infrared reflection film with a coating was prepared and attached to a glass substrate. The protective layer thus obtained had a thickness of 780 nm.

(Example 15)
The thickness of the metal layer (Ag layer) of the infrared reflective layer is 8 nm, the thickness of the optical adjustment layer after drying is 60 nm, the thickness of the medium refractive index layer after drying is 200 nm, and the thickness of the high refractive index layer after drying. And the thickness of the low refractive index layer after drying was changed to 120 nm, an infrared reflective film with a pressure-sensitive adhesive layer provided with a protective layer consisting of four layers was prepared in the same manner as in Example 1 to prepare a glass. It was attached to the substrate. The total thickness of the obtained infrared reflective layer [first metal suboxide layer (TiO _x layer)+metal layer (Ag layer)+second metal suboxide layer (TiO _x layer)] was 12 nm. The ratio of the thickness of the second metal suboxide layer (TiO _x layer) to the total thickness was 16.7%. Further, the thickness of the obtained protective layer was 930 nm.

(Example 16)
Same as Example 1 except that the dried thickness of the medium refractive index layer was changed to 150 nm, the dried thickness of the high refractive index layer was changed to 700 nm, and the dried thickness of the low refractive index layer was changed to 110 nm. As a result, an infrared reflecting film with a pressure-sensitive adhesive layer having a protective layer consisting of four layers was prepared and attached to a glass substrate. The protective layer thus obtained had a thickness of 1010 nm.

(Example 17)
Infrared reflection with a pressure-sensitive adhesive layer provided with a protective layer consisting of 4 layers in the same manner as in Example 1 except that the thickness of the second metal suboxide layer (TiO _X layer) of the infrared reflection layer was changed to 4 nm. A film was prepared and attached to a glass substrate. The total thickness of the obtained infrared reflective layer [first metal suboxide layer (TiO _X layer)+metal layer (Ag layer)+second metal suboxide layer (TiO _X layer)] was 18 nm. The ratio of the thickness of the second metal suboxide layer (TiO _X layer) to the total thickness was 22.2%.

(Example 18)
<Preparation of transparent substrate with infrared reflective layer>
First, using the above-mentioned PET film "A4100" (thickness: 50 μm) having one surface subjected to easy adhesion treatment as a transparent substrate, the first metal from the PET film side was applied to the non-easy adhesion treatment surface side of the PET film. The suboxide layer, the metal layer, and the second metal oxide layer were formed as follows. First, using a titanium target, a 2 nm-thick first metal suboxide layer (TiO _x layer) was formed by a reactive sputtering method. As the sputtering gas in the reactive sputtering method, a mixed gas of Ar/O ₂ was used, and the gas flow volume ratio was Ar 97%/O ₂ 3%. Then, a 13 nm-thick metal layer (Ag layer) was formed on the metal suboxide layer by a sputtering method using a silver target. Ar gas 100% was used as the sputtering gas in the sputtering method. Further, a titanium oxide target was used on the metal layer to form a second metal oxide layer (TiO ₂ layer) having a thickness of 5 nm by a sputtering method. Ar gas 100% was used as the sputtering gas in the sputtering method. As a result, an infrared reflection layer having a three-layer structure of a first metal suboxide layer (TiO _X layer)/metal layer (Ag layer)/second metal oxide layer (TiO ₂ layer) from the transparent substrate side. An attached PET film was produced. The x of the TiO _x layer was 1.5.

An infrared reflective film with a pressure-sensitive adhesive layer provided with a protective layer consisting of 4 layers was prepared in the same manner as in Example 1 except that the PET film with an infrared reflective layer was used, and was bonded to a glass substrate. The total thickness of the obtained infrared reflective layer [first metal suboxide layer (TiO _X layer)+metal layer (Ag layer)+second metal oxide layer (TiO ₂ layer)] was 20 nm, The ratio of the thickness of the second metal oxide layer (TiO ₂ layer) to the total thickness was 25.0%.

(Example 19)
An infrared reflective film with a pressure-sensitive adhesive layer provided with a protective layer composed of 4 layers in the same manner as in Example 18 except that the thickness of the second metal oxide layer (TiO ₂ layer) of the infrared reflective layer was changed to 7 nm. Was prepared and attached to a glass substrate. The total thickness of the obtained infrared reflective layer [first metal suboxide layer (TiO _X layer)+metal layer (Ag layer)+second metal oxide layer (TiO ₂ layer)] was 22 nm, The ratio of the thickness of the second metal oxide layer (TiO ₂ layer) to the total thickness was 31.8%.

