JP7057714B2 - Transparent heat shield and heat insulating member and its manufacturing method - Google Patents

Description

The present invention mainly relates to a transparent heat-shielding and heat-insulating member such as a film for adjusting solar radiation for energy saving throughout the year, which is used by being attached to the indoor side of a window glass or the like. In particular, the present invention relates to a transparent heat-shielding heat-insulating member such as a year-round energy-saving solar radiation adjusting film that has excellent heat-insulating properties and suppresses corrosion deterioration caused by condensation water and human sebum adhesion, and a method for manufacturing the same.

From the viewpoint of preventing global warming and saving energy, it is possible to attach a heat shield film to the windows of buildings, show windows, automobile windows, etc. to block the heat rays (infrared rays) of sunlight and reduce the internal temperature. It is widely done. In recent years, from the viewpoint of further energy saving, not only the heat shield that cuts the heat rays that cause the temperature rise in the summer, but also the heat insulation function that suppresses the outflow of heating heat from the room in the winter and reduces the heating load. A year-round energy-saving heat-shielding and heat-insulating member has been developed and is gradually gaining recognition as it is put on the market.

In view of the active commercialization of films with excellent heat insulating properties due to the diversification of solar radiation adjustment films introduced on the market, the Japanese Industrial Standards (JIS) A5759 for architectural window glass films has been adopted. In 2016, the standard was revised, and in order to clarify the definition of heat insulating property, a new application / performance category was added as "low radiation film".

In JIS A5759-2016, low emissivity films are classified into the following four types A to D according to the combination of visible light transmittance and thermal transmission rate, which is an index of heat insulating performance.
Category A: Visible light transmittance less than 60%, thermal transmissivity 4.2 W / (m ² · K) or less Category B: Visible light transmittance less than 60%, thermal transmissivity more than 4.2 W / (m) ² · K) or less Category C: Visible light transmittance 60% or more, thermal transmissivity 4.2 W / (m ² · K) or less Category D: Visible light transmittance 60% or more, thermal transmissivity over 4.2 4 .8W / (m ²・ K) or less

Among the low emissivity films classified into the above four types, the low emissivity films corresponding to the categories A and C having a thermal transmissivity of 4.2 W / (m ² · K) or less are particularly excellent in heat insulating properties. In the future, low emissivity films that fall into these categories are expected to gradually penetrate the market.

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

Generally, the low emissivity film is composed of an infrared reflective 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 base material. Can be mentioned. The metal oxide layer, the metal layer, and the laminated portion of the metal oxide layer are relatively highly transparent infrared reflective layers, and the metal oxide layer is visible due to the interference effect at the interface with the metal layer that reflects infrared light. By adjusting the light reflectance, the balance between the visible light transmittance and the infrared reflectance of the entire infrared reflective layer is controlled, and at the same time, it also has a role of suppressing corrosion deterioration of the metal layer. However, the infrared reflective layer has insufficient scratch resistance as it is, and in an environment where external environmental factors such as oxygen, moisture, and chloride ions act synergistically strongly when protected by the metal oxide layer alone. Since the metal layer is prone to corrosion deterioration, a transparent protective layer is further provided on the infrared reflective layer for the purpose of improving the scratch resistance and suppressing the influence of the above-mentioned external factors.

However, in order to further improve the heat insulating property by setting the thermal transmissivity of the low emissivity film to 4.2 W / (m ² · K) or less as described above, and further to 4.0 W / (m ² · K) or less. It is necessary to reflect far infrared rays more efficiently (to make the vertical emissivity smaller) to the indoor side, and the thickness of the transparent protective layer needs to be as thin as possible. 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 (in the molecular skeleton, C = O group, CO group, fragrance). (Materials containing a lot of group groups) must be used, and the thicker the protective layer, the greater the absorption of far infrared rays, and as a result, the solar radiation adjustment film itself absorbs far infrared rays. This is because the adjusting film cannot efficiently reflect far infrared rays to the indoor side.

The thickness of the transparent protective layer cannot be unequivocally determined because it depends on the constituent materials of the transparent protective layer, but to explain by giving a specific example, the thermal transmissivity is 3.7 W / ( When a material having m ² · K) is used, for example, in order to reduce the thermal transmissivity as a low emissivity film to 4.2 / (m ² · K) or less, the thickness of the transparent protective layer is approximately. It should be 1.0 μm or less. Similarly, in order for the thermal transmissivity as a low emissivity film to be 4.0 W / (m ² · K) or less, the thickness of the transparent protective layer needs to be about 0.7 μm or less, and further low. In order to make the thermal transmissivity as a radial film 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 prior art, for the purpose of providing an infrared reflective film having excellent heat insulating properties and practical durability, Patent Document 1 mainly contains a first metal oxide layer and silver on a transparent film base material. It is provided with a secondary metal oxide layer composed of a metal layer as a component and a composite metal oxide layer containing zinc oxide and tin oxide, and the secondary 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 with the transparent protective layer.

Further, Patent Document 2 aims to provide an infrared reflective film having excellent heat shielding properties and capable of effectively preventing the face of a resident or the like from being reflected on a window provided with an infrared reflective film. An infrared reflective film in which a first metal oxide layer, an infrared reflective layer, a second metal oxide layer, and a transparent protective layer are laminated in this order on a transparent film substrate, which is the second metal oxidation. The thickness of the material layer is 30 nm or less, the thickness of the first metal oxide layer is thinner than the thickness of the second metal oxide layer, the thickness of the first metal oxide layer and the thickness of the second metal oxide. An infrared reflective film characterized in that the difference from the thickness of the material layer is 2 nm or more is disclosed.

Similarly, Patent Document 3 describes a transparent base material for the purpose of providing a transparent heat-shielding heat-insulating member having excellent heat-insulating properties and appearance (suppression of iris phenomenon and reflection color change due to viewing angle). 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 are provided on top of the protective layer in this order. The protective layer has a total thickness of 200 to 980 nm and is the infrared reflective layer. A transparent heat-shielding and heat-insulating member is disclosed, which comprises at least a high-refractive-index layer and a low-refractive-index layer in this order from the side.

Japanese Unexamined Patent Publication No. 2014-167617 Japanese Unexamined Patent Publication No. 2017-68118 Japanese Unexamined Patent Publication No. 2017-053967

As described in the exemplified prior art literature, it is possible to further reduce the heat transmission coefficient as a low emissivity film by making the thickness of the transparent protective layer thinner, but on the other hand, as described above. As described above, reducing the thickness of the transparent protective layer generally reduces the function of protecting the infrared reflective layer from external environmental factors such as oxygen, moisture, and chloride ions, that is, oxygen. Since the diffusion of water, chloride ions and the like in the depth direction of the protective layer and the permeation time are 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-shielding and heat-insulating function of the low-emissivity film and deterioration of appearance such as discoloration. In addition, reducing the thickness of the transparent protective layer also reduces physical properties such as scratch resistance, so that the film surface (transparent protective layer) is used when the film is applied or when the film is used for a long period of time. ) Is easily scratched, and there are concerns about poor appearance and corrosion deterioration of the metal layer due to the effects of the scratches.

In response to the problem of corrosion deterioration of the metal layer, Patent Document 1 provides chemical stability (durability against acids, alkalis, chloride ions, etc.) as a metal oxide layer provided on the transparent protective layer side of the infrared reflective layer. The solution is attempted by using a composite metal oxide (ZTO) containing excellent zinc oxide and tin oxide.