(Example 20)
<Preparation of transparent substrate with infrared reflective layer>
First, using the above-mentioned PET film "A4100" (thickness: 50 μm) having one surface subjected to easy adhesion treatment as a transparent substrate, the first metal from the PET film side was applied to the non-easy adhesion treatment surface side of the PET film. The oxide layer, the metal layer, and the second metal suboxide layer were formed as follows. First, a 2 nm-thick first metal oxide layer (TiO ₂ layer) was formed by a sputtering method using a titanium oxide target. Ar gas 100% was used as the sputtering gas in the sputtering method. Then, a 12 nm-thick metal layer (Ag layer) was formed on the metal oxide layer by a sputtering method using a silver target. Ar gas 100% was used as the sputtering gas in the sputtering method. Further, a second target metal suboxide layer (TiO _x layer) having a thickness of 2 nm was formed on the metal layer by a reactive sputtering method using a titanium target. As the sputtering gas in the reactive sputtering method, a mixed gas of Ar/O ₂ was used, and the gas flow volume ratio was Ar 97%/O ₂ 3%. As a result, an infrared reflection layer having a three-layer structure of a first metal oxide layer (TiO ₂ layer)/metal layer (Ag layer)/second metal suboxide layer (TiO _x layer) from the transparent substrate side. An attached PET film was produced. The x of the TiO _x layer was 1.5.

An infrared reflective film with a pressure-sensitive adhesive layer provided with a protective layer consisting of 4 layers was prepared in the same manner as in Example 1 except that the PET film with an infrared reflective layer was used, and was bonded to a glass substrate. The total thickness of the obtained infrared reflective layer [first metal oxide layer (TiO ₂ layer)+metal layer (Ag layer)+second metal suboxide layer (TiO _X layer)] was 16 nm, The ratio of the thickness of the second metal suboxide layer (TiO _X layer) to the total thickness was 12.5%.

(Example 21)
<Formation of Middle Refractive Index Layer (Lower Layer)>
First, acrylic copolymer H (isobornyl acrylate (Tg: 94° C.)/4-hydroxybutyl acrylate/crotonic acid=84 parts by mass/15 parts by mass/1 part by mass, solid content concentration 50% by mass, hydroxyl value 57 mgKOH/g, acid value 6 mgKOH/g) 33.32 parts by mass, and Tosoh's isocyanate cross-linking agent "Coronate HX" (trade name, solid content concentration 100% by mass) 3.34 parts by mass (NCO/ OH=1.0) and 963.34 parts by mass of methyl isobutyl ketone as a diluting solvent were mixed with a disper to prepare a medium refractive index coating material K. Next, the medium-refractive-index coating material K was applied onto the infrared reflective layer used in Example 1 by using the microgravure coater so that the thickness after drying was 60 nm, and dried at 120° C. for 2 minutes. By heat-curing it, a medium-refractive index layer (lower layer) having a thickness of 60 nm was formed. The refractive index of the manufactured intermediate refractive index layer (lower layer) was 1.51 as measured by the above method.

<Formation of Middle Refractive Index Layer (Upper Layer)>
Ionizing radiation curable acrylic polymer solution "SMP-250A" (trade name, solid content concentration 50% by mass) manufactured by Kyoeisha Chemical Co., Ltd. and 165.40 parts by mass, and phosphoric acid group-containing methacrylic acid derivative "light ester" manufactured by Kyoeisha Chemical Co., Ltd. P-2M" (brand name) 4.80 parts by mass and Fluorine-containing urethane (meth)acrylate monomer "Fomblin MT70" (brand name, solid content concentration 80 mass%) manufactured by Solvay Specialty Polymers Japan 8.30 parts by mass Part, 1.30 parts by mass of a silicone-modified acrylate "TEGO Rad 2650" manufactured by Evonik Degussa Japan, 4.80 parts by mass of a photopolymerization initiator "IRGACURE 819" (trade name) manufactured by BASF, and a diluent solvent. Was mixed with 815.40 parts by mass of methyl isobutyl ketone by a disper to prepare a medium refractive index coating material L. Next, the medium-refractive-index coating material L is applied onto the medium-refractive-index layer (lower layer) using the microgravure coater so that the thickness after drying is 920 nm, and after drying, the high-pressure mercury lamp is used. At 300 mJ/cm ² , ultraviolet rays having a light amount of 300 mJ/cm ² were irradiated to cure the layer, and thereby a middle refractive index layer (upper layer) having a thickness of 920 nm was formed. The refractive index of the manufactured medium refractive index layer (upper layer) was 1.49 when measured by the above-mentioned method.

As described above, an infrared reflective film having a protective layer composed of a medium refractive index layer (lower layer) and a medium refractive index layer (upper layer) was produced. A protective layer comprising two layers of a medium refractive index layer (lower layer) and a medium refractive index layer (upper layer) was provided in the same manner as in Example 1 except that the PET film with the infrared reflecting layer provided with the above protective layer was used. An infrared reflective film with a pressure-sensitive adhesive layer was prepared and attached to a glass substrate. The protective layer thus obtained had a thickness of 980 nm.

(Example 22)
A protective layer comprising two layers of a middle refractive index layer (lower layer) and a middle refractive index layer (upper layer) was provided in the same manner as in Example 21 except that the thickness of the middle refractive index layer (upper layer) was changed to 620 nm. An infrared reflective film with a pressure-sensitive adhesive layer was prepared and attached to a glass substrate. The thickness of the resulting protective layer was 680 nm.

(Example 23)
<Preparation of medium refractive index paint>
First, acrylic copolymer I (n-butyl methacrylate (Tg: 20° C.)/isobornyl methacrylate (Tg: 155° C.)/4-hydroxybutyl acrylate=40 parts by mass/50/10 parts by mass, solid content 35.28 parts by mass of a solution having a concentration of 50% by mass and a hydroxyl value of 38 mgKOH/g, and 2.39 parts by mass of an isocyanate-based crosslinking agent "Coronate HX" (trade name, solid content concentration 100% by mass) manufactured by Tosoh Corporation (NCO). /OH=1.0) and 962.33 parts by mass of methyl isobutyl ketone as a diluting solvent were mixed with a disper to prepare a medium refractive index coating material M.

An infrared reflective film with a pressure-sensitive adhesive layer provided with a protective layer consisting of four layers was prepared in the same manner as in Example 1 except that the medium refractive index coating material M was used, and was bonded to a glass substrate. The refractive index of the manufactured medium refractive index layer was 1.50 when measured by the above-mentioned method.

(Example 24)
<Preparation of medium refractive index paint>
First, acrylic copolymer J (isobornyl methacrylate (Tg: 155° C.)/isobutene/4-hydroxybutyl acrylate=75 parts by mass/15 parts by mass/10 parts by mass, solid content concentration 50% by mass, hydroxyl value 38 mgKOH 35.28 parts by mass of a solution of a solution of 1 g/g) and 2.39 parts by mass (NCO/OH=1.0) of an isocyanate cross-linking agent "Coronate HX" (trade name, solid content concentration 100% by mass) manufactured by Tosoh Corporation. Then, as a diluting solvent, methyl isobutyl ketone/toluene=866.10/96.23 parts by mass was blended with a disper to prepare a medium refractive index coating material N.

An infrared reflective film with a pressure-sensitive adhesive layer provided with a protective layer consisting of four layers was prepared in the same manner as in Example 1 except that the medium refractive index coating material N was used, and the infrared reflective film was attached to a glass substrate. The refractive index of the manufactured medium refractive index layer was 1.51 as measured by the above method.

(Comparative Example 1)
An infrared reflective film with a pressure-sensitive adhesive layer provided with a protective layer consisting of four layers was prepared in the same manner as in Example 13 except that the formation of the medium refractive index layer was changed to the following, and this was laminated on a glass substrate.

<Formation of medium refractive index layer>
96.47 parts by mass of hard coating agent "Z-773" (trade name, solid content concentration 34% by mass, refractive index 1.53 [nominal value]) manufactured by Aika Kogyo Co., Ltd., and butyl acetate 903.53 parts as a diluting solvent. Were mixed with a disper to prepare a medium refractive index coating material O. The medium refractive index coating material O was coated on the optical adjustment layer using the microgravure coater so that the thickness after drying was 60 nm, and after drying, it was dried at 300 mJ/cm ^{2 with} a high pressure mercury lamp. A medium-refractive-index layer having a thickness of 60 nm was formed by irradiating and curing with a light amount of ultraviolet rays. The refractive index of the manufactured medium refractive index layer was 1.52 as measured by the above method.