However, although 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, it is a transparent protective layer. Since the thickness is extremely thin, 30 nm to 150 nm, there is room for improvement in terms of scratch resistance, and when a person's hand or finger touches the surface of the infrared reflective film, chlorides contained in human skin oil adhere to it. When used for a long period of time in a harsh environment where dew 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 in that it can be promoted to reduce thermal insulation and poor appearance. Further, since the thickness of both the first metal oxide layer and the ZTO layer used as the second metal oxide layer is as thick as about 30 nm, the visible light transmittance is relatively high and the visible light reflectance is relatively low. , It is estimated that the solar 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, and there is a concern that the window glass may cause thermal cracking.

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

However, the infrared reflective film disclosed in Patent Document 2 also 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, but is a transparent protective layer. Since the thickness is extremely thin, 50 nm to 70 nm (range of examples), there is room for improvement in terms of scratch resistance, and chloride contained in human skin oil when the surface of the infrared reflective film is touched by human hands or fingers. When used for a long period of time in a harsh environment where dew condensation is extremely likely to occur with objects attached, corrosion deterioration of the metal layer may be promoted, resulting in deterioration of the heat-shielding and heat-insulating function and poor appearance. There are still concerns. The thickness of the first metal oxide layer (ZTO layer) is still thick at 4 to 15 nm, the thickness of the second metal oxide layer (ZTO layer) is still thick at 10 to 25 nm, and the solar radiation absorption rate is 22 to 35%. When the infrared reflective film is attached to the window glass, the temperature near the center of the window glass becomes high depending on the type of window glass, the orientation of the window glass, the condition of the shadow of the window glass, etc. There is also concern that it may cause thermal cracking.

Further, Patent Document 3 discloses a metal in a corrosion resistance test in which a metal suboxide layer in which a metal is partially oxidized is provided on the metal layer and 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 corrosion deterioration of the layer. The transparent heat-shielding and heat-insulating member disclosed in Patent Document 3 has a relatively thin visible light reflectance because the thickness of the TiO _X layer used as the metal suboxide layer is set as thin as 2 to 6 nm. 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 heat cracking of the window glass when the transparent heat shield and heat insulating member is attached to the window glass is reduced. Further, since the thickness of the TiO _X layer is thin, improvements are made in terms of cost and manufacturing efficiency at the time of sputtering film formation.

However, in the transparent heat-shielding and heat-insulating member disclosed in Patent Document 3, the thickness of the TiO _X layer used as the metal hydroxide layer is as thin as 2 to 6 nm, and the protective layer formed on the layer is as thin as 2 to 6 nm. Since the thickness is relatively thin, 210 to 930 nm, there is no problem in the corrosion resistance test in which it is left in an environment with a temperature of 50 ° C. and a relative humidity of 90% for 168 hours. If it is used for a long period of time in a harsh environment where dew condensation is extremely likely to occur with chlorides contained in human skin oil adhering to it when it is touched by a finger or a finger, the corrosion deterioration of the metal layer is promoted and the metal layer is shielded. There is concern that the thermal insulation function will deteriorate and the appearance will be poor.

As described above, in the low emissivity film in which the thermal transmissivity is 4.2 W / (m ² · K) or less, further 4.0 W / (m ² · K) or less, and the heat insulating property is further improved, oxygen is used. It has excellent corrosion resistance and deterioration resistance when used for a long period of time in an extremely harsh environment where external environmental factors such as moisture and chloride ions have a synergistic effect, and also has practical scratch resistance. Nothing has been obtained at present. Further, there is still room for improvement in reducing the risk of heat cracking of the glass when the film is attached to the window glass, that is, in reducing the solar radiation absorption rate.

It is said that the present invention cannot achieve the above-mentioned problem, that is, the contradictory requirements of improving the heat insulating performance of the transparent heat-shielding and heat-insulating member and suppressing the corrosion deterioration when used for a long period of time in a harsh environment. It solves the problem, and in particular, it has excellent heat insulation and is a transparent shield such as a year-round energy-saving solar radiation adjustment film that has practical scratch resistance and suppresses corrosion deterioration caused by condensation water and human skin oil adhesion. It provides a thermal insulation member. Further, the present invention provides a transparent heat-shielding and heat-insulating member that also reduces the solar absorption rate.

First, in order to solve the above-mentioned problems, the present inventors first, with respect to the heat-shielding and heat-insulating member disclosed in Patent Document 3, assuming a harsh usage environment, sodium chloride having a temperature of 50 ° C. and a concentration of 5% by mass. A salt water resistance test of immersing in an aqueous solution for 10 days was performed, and the transmission spectrum in the wavelength range of 300 to 1500 nm was measured before and after immersion. As a result, the transmission spectrum changed after immersion, and the near-infrared reflection function tended to deteriorate. It turned out that there was. In this case, the far-infrared reflection function having a wavelength of 5.5 to 25.2 μm is also deteriorated. Further, when the heat-shielding and heat-insulating member was taken out during the test and the surface thereof was observed, it was found that the corrosion-deteriorated portion was mainly present as dots in the initial state of the corrosion deterioration. This heat-shielding and heat-insulating member has a structure in which a thin metal suboxide layer and a protective layer are formed on the metal layer, but nevertheless, the metal layer when used in a harsh environment. As a result of diligent examination based on the above situation, it was estimated that the cause was as follows.

In the heat-shielding and heat-insulating member, when a first metal suboxide layer, a metal layer, and a second metal suboxide layer are formed as an infrared reflective layer on a transparent substrate by sputtering in this order, the metal suboxide is formed. As the thickness of the layer, from the viewpoint of imparting corrosion resistance in an environment with a temperature of 50 ° C. and a relative humidity of 90%, and suppression of a decrease in the visible light transmittance of the infrared reflective layer due to the influence of light absorption of metal suboxide. From the viewpoint of the above and the processing speed of sputtering, that is, from the viewpoint of improving productivity, the thickness of the metal suboxide layer is extremely thin to several nm. It is presumed that this is the effect, but when SEM / EDX analysis of the surface of the infrared reflective layer is performed, microprojections on the transparent substrate (spike filler in the substrate, slipper filler in the easy-adhesion layer of the substrate, etc. On (foreign matter, etc.), (1) the metal layer is not completely covered by the second metal suboxide layer, and (2) the infrared reflective layer itself is partially torn and peeled off. It was found that there were very small parts (the end face of the torn layer had the metal layer exposed). In addition, although the exact reason is not clear, surprisingly, (3) it seems to be a very small aggregate or a very small uplift of the metal derived from the metal layer that seems to have penetrated the second metal suboxide layer. There are also (4) minute aggregates of metal presumed to be caused by arc generation during sputtering, and (5) shards of metal presumed to be caused by the fall of contaminants in the sputtering chamber. I noticed that I was there.