(Comparative example 2)
<Preparation of transparent substrate with infrared reflective layer>
First, using the above-mentioned PET film "A4100" (thickness: 50 μm) having one surface subjected to easy adhesion treatment as a transparent substrate, the first metal from the PET film side was applied to the non-easy adhesion treatment surface side of the PET film. The oxide layer, the metal layer, and the second metal oxide layer were formed as follows. First, a target having a metal composition of tin/zinc=90% by mass/10% by mass was used to form a first metal oxide layer (ZTO layer) having a thickness of 10 nm by the reactive sputtering method. As the sputtering gas in the reactive sputtering method, a mixed gas of Ar/O ₂ was used, and the gas flow volume ratio was Ar 97%/O ₂ 3%. Then, a 12 nm-thick metal layer (Ag layer) was formed on the metal oxide layer by a sputtering method using a silver target. Ar gas 100% was used as the sputtering gas in the sputtering method. Further, a second metal oxide layer (ZTO layer) having a thickness of 10 nm is formed on the metal layer by a reactive sputtering method using a target having a metal composition of tin/zinc=90% by mass/10% by mass. did. As the sputtering gas in the reactive sputtering method, a mixed gas of Ar/O ₂ was used, and the gas flow volume ratio was Ar 97%/O ₂ 3%. Thereby, a PET film with an infrared reflective layer having a three-layer structure of a first metal oxide layer (ZTO layer)/metal layer (Ag layer)/second metal oxide layer (ZTO layer) from the transparent substrate side. Was produced.

The total thickness of the infrared reflective layer [first metal oxide layer (ZTO layer)+metal layer (Ag layer)+second metal oxide layer (ZTO layer)] obtained by the above method is 32 nm, The ratio of the thickness of the second metal oxide layer (ZTO layer) to the total thickness was 31.3%.

<Formation of low refractive index layer>
The low-refractive-index coating material A used in Example 1 was applied onto the infrared reflective layer using the microgravure coater (manufactured by Rensai Seiki Co., Ltd.) so that the thickness after drying was 60 nm, and dried. After that, a low-refractive index layer having a thickness of 60 nm was formed by irradiating with a high-pressure mercury lamp an ultraviolet ray of a light amount of 300 mJ/cm ² to cure the layer. The refractive index of the manufactured low refractive index layer was 1.37 when measured by the above-mentioned method.

As described above, an infrared reflective film having a protective layer composed of one low refractive index layer was prepared. An infrared reflective film with a pressure-sensitive adhesive layer having a protective layer consisting of one low refractive index layer was prepared in the same manner as in Example 1 except that the PET film with an infrared reflective layer having the above protective layer was used to prepare a glass. It was attached to the substrate.

(Comparative example 3)
<Formation of medium refractive index layer>
The medium-refractive-index coating material L used in Example 21 was applied onto the infrared reflective layer used in Comparative Example 2 by using the microgravure coater (manufactured by Rensai Seiki Co., Ltd.) so that the thickness after drying was 680 nm. After working and drying, a medium-refractive index layer having a thickness of 680 nm was formed by irradiating a high-pressure mercury lamp with ultraviolet rays having a light amount of 300 mJ/cm ² to cure the layer. The refractive index of the manufactured medium refractive index layer was 1.49 as measured by the above-mentioned method.

As described above, an infrared reflective film having a protective layer composed of one medium refractive index layer was prepared. An infrared reflective film with a pressure-sensitive adhesive layer having a protective layer consisting of one medium refractive index layer was prepared in the same manner as in Example 1 except that the PET film with an infrared reflective layer having the protective layer was used to prepare a glass. It was attached to the substrate.

(Comparative Example 4)
Instead of the low refractive index layer, which is the outermost surface layer of the protective layer of Comparative Example 1, the medium refractive index layer of Example 1 was the outermost surface layer of the protective layer (thickness after drying). Except for coating and forming (drying at 120° C. for 2 minutes and thermosetting), an infrared reflection film with a pressure-sensitive adhesive layer provided with a protective layer consisting of four layers was prepared in the same manner as in Comparative Example 1. And attached to a glass substrate.

(Comparative example 5)
<Preparation of medium refractive index paint>
First, acrylic copolymer K (methyl methacrylate (Tg: 105° C.)/ethyl methacrylate (Tg: 65° C.)/4-hydroxybutyl acrylate=70 parts by mass/25 parts by mass/5 parts by mass, solid content 37.49 parts by weight of a solution having a concentration of 50% by mass and a hydroxyl value of 19 mgKOH/g) and 1.26 parts by mass of an isocyanate-based cross-linking agent "Coronate HX" (trade name, solid content concentration 100% by mass) manufactured by Tosoh Corporation (NCO). /OH=1.0) and 961.25 parts by mass of methyl isobutyl ketone as a diluting solvent were mixed with a disper to prepare a medium refractive index coating material P.

An infrared reflective film with a pressure-sensitive adhesive layer provided with a protective layer consisting of four layers was prepared and bonded to a glass substrate in the same manner as in Example 13 except that the above medium refractive index coating material P was used. The refractive index of the manufactured medium refractive index layer was 1.49 as measured by the above-mentioned method.