In any case, on the surface of the infrared reflective layer, the metal layer derived from the metal layer is exposed because the metal layer is not completely covered by the second metal suboxide layer as described in (1) to (5) above. It was found that there are tiny parts (including tiny aggregates of metal, tiny bumps and shards of metal) that are stubborn, and these are the harsh ones mentioned above. When used in the environment, it was considered to be the main cause of corrosion deterioration of the metal layer of the heat shield and heat insulating member. That is, although a protective layer containing organic substances and inorganic oxides is formed on the infrared reflective layer, the thickness of the protective layer is as thin as 210 to 930 nm, and diffusion of oxygen, water, and chloride ions. It is difficult to completely suppress the penetration, and when used in a harsh environment, oxygen, water and chloride ions gradually diffuse and permeate the fine gaps of the protective layer, and the above-mentioned "metal layer When the metal is not completely covered by the second metal suboxide layer and the metal derived from the metal layer is exposed, the metal is corroded starting from the minute part. It is presumed that deterioration begins, and in some cases, the onset of corrosion deterioration of the metal triggers the peeling of the protective layer, causing a phenomenon in which the corrosion deterioration gradually spreads and progresses to the entire metal layer.

As a result of diligent studies to solve the above problems, the present inventors have arranged the transparent base material and at least the metal layer and the metal suboxide layer or the metal oxide layer formed on the transparent base material in this order. A coating type protective layer composed of a plurality of layers is provided on the infrared reflective layer including the infrared reflective layer, and at least one of the coating type protective layers other than the layer located on the outermost surface side is provided. The layer is formed of a layer containing a fluorine-containing resin having a curable functional group and a cross-linking agent that reacts with the curable functional group as a pre-curing resin component, and is the outermost of the above-mentioned coating type protective layers. If the layer located on the surface side is formed of a layer containing an ionizing radiation curable resin as a pre-curing resin component, the layer containing the fluorine-containing resin after being cured by the cross-linking agent can be, for example, the surface of an infrared reflective layer. "The metal layer is not completely covered by the second metal suboxide layer, and the metal derived from the metal layer is exposed. In contrast, it can function as a layer that protects from external environmental factors such as oxygen, water, and chloride ions, that is, a barrier layer, and diffuses oxygen, water, chloride ions, etc. in the depth direction of the protective layer. The present invention has been found that the penetration is significantly suppressed, and as a result, the progress of corrosion deterioration of the metal layer is remarkably suppressed, and that the coating type protective layer composed of the above-mentioned multiple layers has practical scratch resistance. I came to make a metal.

Further, in addition to the configuration of the coating type protective layer, in the heat shield heat insulating member, the infrared reflective layer is provided from the transparent substrate side to the first metal suboxide layer or the metal oxide layer, or the metal. The layer, the second metal suboxide layer or the metal oxide layer are included in this order, the total thickness of the infrared reflective layer is 7 to 25 nm or less, and the second metal suboxide layer or the metal oxide is formed. We have found that if the thickness of the layer is 25% or less of the total thickness of the infrared reflective layer, the metal layer is excellent in corrosion resistance and deterioration, and the solar radiation absorption rate of the transparent heat-shielding and heat-insulating member can be reduced. It came to.

The transparent heat-shielding and heat-insulating member of the present invention is a transparent heat-shielding and heat-insulating member including a transparent base material and a functional layer formed on the transparent base material, and the functional layer is from the transparent base material side. The infrared reflective layer and the coating type protective layer are included in this order, and the infrared reflective layer contains at least a metal layer and a metal suboxide layer or a metal oxide layer in this order from the transparent base material side, and the coating is performed. 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 mold has a curable functional group as a pre-curing resin component. The layer composed of a fluorine-containing resin and a cross-linking agent that reacts with the curable functional group, and the layer located on the outermost surface side of the coating type protective layer is an ionizing radiation as a pre-curing resin component. It is characterized by being composed of a layer containing a curable resin.

In the above aspect, the content of the fluororesin having a curable functional group is a resin composition of a layer containing the fluororesin having the curable functional group and a cross-linking agent that reacts with the curable functional group. It is preferably 34% by mass or more and 94% by mass or less with respect to the total mass.

Further, the layer containing the fluorine-containing resin having the curable functional group and the cross-linking agent that reacts with the curable functional group is after the curing of the layer measured by elemental analysis by energy dispersive X-ray (EDX) analysis. The ratio (F / C) of the fluorine atom F (at%: atomic percent) to the carbon atom C (at%: atomic percent) in the resin composition of is preferably 0.08 or more and 0.30 or less.

Further, it is more preferable that the curable functional group of the fluororesin having the curable functional group is a hydroxyl group and the cross-linking agent is a polyisocyanate compound.

The fluororesin having a curable functional group is composed of a hydroxyl group-containing perfluoroolefin polymer mainly composed of a perfluoroolefin unit and a hydroxyl group-containing chlorotrifluoroethylene polymer mainly composed of a chlorotrifluoroethylene unit. It is preferably at least one copolymer polymer selected from the group.

Further, the coating type protective layer includes a medium refractive index layer, a high refractive index layer and a low refractive index layer in this order from the infrared reflective layer side, and the medium refractive index layer is described as a pre-curing resin component. It is preferable to contain a fluororesin having a curable functional group and a cross-linking agent that reacts with the curable functional group.

Further, 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 reflective layer side, and the medium refractive index layer is cured. It is more preferable that the preresin component contains a fluorine-containing resin having the curable functional group and a cross-linking agent that reacts with the curable functional group.

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

Further, among the coating type protective layers, at least the layer in contact with the metal suboxide layer or the metal oxide layer preferably contains a corrosion inhibitor for the metal.

Further, 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 includes a first metal suboxide layer or a metal oxide layer, a metal layer, a second metal suboxide layer or a metal oxide layer in this order from the transparent substrate side. 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. Is preferable.

Further, 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 reflecting layer contains a titanium component.

Further, it is more preferable that 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.

Further, the transparent heat-shielding and heat-insulating member has a visible light transmittance of 60% or more, a thermal shielding coefficient of 0.69 or less, a thermal transmission rate of 4.0 W / (m ² · K) or less, and solar radiation. The absorption rate is preferably 20% or less.

Further, when the transparent heat-shielding and heat-insulating member is immersed in a sodium chloride aqueous solution having a temperature of 50 ° C. and a concentration of 5% by mass for 30 days, the transparent heat-shielding and heat-insulating member measured before the salt-water resistance test is performed. The transmittance of light having a transmittance of 1100 nm in the transmission spectrum wavelength range of 300 to 1500 nm of the member is _TB %, and the transmittance of the transmission spectrum in the wavelength range of 300 to 1500 nm of the transparent heat shield and heat insulating member measured after the salt water resistance test is 1100 nm. It is preferable that the value of TA _{- TB} is less than 10 points, where the transmittance of the light is _TA %.

Further, in the reflection spectrum measured according to JIS R3106-1998, it corresponds to the wavelength 535 nm on the virtual line a showing 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 A is a point A, and the point corresponding to the wavelength 700 nm on the virtual line b showing 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 defined as the point A and the above. The straight line passing through the point B was extended in the range of the wavelength range of 500 to 780 nm to form the reference straight line AB, and the reflectance value of the reflection spectrum and the reflectance value of the reference straight line AB in the range of the wavelength range of 500 to 570 nm were compared. When the absolute value of the difference between the reflectance values at the wavelength at which the difference between the reflectance values is maximum is defined as the maximum variation difference ΔA, the value of the maximum variation difference ΔA is in% unit of the reflectance. When comparing the reflectance value of the reflectance spectrum and the reflectance value of the reference straight line AB in the wavelength range of 620 to 780 nm, the difference between the reflectance values becomes maximum. When the absolute value of the difference between the values of the reflectance at the wavelength is defined as the maximum fluctuation difference ΔB, it is preferable that the value of the maximum fluctuation difference ΔB is 9% or less in% units of the reflectance.