<Evaluation of transparent heat insulating and heat insulating member>
Regarding Examples 1 to 24 and Comparative Examples 1 to 5 described above, the visible light transmittance, visible light reflectance, and visible light reflectance of the infrared reflective film (transparent heat insulating and heat insulating member) attached to the glass substrate The maximum variation difference, the solar radiation absorption rate, the shielding coefficient, and the heat transmission coefficient were measured as follows, and the infrared reflection film was evaluated for salt water resistance, scratch resistance, and appearance.

[Visible Light Transmittance]
The visible light transmittance was measured using a UV-visible near-infrared spectrophotometer "Ubest V-570 Model" (trade name) manufactured by JASCO Corporation in the wavelength range of 380 to 780 nm with the glass substrate side as the incident light side. The spectral transmittance was measured and calculated according to JIS A5759-2008.

[Visible light reflectance]
As for the visible light reflectance, the spectral reflectance was measured using the UV-visible near-infrared spectrophotometer "Ubest V-570 type" in the wavelength range of 380 to 780 nm with the glass substrate side as the incident light side. Calculated according to R3106-1998.

[Maximum difference in reflectance]
Spectral reflectance was measured according to JIS R3106-1998 using the UV-visible near-infrared spectrophotometer "Ubest V-570 type" in the range of 300 to 800 nm with the glass substrate side as the incident light side. The “maximum variation difference ΔA” and “maximum variation difference ΔB” of the reflectance were obtained from the measured visible light reflection spectrum by the method described above.

[Solar absorption rate]
The solar absorptance is measured by using the UV-visible near-infrared spectrophotometer "Ubest V-570 type" in the wavelength range of 300 to 2500 nm with the glass substrate side as the incident light side. Then, it was calculated from the values of the solar radiation transmittance and the solar reflectance calculated according to JIS A5759-2008.

[Shielding factor]
The shielding coefficient was measured by measuring the spectral transmittance and the spectral reflectance using the UV-visible near-infrared spectrophotometer "Ubest V-570 type" in the wavelength range of 300 to 2500 nm with the glass substrate side as the incident light side. The solar radiation transmittance and the solar reflectance were obtained according to JIS A5759, the vertical emissivity was obtained according to JIS R3106-2008, and the values were obtained from the values of the solar radiation transmittance, solar reflectance and vertical emissivity.

[Heat transmission coefficient]
For the heat transmission coefficient, an attachment for specular reflection measurement was attached to an infrared spectrophotometer "IR Prestige21" (trade name) manufactured by Shimadzu Corporation, and the specular specular reflectance on the protective layer side and the glass substrate side of the infrared reflection film was measured at a wavelength of 5 Measured in the range of 0.5 to 25.2 μm, the vertical emissivity of the protective layer side and the glass substrate side of the infrared reflective film is determined according to JIS R3106-2008, and based on this, the thermal emissivity is determined according to JIS A5759-2008. The penetration rate was calculated.

[Salt water resistance]
First, the UV-visible near-infrared spectrophotometer "Ubest V-570 type" was used to measure the spectral transmittance of the infrared reflective film attached to the glass substrate in the wavelength range of 300 to 1500 nm, and the light of wavelength 1100 nm was measured. The transmittance T _B (unit: %) of each was measured. Then, the infrared reflection film attached to the glass substrate was immersed in a 5% by mass sodium chloride aqueous solution, and in this state, it was placed in a constant temperature and humidity bath at 50° C. and stored for 30 days to perform a salt water resistance test. After the salt water resistance test was completed, the infrared reflection film attached to the glass substrate was washed with pure water and naturally dried. Subsequently, the transmittance T _A (% unit) of light having a wavelength of 1100 nm of the infrared reflective film attached to the glass substrate after the salt water resistance test was measured in the same manner as above. From the above measurement results, a point value of T _A -T _B was calculated as a difference in transmittance of light having a wavelength of 1100 nm before and after the salt water resistance test.

[Scratch resistance]
The scratch resistance of the protective layer of the transparent heat-insulating and heat-insulating member is determined by arranging a white flannel cloth on the protective layer and applying a load of 1000 g/cm ² and reciprocating the white flannel cloth 1000 times. In the above, the state of the surface of the protective layer was visually observed and evaluated according to the following three grades.
Excellent: No scratches were found. Good: Several scratches (5 or less) were confirmed. Poor: Many scratches (6 or more) were confirmed.