Further, in the method for manufacturing a transparent heat-shielding and heat-insulating member of the present invention, a step of forming an infrared reflective layer on a transparent base material by a dry coating method and a protective layer composed of a plurality of layers are formed on the infrared reflective layer. It is characterized by including a step of forming by a wet coating method.

According to the present invention, a transparent heat shield having high visible light transmittance, particularly excellent heat insulating properties, and practical scratch resistance that significantly suppresses corrosion deterioration caused by condensation water and human sebum adhesion. Insulation members can be provided. Further, it is possible to provide a transparent heat-shielding and heat-insulating member that also reduces the solar absorption rate. That is, the transparent heat-shielding 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, moisture, and chloride ions have a synergistic effect. Even so, the heat-shielding and heat-insulating function and good appearance can be maintained. Further, it is possible to reduce the risk of heat cracking of the glass when it is attached to the window glass.

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

(Transparent heat shield and heat insulating member)
First, an embodiment of the transparent heat-shielding and heat-insulating member of the present invention will be described. One embodiment of the transparent heat-shielding 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 includes an infrared reflective layer and an infrared reflective layer from the transparent base material side. The coating type protective layer is included in this order, and the infrared reflective layer includes at least a metal layer and a metal suboxide layer or a metal oxide layer in this order from the transparent base material side, and the coating type protective layer is included. Is composed of a plurality of layers, and among the above-mentioned coating type protective layers, at least one layer other than the layer located on the outermost surface side is a fluorine-containing resin having a curable functional group as a pre-curing resin component. The layer composed of a layer containing a cross-linking agent that reacts with the curable functional group and located on the outermost surface side of the above-mentioned coating type protective layer contains an ionizing radiation curable resin as a pre-curing resin component. Consists of layers containing.

With the above 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 cross-linking agent is used. The layer containing the fluorine-containing resin after being cured has oxygen, water, and chloride with respect to the above-mentioned "microscopic portion where the metal derived from the metal layer is exposed" existing on the surface of the infrared reflective layer. It can function as a layer that protects from external environmental factors such as substance ions, that is, a barrier layer, and the diffusion and penetration of the protective layer such as oxygen, moisture, and chloride ions in the depth direction are significantly suppressed. As a result, it is considered that the progress of corrosion deterioration of the metal layer is remarkably suppressed. Further, the layer containing the fluororesin after being cured by the cross-linking agent naturally functions as a barrier layer for the infrared reflective layer including the metal layer. As a result, the transparent heat-shielding and heat-insulating member of the present embodiment has a large visible light transmittance, can reduce the thermal transmission rate, and significantly suppresses corrosion deterioration caused by dew condensation water and human sebum adhesion. Can be done. Further, since the layer located on the outermost surface side of the coating type protective layer is cured by ionizing radiation irradiation, practical scratch resistance can be imparted.

Further, one embodiment of the transparent heat-shielding 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 from the transparent base material side. The infrared reflective layer and the coating type protective layer are included in this order, and the infrared reflective layer includes a first metal suboxide layer or a metal oxide layer, a metal layer, and a second metal suboxidation from the transparent substrate side. The physical layer or the metal oxide layer is included 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 the infrared ray. The total thickness of the reflective layer is 25% or less, and the coating type protective layer is composed of a plurality of layers, and at least one of the above coating type protective layers other than the layer located on the outermost surface side. The layer is composed of a layer containing a fluorine-containing resin having a curable functional group and a cross-linking agent that reacts with the curable functional group as a pre-curing resin component, and is the outermost surface of the above-mentioned coating type protective layer. The layer located on the side is composed of a layer containing an ionizing radiation curable resin as a pre-curing resin component.

With the above configuration, in order to reduce the solar radiation absorption rate, the second metal suboxide layer or the metal oxide layer is formed thinly, the heat transmission coefficient is lowered, and the heat insulating property is further improved. Therefore, even if the protective layer composed of the plurality of coating type layers of the infrared reflective layer is thinly formed, the layer containing the fluorine-containing resin after being cured by the cross-linking agent is the surface of the infrared reflective layer described above. "Extremely minute parts where the metal layer is not completely covered by the second metal suboxide layer and the metal derived from the metal layer is exposed" as in (1) to (5). And an infrared reflective layer can function as a layer that protects against external environmental factors such as oxygen, water, and chloride ions, that is, a barrier layer, and protects layers such as oxygen, water, and chloride ions in the depth direction. It is considered that diffusion and permeation into the metal 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-shielding and heat-insulating member of the present embodiment has a large visible light transmittance, can reduce the thermal transmission rate and the solar radiation absorption rate, and significantly deteriorates corrosion due to condensation water and human sebum adhesion. Can be suppressed.

Hereinafter, each component of the transparent heat-shielding and heat-insulating member of the present embodiment will be described.

<Transparent substrate>
The transparent base material constituting the transparent heat-shielding and heat-insulating member of the present embodiment is not particularly limited as long as it is made of a translucent material. Examples of the transparent substrate include polyester resins (eg, polyethylene terephthalate, polyethylene naphthalate, etc.), polycarbonate resins, polyacrylic acid ester resins (eg, polymethyl methacrylate, etc.), alicyclic polyolefin resins, and the like. 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 or a sheet can be used. Examples of the method for processing the resin into a film or sheet include an extrusion molding method, a calendar molding method, a compression molding method, an injection molding method, and a method in which the resin is dissolved in a solvent and cast. Additives such as antioxidants, flame retardants, heat stabilizers, ultraviolet absorbers, lubricants, and antistatic agents may be added to the resin. The thickness of the transparent substrate is, for example, 10 μm or more and 500 μm or less, and is preferably 25 μm or more and 125 μm or less in consideration of processability and cost.

<Infrared reflective layer>
The infrared reflective layer constituting the transparent heat-shielding and heat-insulating member of the present embodiment is particularly limited as long as it includes at least a metal layer and a metal suboxide layer or a metal oxide layer in this order from the transparent substrate side. However, from the transparent substrate side, a first metal suboxide layer or a metal oxide layer, a metal layer, a second metal suboxide layer or a metal oxide layer is provided in this order, and the above is provided. 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 set to 25% or less of the total thickness of the infrared reflective layer. It is preferable to have. The lower limit of the total thickness of the infrared reflective layer is preferably 7 nm or more in order to exert 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 is lowered, the shielding coefficient and the thermal transmission rate are increased, and the heat shielding performance and the heat insulating performance may be deteriorated.

The transparent heat-shielding heat-insulating member can have a heat-shielding function and a heat-insulating function by providing the infrared reflective layer. Further, in the transparent heat-shielding and heat-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. If the total thickness of the infrared reflective layer exceeds 25 nm, the visible light transmittance may be low and the transparency may be inferior.

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 reflecting layer, the thickness of the metal layer greatly contributes to the infrared reflecting function. The thickness can be made relatively thick 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 thermal transmission coefficient can be decreased.

Further, by making the metal layer thicker, the thickness of the first metal suboxide layer or the metal oxide layer and the thickness of the second metal suboxide layer or the metal oxide layer can be reduced to that of the infrared reflective 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 transmission rate, solar radiation reflectance, solar radiation absorption rate) of the infrared reflective layer formed on the transparent base material differ depending on the type of metal, metal suboxide, and 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 the metal oxide layer and the thickness of the second metal suboxide layer or the metal oxide layer of the present embodiment are the same. Compared with the infrared reflective layer thicker than the range, it has the following features.

That is, the infrared reflective layer of the present embodiment has the same thickness of the metal layer, and the thickness of the first metal suboxide layer or the metal oxide layer and the thickness of the second metal suboxide layer or the metal oxide layer. (A) The solar transmittance tends to be low in the wavelength range of 380 to 780 nm and high in the wavelength range of 790 to 2500 nm as compared with the infrared reflectance layer having a thickness thicker than the range of the present embodiment. Yes, (B) the solar reflectance tends to be high in the wavelength range of 380 to 780 nm, and tends to be low in the wavelength range of 790 to 2500 nm, and (C) the solar transmittance and the solar reflectance are further determined. The added value tends to be high. In other words, the solar absorption rate, which is the value obtained by subtracting the solar transmittance and the solar reflectance from 100%, tends to be low. By further providing a protective layer described later on the infrared reflective layer having such solar radiation characteristics, the balance between the solar radiation transmittance and the solar reflectance is controlled at a high level, and the heat shield having a relatively low solar radiation absorption rate. It can be a heat insulating member. As a result, when the infrared reflective film is attached to the window glass, the temperature rise near the center of the window glass can be suppressed as compared with the conventional infrared reflective film having heat insulating properties, and the window glass causes thermal cracking. 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 as thin as 25% or less of the total thickness of the infrared reflective layer, the heat insulating 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, the above-mentioned "metal layer" such as (1) to (5) is used. There may be "microscopic sites" that are not completely covered by the second metal suboxide layer or the metal oxide layer and the metal derived from the metal layer is exposed. The original protective function of the second metal suboxide layer or the metal oxide layer against the metal layer is deteriorated, and the metal layer is liable to be corroded and deteriorated, which greatly contributes to the infrared reflection function, under a harsh usage environment. Become. However, in the transparent heat-shielding and heat-insulating member of the present embodiment, as described above, at least one layer other than the layer located on the outermost surface side is included in the protective layer composed of the plurality of coating type layers. Since it is composed of a layer containing a fluorine resin, the layer containing the fluorine-containing resin is not completely covered with the second metal suboxide layer or the metal oxide layer, which is present on the surface of the infrared reflective layer. It can function as a layer that protects "microscopic parts where the metal derived from the metal layer is exposed" from external environmental factors such as oxygen, water, and chloride ions, that is, a barrier layer. The progress of corrosion deterioration of the metal layer can be significantly suppressed.

More specific preferred embodiments of the infrared reflective layer include, for example, (A) transparent base material / first metal suboxide layer / metal layer / second metal suboxide layer, (B) transparent base material / first. 1 Metal Oxide Layer / Metal Layer / Second Metal Oxide Layer, (C) Transparent Base Material / First Metal Suboxide Layer / Metal Layer / Second Metal Oxide Layer, (D) Transparent Base Material / First Examples thereof include 1 metal oxide layer / metal layer / second metal oxide layer, (E) transparent base material / metal layer / metal suboxide layer, and the like. One of the configurations may be selected according to the main purpose. For example, from the viewpoint of improving the corrosion deterioration resistance of the metal layer of the infrared reflective layer and further enhancing the effect of reducing the solar radiation absorption rate, among these, among these. The configuration of (A) to (C) including at least the metal suboxide layer is preferable, and the second metal suboxide layer is laminated on the metal layer of (A) and (B). The configuration is more preferred. Further, when it is desired to increase the visible light transmittance as much as possible, it is preferable to use the configurations (B) to (D) including at least the above metal oxide layer.

Further, a hard coat layer, an adhesion improving layer (easy-adhesive layer), or the like may be provided between the infrared reflective layer and the transparent substrate. When the above hard coat layer is provided, a normal hard coat material can be used, but among them, an ultraviolet curable hard coat material made of an acrylic oligomer, a polymer, or the like having low shrinkage and bending resistance is used. It is preferable to use it. By using such a hard coat material, for example, even if the heat shield heat insulating film is accidentally bent, bent, or dented during the construction work of attaching the heat shield heat insulating film to the window glass, the hard coat layer can be 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 there is a risk that the function of the infrared reflective layer and the corrosion resistance deterioration resistance of the metal layer will be impaired. Can be reduced. The thickness of the hard coat layer is preferably 0.3 μm or more and 2.0 μm or less, and more preferably 0.5 μm or more and 1.0 μm or less.

The metal layer is mainly composed of a metal, and among general metals, silver (refraction rate n = 0.12) and copper (n =), which have high electrical conductivity and excellent far-infrared reflection performance. Metallic materials such as 0.95), gold (n = 0.35), and aluminum (n = 0.96) can be used as appropriate, among which silver, which absorbs relatively little visible light and has the highest electrical conductivity. It is preferable to use. 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 or more kinds of palladium, gold, copper, aluminum, bismuth, nickel, niobium, magnesium, zinc and the like. The metal 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, or a plasma CVD method. The thickness of the metal layer per layer is preferably 5 nm or more and 20 nm or less, and more preferably 8 nm or more and 16 nm or less, from the viewpoint of the balance between the visible light transmittance and the infrared reflectance. When the thickness of the metal layer is less than 5 nm, the reflectance of infrared rays is lowered and the shielding coefficient and the thermal transmission rate are increased, so that the heat shielding performance and the heat insulating performance may be deteriorated. On the other hand, if the thickness of the metal layer exceeds 20 nm, the visible light transmittance is lowered, so that the transparency may be inferior.

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. Be done. In the first metal oxide layer or metal oxide layer and the second metal oxide layer or metal oxide layer, the "metal oxide" means oxidation according to the chemical quantitative composition of the metal. It means a partial oxide (incomplete oxide) having a lower content of oxygen element than a substance, and "metal oxide" means an oxide according to the chemical quantitative composition of a metal. Further, the metal suboxide layer does not necessarily have to consist of a layer containing only a partial oxide having a lower oxygen element content than an oxide according to the chemical composition of the metal, and is formed by, for example, oxidation. It may be composed of an oxide layer according to the chemical quantitative composition and an unoxidized layer remaining without being oxidized. Specifically, the surface side directly in contact with the metal layer may be an unoxidized layer (as it is a metal layer), and the surface opposite to the surface directly in contact with the metal layer may be oxidized.