[Appearance]
The appearance of the transparent heat insulating and heat insulating member (change in reflection color depending on the iris pattern and viewing angle) is visually observed under a three-wavelength fluorescent lamp on the surface of the protective layer side of the transparent heat insulating and heat insulating member, and the following three stages are available. It was evaluated by.
Excellent: When almost no change in reflected color due to iris pattern and viewing angle was observed. Good: When slight change in reflected color due to iris pattern and/or viewing angle was observed. Poor: Reflection due to iris pattern and/or viewing angle. When a color change is clearly observed

The above results are shown in Tables 1 to 8 together with the layer structure of the infrared reflecting film (transparent heat insulating/insulating member).

As shown in Tables 1 to 6, the infrared reflective films (transparent heat insulating/insulating members) of all the other examples except Examples 9 and 11 were good even in the salt water resistance test assuming a harsh external environment. The results show that even if dew condensation water, human sebum, sweat, etc. adhere to the film surface, the metal layer of the infrared reflective layer is not corroded and deteriorated in a short period of time. Further, since the visible light transmittance is large and the variation in the visible light reflectance is small, the transparency and the appearance are not impaired even when it is attached to a window glass. Moreover, the shielding coefficient and the heat transmission coefficient are small, and both the heat shielding performance in summer and the heat insulating performance in winter are excellent. In addition, the scratch resistance is at a practically acceptable level. Further, since the solar radiation absorption rate is small, it is difficult for the glass to undergo thermal cracking after installation on the window glass. That is, it can be seen that a practically well-balanced transparent heat shield and heat insulating member was obtained.

In each of Examples 9 and 11, the optical adjustment layer containing a large amount of inorganic fine particles and the high refractive index layer were layers containing a (meth)acrylic copolymer having a hydroxyl group and a crosslinking agent that reacts with the hydroxyl group. Therefore, a salt water resistance test is performed in comparison with other examples in which the medium refractive index layer containing no inorganic fine particles is a layer containing a (meth)acrylic copolymer having a hydroxyl group and a crosslinking agent that reacts with the hydroxyl group. It was a little inferior.

In Example 13, since the layer directly contacting the metal suboxide layer did not contain the corrosion inhibitor for the metal, the layer directly contacting the metal suboxide layer contained the corrosion inhibitor for the metal. Compared to Example 1 and Example 12, the salt water resistance test was slightly inferior.

Although Example 16 showed good results in the salt water resistance test, the total thickness of the protective layer was 1010 nm, which was rather large, and thus the heat transmission coefficient was 4.3 W/(m ² ·K), which was rather large, and the protection was achieved. The thermal insulation performance was slightly inferior compared to the other examples in which the total layer thickness was 980 nm or less.

Although Example 19 showed good results in the salt water resistance test, the thickness of the second metal oxide layer (TiO ₂ layer) of the infrared reflective layer was 7 nm, and the total thickness of the infrared reflective layer was Since it corresponds to 31.8% which exceeds 25%, the solar radiation absorption rate is as large as 21.3%, and when compared with other examples in which the solar radiation absorption rate is 20% or less, when applied to window glass. The risk of heat cracking of glass has become high.

Examples 21 and 22 showed good results in the salt water resistance test, but since the protective layer had a two-layer structure of a medium refractive index layer, another example in which the protective layer had a laminated structure with different refractive index ranges was used. Compared with the examples, the visible light transmittance and the appearance were inferior.

On the other hand, as shown in Tables 7 and 8, in Comparative Examples 1 and 5, among the protective layers composed of a plurality of layers, any of the layers other than the layer located on the outermost surface side has a hydroxyl group. A copolymer and a (meth)acrylic acid alkyl ester monomer having a carbon number of the alkyl group capable of forming a homopolymer having a glass transition temperature of 20° C. or more and 155° C. or less and 4 or more and 10 or less as a copolymer unit ( Since the (meth)acrylic copolymer and the polyisocyanate crosslinking agent that reacts with the hydroxyl group are not contained, the infrared reflective layer causes corrosion deterioration in the salt water resistance test, and the protective layer peels off. the value of _a -T _B also, each 50.0 points, was as large as 40.2 points. That is, it has almost no heat insulation function.

In Comparative Examples 2 and 3, the protective layers each consist of one layer of a low refractive index layer and a medium refractive index layer, and a monomer having a hydroxyl group and a glass transition temperature of 20° C. or higher are provided in the layer. A (meth)acrylic copolymer containing, as a copolymer unit, a (meth)acrylic acid alkyl ester monomer having an alkyl group having a carbon number of 4 or more and 10 or less capable of forming a homopolymer at 155° C. or less; Since it does not contain a polyisocyanate cross-linking agent that reacts with hydroxyl groups, in the salt water resistance test, the infrared reflective layer causes corrosion deterioration and the protective layer peels off, and the values of T _A -T _B are It increased to 35.0 points and 29.5 points. That is, it has almost no heat insulation function. The total thickness of the infrared reflective layer is 32 nm, and the thickness of the second metal oxide layer (ZTO layer) of the infrared reflective layer is 10 nm, which exceeds 25% of the total thickness of the infrared reflective layer. Since it corresponds to 3%, the solar radiation absorptances are large at 20.9% and 21.5%, respectively, and the risk of thermal cracking of the glass when applied to window glass is high. Furthermore, Comparative Example 2 was inferior in scratch resistance because the thickness of the protective layer was as thin as 60 nm. Furthermore, in Comparative Example 3, the protective layer was one layer of the medium refractive index layer, and the thickness was 680 nm, which overlaps with the wavelength region of visible light, and therefore the appearance was poor.

Further, in Comparative Example 4, it is possible to form a monomer having a hydroxyl group and a homopolymer having a glass transition temperature of 20° C. or higher and 155° C. or lower in a layer located on the outermost surface side of the protective layer including a plurality of layers. A (meth)acrylic copolymer containing, as a copolymer unit, a (meth)acrylic acid alkyl ester monomer having an alkyl group having 4 to 10 carbon atoms, and a polyisocyanate crosslinking agent that reacts with the hydroxyl group. Since a medium refractive index layer containing a is applied, it showed good results in a salt water resistance test, but since the middle refractive index layer located on the outermost surface side does not contain an ionizing radiation curable resin, scratch resistance Was inferior to

The present invention can provide a transparent heat insulating and heat insulating member excellent in corrosion resistance deterioration in salt water resistance test assuming a severe external environment while maintaining high heat insulating performance and heat insulating performance. In addition, it is possible to provide a transparent heat insulating and heat insulating member having a low solar radiation absorption rate and a reduced risk of thermal cracking of glass when applied to a window glass or the like and having excellent appearance.

10 Transparent Thermal Insulation Member 11 Transparent Substrate 12 First Metal Suboxide Layer or Metal Oxide Layer 13 Metal Layer 14 Second Metal Suboxide Layer or Metal Oxide Layer 15 Optical Adjustment Layer 16 Medium Refractive Index Layer 17 High Refractive Index Layer 18 Low Refractive Index Layer 19 Adhesive Layer 21 Infrared Reflective Layer 22 Coating Protective Layer 23 Functional Layer