By providing the metal suboxide layer on either the top, bottom, top, or bottom of the metal layer with a predetermined thickness described later, the corrosion resistance deterioration resistance of the metal layer of the infrared reflective layer is improved and the solar radiation absorption rate is improved. Both reductions can be achieved 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 portion of a metal 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 a sputtering method using the above metal target, an oxidizing gas such as oxygen is added to an inert gas such as argon gas as an atmospheric gas (oxidation when forming a metal oxide film). It is possible to form a metal partial (incomplete) oxide layer, that is, a metal suboxide layer, which contains an oxygen element according to the concentration of the oxidizing gas. Further, a reducing oxide composed of an oxide lacking oxygen with respect to the stoichiometric composition of the metal can be used as a target, and a metal suboxide layer can be formed by a sputtering method in an inert gas atmosphere. Further, it is also possible to form a metal thin film or a partially oxidized metal thin film by a sputtering method or the like, and then post-oxidize it by heat treatment, atmospheric exposure or the like to form a metal suboxide layer. When the metal suboxide layer is formed on the metal layer, the atmosphere gas is limited to the inert gas from the viewpoint of suppressing the oxidation of the metal layer by the oxidizing gas and from the viewpoint of productivity. The metal suboxide layer is formed by a sputtering method using only the metal contained in the metal suboxide, and then the surface of the metal thin film is post-oxidized by exposure to the atmosphere to form the metal suboxide layer. preferable.

As a preferred embodiment of the method for forming the metal suboxide layer in the present embodiment, specifically, a first metal suboxide layer as a target is first placed on the transparent substrate under an inert gas atmosphere. A first metal thin film corresponding to the precursor of the first metal suboxide layer is formed by a sputtering method using only the metal contained in the first metal, and then the first metal 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, the metal layer such as silver is continuously formed as a target without breaking the vacuum. A second metal thin film corresponding to the precursor of the second metal suboxide layer is formed by a sputtering method using only the metal contained in the metal suboxide layer of 2, and then wound as a roll. A method of slowly oxidizing the surface of the second metal thin film while rewinding the roll in the atmosphere to transform it into the second metal suboxide layer can be mentioned. In this case, when the first metal thin film is formed on the transparent substrate by a 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 the metal suboxide layer 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 in direct contact with the metal layer such as silver becomes an unoxidized layer (metal layer, for example, a 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, and chloride ions as much as possible. It is also suitable from the viewpoint of being able to do it.

Further, by providing the metal oxide layer above, below, above, or below the metal layer with a predetermined thickness described later, both improvement of the visible light transmittance of the infrared reflecting layer and reduction of the solar radiation absorption rate are achieved. be able to. Examples of the metal oxide include indium tin oxide (refractive index n = 1.92), indium zinc oxide (n = 2.00), indium oxide (n = 2.00), and 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) and other metal oxides can be used as appropriate. The metal oxide layer can be formed by forming a film of these materials by, for example, a dry coating method such as a sputtering method, a vapor deposition method, or an ion plating method. Further, the metal of the metal oxide may be used as a target and formed by a reactive sputtering method under an atmospheric gas in which the concentration of the oxidizing gas is sufficiently increased.

When the metal suboxide layer is formed of a titanium (Ti) metal partial oxide (TiO _X ) layer, the x of TIO _X in the layer is the corrosion resistance and deterioration resistance of the metal layer of the infrared reflective layer. From the viewpoint of further enhancing the effects of improvement and reducing the solar radiation absorption rate and balancing with the visible light transmittance, the range is preferably 0.5 or more and less than 2.0. When x in the TiO _X is less than 0.5, the effect of reducing the corrosion deterioration resistance and the solar radiation absorption rate of the metal layer of the infrared reflecting layer is improved, but the visible light transmittance of the infrared reflecting layer is lowered. There is a risk of poor transparency. When x in the TiO _X is 2.0 or more, the visible light transmittance of the infrared reflective layer becomes high, but the corrosion deterioration resistance of the metal layer of the infrared reflective layer and the effect of reducing the solar radiation absorption rate may decrease. There is. The x of TiO _X can be analyzed and calculated by 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 within this range, the effect of improving the corrosion deterioration resistance of the metal layer of the infrared reflective layer and reducing the solar transmittance is further improved. At the same time as increasing it, it can be balanced with the visible light transmittance. The thickness of the metal oxide layer is preferably 1 nm or more and 6 nm or less, and when the thickness is within this range, the effect of reducing the solar absorption rate of the infrared reflective layer and the visible light transmittance are balanced. Can be done. 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 "metal layer is the second metal suboxide layer or metal oxide". There is an increased risk that "minimal parts where the metal derived from the metal layer is exposed and not completely covered by the layer" will increase, and there is a risk that sufficient corrosion resistance and deterioration resistance cannot be ensured, and the visible light transmission rate will increase. It may be low and less transparent. Further, if the thickness of the metal suboxide layer or the metal oxide layer exceeds 6 nm, the solar radiation absorption rate may increase particularly in the case of the metal oxide layer.

<Coating type protective layer>
The coating-type protective layer constituting the transparent heat-shielding and heat-insulating member of the present embodiment includes a plurality of layers, and among the above-mentioned coating-type protective layers, at least one layer other than the layer located on the outermost surface side is at least one layer. As a pre-curing resin component, it is composed of a layer containing a fluororesin having a curable functional group and a cross-linking agent that reacts with the curable functional group, and is on the outermost surface side of the above-mentioned coating type protective layer. The located layer is composed of a layer containing an ionizing radiation curable resin as a pre-curing resin component. With the above configuration, even if the protective layer composed of a plurality of layers of the coating type is thinly formed for the purpose of reducing the heat recirculation rate and further improving the heat insulating property, the solar radiation absorption rate is further increased. Even if the above-mentioned second metal suboxide layer or metal oxide layer is thinly formed for the purpose of reducing the amount of the metal oxide, as described above, the layer containing the fluorine-containing resin after being cured by the above-mentioned cross-linking agent. However, as a layer that protects "microscopic parts 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, that is, as a barrier layer. It can function and the diffusion and permeation of oxygen, water, chloride 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 can be significantly suppressed. Further, since the layer located on the outermost surface side of the coating type protective layer is cured by the ionizing radiation curable resin, practical scratch resistance can be imparted.

Of the above-mentioned coating type protective layers, at least one layer other than the layer located on the outermost surface side reacts with the fluororesin having a curable functional group as a pre-curing resin component and the curable functional group. The layer containing the cross-linking agent is applied, and the layer containing the ionizing radiation curable resin as the pre-curing resin component is applied to the layer located on the outermost surface side of the above-mentioned coating type protective layer. For the following reasons.

After curing, the layer containing the fluororesin having a curable functional group and the cross-linking agent that reacts with the curable functional group has a "microscopic state in which the metal derived from the metal layer is exposed" of the infrared reflective layer. It was found that it has a high function (barrier function) to protect "parts" and infrared reflective layers from external environmental factors such as oxygen, moisture, and chloride ions, but on the other hand, it has physical properties such as scratch resistance. Is insufficient, and when the layer is arranged on the layer located on the outermost surface side of the coating type protective layer, the film surface (transparent protective layer) is used when the film is applied or when the film is used for a long period of time. There were problems of poor appearance and corrosion deterioration of the metal layer due to the influence of the scratches. That is, it was not possible to achieve both the function of protecting from external environmental factors such as oxygen, moisture 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 the barrier function is imparted to at least one of the above coating type protective layers other than the layer located on the outermost surface side. For the purpose, a layer containing a fluororesin having a curable functional group and a cross-linking agent that reacts with the curable functional group is arranged as a pre-curing resin component, and the outermost of the above-mentioned coating type protective layers. By arranging a layer containing an ionizing radiation curable resin as a pre-curing resin component on the layer located on the surface side for the purpose of imparting scratch resistance, the above-mentioned problems are solved and the coating type composed of the plurality of layers is formed. As a whole, it is possible to achieve both the function of protecting from external environmental factors such as oxygen, moisture and chloride ions and the physical properties such as scratch resistance.