Claims

A transparent heat insulating and heat insulating member comprising a transparent substrate and a functional layer formed on the transparent substrate,
The functional layer includes an infrared reflective layer and a coating type protective layer in this order from the transparent substrate side,
The infrared reflective layer, from the transparent substrate side, at least a metal layer, and, and includes a metal suboxide layer or a metal oxide layer in this order,
The coating type protective layer comprises a plurality of layers,
At least one layer of the coating type protective layers other than the layer located on the outermost surface side reacts with a (meth)acrylic copolymer having a hydroxyl group as a pre-curing resin component, and the hydroxyl group. Consisting of a layer containing a polyisocyanate crosslinking agent,
The (meth)acrylic copolymer is a monomer having a hydroxyl group and an alkyl group capable of forming a homopolymer having a glass transition temperature of 20° C. or higher and 155° C. or lower (C) having 4 to 10 carbon atoms (meth). Containing an acrylic acid alkyl ester monomer as a copolymer unit,
The transparent heat-shielding and heat-insulating member, wherein the outermost surface side layer of the coating type protective layer comprises a layer containing an active energy ray-curable resin as a pre-curing resin component.
The transparent heat insulating and heat insulating member according to claim 1, wherein the (meth)acrylic copolymer has a hydroxyl value of 30 mgKOH/g or more and 200 mgKOH/g or less.
The coating type protective layer includes, from the infrared reflective layer side, a medium refractive index layer, a high refractive index layer and a low refractive index layer in this order, and the medium refractive index layer has the hydroxyl group as a pre-curing resin component. The transparent heat insulating/insulating member according to claim 1 or 2, which comprises the (meth)acrylic copolymer having the above and a polyisocyanate crosslinking agent which reacts with the hydroxyl group.
The coating type protective layer includes an optical adjustment layer, a medium refractive index layer, a high refractive index layer and a low refractive index layer in this order from the infrared reflecting layer side, and the middle refractive index layer serves as a pre-curing resin component. The transparent heat insulating and heat insulating member according to claim 1 or 2, comprising a (meth)acrylic copolymer having a hydroxyl group, and a polyisocyanate crosslinking agent that reacts with the hydroxyl group.
The transparent shielding film according to any one of claims 1 to 4, wherein the (meth)acrylic acid alkyl ester monomer is at least one selected from the group consisting of t-butyl methacrylate and t-butyl acrylate. Thermal insulation member.
The transparent thermal insulation member according to any one of claims 1 to 5, wherein the total thickness of the coating type protective layer is 200 nm or more and 980 nm or less.
7. The transparent shield according to claim 1, wherein at least a layer of the coating type protective layer which is in direct contact with the metal suboxide layer or the metal oxide layer contains a corrosion inhibitor for metal. Thermal insulation member.
The transparent heat insulating and heat insulating member according to claim 7, wherein the corrosion inhibitor for the metal contains at least one compound selected from a compound having a nitrogen-containing group and a compound having a sulfur-containing group.
The infrared reflection layer includes, from the transparent substrate side, a first metal suboxide layer or metal oxide layer, a metal layer, a second metal suboxide layer or metal oxide layer in this order, and the infrared ray The total thickness of the reflective layer is 7 nm or more and 25 nm or less, and the thickness of the second metal suboxide layer or the metal oxide layer is 25% or less of the total thickness of the infrared reflective layer. 9. The transparent heat insulating/insulating member according to any one of 1 to 8.
The transparent heat insulating/insulating member according to claim 9, wherein the metal suboxide or the metal oxide contained in the second metal suboxide layer or the metal oxide layer of the infrared reflecting layer contains a titanium component.
The transparent heat insulating and heat insulating member according to any one of claims 1 to 10, wherein the metal layer of the infrared reflecting layer contains silver, and the thickness of the metal layer is 5 nm or more and 20 nm or less.
The transparent heat insulating/insulating member has a visible light transmittance of 60% or more, a shielding coefficient of 0.69 or less, a heat transmission coefficient of 4.0 W/(m 2 ·K) or less, and a solar radiation absorptivity of 20. % Or less, and the transparent heat-insulating and heat-insulating member according to any one of claims 1 to 11.
When the salt water resistance test in which the transparent heat insulation heat insulating member is immersed in an aqueous sodium chloride solution having a temperature of 50° C. and a concentration of 5 mass% for 30 days is performed, the wavelength of the transparent heat insulation heat insulating member measured before the salt water resistance test is 300. The transmittance of light having a wavelength of 1100 nm in the transmission spectrum in the range of up to 1500 nm is T B %, and the transmission of light having a wavelength of 1100 nm in the transmission spectrum in the range of wavelength of 300 to 1500 nm of the transparent heat insulating/insulating member measured after the salt water resistance test. The transparent heat insulating and heat insulating member according to any one of claims 1 to 12, wherein the value of T A -T B is less than 10 points, where T A % is the ratio.
In the reflection spectrum measured according to JIS R3106-1998,
The point corresponding to the wavelength 535 nm on the virtual line a indicating the average value of the maximum reflectance and the minimum reflectance in the wavelength range of 500 to 570 nm of the reflection spectrum is set as point A, and the point in the wavelength range of 620 to 780 nm of the reflection spectrum is set. A point corresponding to a wavelength of 700 nm on an imaginary line b indicating the average value of the maximum reflectance and the minimum reflectance is defined as a point B, and a straight line passing through the points A and B is extended in the wavelength range of 500 to 780 nm. As a reference straight line AB,
When the reflectance value of the reflectance spectrum in the wavelength range of 500 to 570 nm and the reflectance value of the reference line AB are compared, the reflectance value at the wavelength at which the difference between the reflectance values is maximum. When the absolute value of the difference is defined as the maximum variation difference ΔA, the value of the maximum variation difference ΔA is 7% or less in% of reflectance,
When the reflectance value of the reflectance spectrum in the wavelength range of 620 to 780 nm and the reflectance value of the reference line AB are compared, the reflectance value at the wavelength at which the difference between the reflectance values becomes maximum. The transparent heat shield according to any one of claims 1 to 13, wherein when the absolute value of the difference is defined as the maximum fluctuation difference ΔB, the value of the maximum fluctuation difference ΔB is 9% or less in% of reflectance. Insulation member.
A method for manufacturing a transparent heat insulating/insulating member according to any one of claims 1 to 14,
A step of forming an infrared reflective layer on a transparent substrate by a dry coating method,
Forming a protective layer composed of a plurality of layers on the infrared reflective layer by a wet coating method.