The type of the fluororesin having a curable functional group is not particularly limited as long as it is soluble in a solvent and can be applied as a resin solution, and the resin polymer having a definite melting point is used. It may be an elastomeric polymer exhibiting rubber elasticity, or a thermoplastic elastomeric polymer in between. As the solvent, a known solvent can be used, and specifically, aromatic hydrocarbons (benzene, toluene, xylene, etc.), aliphatic hydrocarbons (hexane, cyclohexane, etc.), ketones (acetone, methylethylketone, methyl, etc.) can be used. Isobutyl ketone, cyclohexanone, dimethyl sulfoxide, etc.) and amides (dimethylformiamide, N? Methylpyrrolidone) and the like can be mentioned. In addition to these, "Sorbesso (registered trademark) 100" (aromatic hydrocarbon solvent), "Sorbesso (registered trademark) 150" (aromatic hydrocarbon solvent), anon (cyclohexanone) and the like can also be used.

Examples of the curable functional group of the fluorine-containing resin having the curable functional group include a hydroxyl group, a carboxyl group, a group represented by -COOCO- derived from an acid anhydride, an amino group, a glycidyl group, a silyl group, and an isocyanate. The group etc. can be mentioned. The curable functional group is usually introduced into a fluororesin by copolymerizing a monomer having a curable functional group. Among these, as the curable functional group, a group represented by -COOCO- derived from a hydroxyl group, a carboxyl group, and an acid anhydride, an amino group, or a silyl group is preferable because of its good curing reactivity. A hydroxyl group is more preferable because the reactivity of the weight is good.

The fluororesin having a hydroxyl group preferably has a hydroxyl value of 20 mgKOH / g or more and 200 mgKOH / g or less. If the hydroxyl value is less than 20 mgKOH / g, the hardness, salt water resistance (barrier property) and interlayer adhesion of the obtained coating film after curing may be inferior. If the hydroxyl value exceeds 200 mgKOH / g, the solvent solubility may be inferior and the flexibility of the obtained coating film after curing may be lowered. The hydroxyl value is a value obtained by measuring by a method according to JIS K 0070, and is the amount of potassium hydroxide (KOH) required for acetylating the OH group contained in 1 g of the object (mg). Is.

The fluororesin having a hydroxyl group preferably contains a polymerization unit based on the following fluorine-containing monomer and a polymerization unit based on the hydroxyl group-containing monomer.

Examples of the fluorine-containing monomer include tetrafluoroethylene, chlorotrifluoroethylene, vinylidene fluoride, vinyl fluoride, fluorovinyl ether and the like, and one or more of these can be used. Among these, the fluorine-containing monomer is preferably at least one selected from the group consisting of tetrafluoroethylene, chlorotrifluoroethylene, and vinylidene fluoride, and is preferably tetrafluoroethylene and chlorotrifluoroethylene. It is more preferable that it is at least one selected from the group consisting of.

Examples of the hydroxyl group-containing monomer include 2-hydroxyethyl vinyl ether, 3-hydroxypropyl vinyl ether, 2-hydroxypropyl vinyl ether, 2-hydroxy-2-methylpropyl vinyl ether, 4-hydroxybutyl vinyl ether, and 4-hydroxy-2. -Hydroxide-containing vinyl ethers such as methylbutyl vinyl ether, 5-hydroxypentyl vinyl ether and 6-hydroxyhexyl vinyl ether; hydroxyl group-containing allyl ethers such as 2-hydroxyethyl allyl ether, 4-hydroxybutyl allyl ether and glycerol monoallyl ether. Can be mentioned. Among these, as the hydroxyl group-containing monomer, hydroxyl group-containing vinyl ethers are preferable in terms of excellent polymerization reactivity and curability of functional groups, and 4-hydroxybutyl vinyl ether, 2-hydroxyethyl vinyl ether, and 2-hydroxyethyl are preferable. At least one monomer selected from the group consisting of allyl ether and 4-hydroxybutyl allyl ether is more preferable.

Examples of other hydroxyl group-containing monomers include hydroxyalkyl esters of (meth) acrylic acid such as 2-hydroxyethyl acrylate and 2-hydroxyethyl methacrylate.

The polymerization unit based on the hydroxyl group-containing monomer is preferably 8 mol% or more and 30 mol% or less with respect to all the polymerization units constituting the fluororesin having a curable functional group, and is preferably 10 mol% or more and 20. It is more preferably mol% or less. When the polymerization unit based on the hydroxyl group-containing monomer is less than 8 mol% with respect to the total polymerization units constituting the fluororesin having a curable functional group, the hardness and salt resistance of the obtained coating film after curing are obtained. There is a risk that the water-based (barrier property) will be insufficient and the interlayer adhesion will be inferior. When the polymerization unit based on the hydroxyl group-containing monomer exceeds 30 mol% with respect to the total polymerization units constituting the fluororesin having a curable functional group, the viscosity of the coating composition becomes high and the coatability becomes high. Since it is inferior, the appearance of the obtained coating film may be deteriorated.

The fluororesin having a hydroxyl group may further contain at least one polymerization unit selected from the group consisting of a carboxyl group-containing monomer, an amino group-containing monomer, and a silyl group-containing monomer. good. The polymerization unit based on these functional group-containing monomers is preferably 8 mol% or more and 30 mol% or less with respect to all the polymerization units constituting the fluororesin having a curable functional group, and is preferably 10 mol%. It is more preferably 20 mol% or more. When these functional group-containing monomers are contained within the above range, the dispersibility and interlayer adhesion of pigments such as inorganic fine particles are excellent.

Examples of the carboxyl group-containing monomer include acrylic acid, methacrylic acid, vinyl acetic acid, crotonic acid, pentenoic acid, hexenoic acid, heptenoic acid, octenoic acid, noneic acid, decenoic acid, undecylene acid, dodecenoic acid and tridecenoic acid. , Tetradecenoic acid, pentadecenoic acid, hexadecenoic acid, heptadecenoic acid, octadecenoic acid, nonadecenoic acid, eicosenoic acid, 22-tricosenic acid, cinnamon acid, itaconic acid, itaconic acid monoester, maleic acid, maleic acid monoester, maleic acid 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, the above-mentioned carboxyl group-containing monomer has low homopolymerizability and it is difficult to form a homopolymer. Therefore, crotonic acid, undecylenic acid, itaconic acid, maleic acid, maleic acid monoester, fumaric acid, and fumaric acid are used. At least one acid selected from the group consisting of acid monoesters, 3-allyloxypropionic acid, and 3- (2-allyloxyethoxycarbonyl) propionic acid is preferred.

Examples of the amino group-containing monomer include aminovinyl ethers, allylamines, aminomethylstyrene, vinylamine, acrylamide, vinylacetamide, vinylformamide and the like.

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

The fluororesin having a curable functional group preferably contains a polymerization unit based on at least one fluorine-free vinyl monomer selected from the group consisting of a carboxylic acid vinyl ester, an alkyl vinyl ether and a non-fluorinated olefin.

The carboxylic acid vinyl ester has an action of improving compatibility. Examples of the carboxylic acid vinyl ester include vinyl acetate, vinyl propionate, vinyl butyrate, vinyl isobutyrate, vinyl pivalate, vinyl caproate, vinyl versatic acid, vinyl laurate, vinyl stearate, vinyl cyclohexylcarboxylate, and vinyl benzoate. , Para-t-butyl vinyl 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 non-fluorinated olefin include ethylene, propylene, n-butene, isobutene and the like.

Examples of the fluororesin having a curable functional group include (A) a perfluoroolefin polymer mainly composed of a perfluoroolefin unit and (B) a CTFE polymer mainly composed of a chlorotrifluoroethylene (CTFE) unit. , (C) VdF-based polymer mainly composed of vinylidene fluoride (VdF) unit, (D) fluoroalkyl group-containing polymer mainly composed of fluoroalkyl unit, (E) vinyl acetate-based polymer mainly composed of vinyl acetate unit, etc. Can be mentioned. Among these, as the fluororesin having a curable functional group, the polymers (A) and (B) are preferable from the viewpoint of weather resistance and salt water resistance (barrier property).

The perfluoroolefin-based polymer mainly composed of the above-mentioned perfluoroolefin-based polymer preferably has a perfluoroolefin unit of 20 mol% or more and 70 mol% or less, preferably 30 mol% or less, based on the total polymerization units of the perfluoroolefin-based polymer. More preferably, it is% or more and 50 mol% or less. If the perfluoroolefin unit is less than 20 mol% with respect to the total polymerization unit of the perfluoroolefin polymer, the weather resistance and salt water resistance (barrier property) of the obtained coating film after curing may be inferior. If the perfluoroolefin unit exceeds 70 mol% with respect to the total polymerization unit of the perfluoroolefin polymer, the interlayer adhesion, recoatability and solvent solubility may be deteriorated.

Examples of the perfluoroolefin include tetrafluoroethylene (TFE), hexafluoropropylene (HFP), perfluoro (alkyl vinyl ether) (PAVE) and the like. Among these, as the perfluoroolefin, TFE is preferable in that it is excellent in pigment dispersibility, weather resistance, copolymerizability and chemical resistance.

The perfluoroolefin-based polymer preferably contains a unit of another monomer copolymerizable with the perfluoroolefin.

Examples of the other copolymerizable monomer include vinyl acetate, vinyl propionate, vinyl butyrate, vinyl isobutyrate, vinyl pivalate, vinyl caproate, vinyl versatic acid, vinyl laurate, vinyl stearate, and cyclohexyl. Carboxylic acid vinyl esters such as vinyl carboxylate, vinyl benzoate, parat-butyl vinyl benzoate; alkyl vinyl ethers such as methyl vinyl ether, ethyl vinyl ether, butyl vinyl ether, cyclohexyl vinyl ether; ethylene, propylene, 1-butene, isobutene Non-fluoroolefins such as vinylidene fluoride (VdF), chlorotrifluoroethylene (CTFE), vinyl fluoride (VF), fluorovinyl ether and the like, and the like.

Among the perfluoroolefin-based polymers mainly composed of the perfluoroolefin unit, the TFE-based polymer mainly composed of the tetrafluoroethylene (TFE) unit includes, for example, TFE / isobutene / hydroxybutylvinyl ether / other monomers. Examples thereof include copolymers of TFE / vinyl versatic acid / hydroxybutyl vinyl ether / other monomer copolymers, TFE / VdF / hydroxybutyl vinyl ether / other monomer copolymers, and the like. Among these, the TFE-based polymer includes a copolymer of TFE / isobutene / hydroxybutyl vinyl ether / other monomer, and a copolymer of TFE / vinyl versatic acid / hydroxybutyl vinyl ether / other monomer. At least one copolymer selected from the group consisting of the above is preferable. Examples of the copolymer of the TFE-based polymer having such a curable functional group include "Zeffle (registered trademark) GK series" manufactured by Daikin Industries, Ltd.

Examples of the CTFE-based polymer mainly composed of the chlorotrifluoroethylene (CTFE) unit include a copolymer of CTFE / hydroxybutyl vinyl ether / other monomer. Examples of the copolymer of such a CTFE polymer having a curable functional group include "Obligard" (registered trademark) manufactured by AGC Cortec, "Lumiflon" (registered trademark) manufactured by Asahi Glass Co., Ltd., and DIC Co., Ltd. Examples include "Fluoronate" (registered trademark) manufactured by Central Glass Co., Ltd. and "Cefral Coat" (registered trademark) manufactured by Central Glass Co., Ltd.

The fluororesin having a curable functional group preferably has a number average molecular weight of 5,000 or more and 50,000 or less. If the number average molecular weight is less than 5,000, the hardness of the obtained coating film may be insufficient and the salt water resistance (barrier property) may be lowered. If the number average molecular weight exceeds 50,000, the viscosity of the coating composition becomes high and the coatability is poor, so that the appearance of the obtained coating film may be deteriorated. The number average molecular weight is a value obtained in terms of polystyrene by a gel permeation chromatography (GPC) method.

The fluororesin having a curable functional group can be produced, for example, by the methods disclosed in JP-A-2004-204205, JP-A-2013-177536, and the like. The composition of the fluororesin having a curable functional group can be measured by elemental analysis, NMR analysis, FT-IR analysis, fluorescent X-ray analysis and the like.

The fluororesin having the curable functional group has a fluorine-containing functional group having the curable functional group, if necessary, such as blocking, coatability, interlayer adhesion, and hardness improvement, as long as the effect of the present invention is not impaired. It may be mixed with a non-fluorine-based resin compatible with the resin and used. That is, the layer containing the fluororesin having the curable functional group may contain a non-fluorine-based resin compatible with the fluororesin having the curable functional group. Here, compatibility with the fluororesin having a curable functional group means that when each resin is mixed, the transparency of the obtained coating film is not significantly impaired without layer separation. When the non-fluorine-based resin is used in combination, the content of the non-fluorine-based resin is the solid content with respect to the total solid content mass of the fluororesin having the curable functional group and the non-fluorine-based resin. It is preferably 1% by mass or more and 50% by mass or less. If the content of the non-fluorine-based resin exceeds 50% by mass, the salt water resistance (barrier property) after curing of the coating film obtained by mixing with the fluororesin having a curable functional group may be inferior. ..

The non-fluorine-based resin is not particularly limited as long as it is compatible with the fluororesin having a curable functional group, but is not particularly limited, but is a thermoplastic acrylic resin, an acrylic polyol resin, an acrylic silicone resin, and a polyester. Examples thereof include resin and polyurethane resin. From the viewpoint of versatility, thermoplastic acrylic resin and acrylic polyol resin are preferable.

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

Examples of the acrylic polyol resin include (a) hydroxyl group-containing (meth) acrylic acid ester, hydroxyvinyl ether, allyl alcohol and other hydroxyl group-containing ethylenically unsaturated monomers, and (b) hydroxyl group-free olefins and vinyl ether. , Allyl ether, vinyl ester, propenyl ester, (meth) acrylic acid ester, vinyl aromatic compound, (meth) acrylonitrile, carboxyl group-containing unsaturated monomer, epoxy group-containing unsaturated monomer, amino group-containing unsaturated Examples thereof include a polymer with a hydroxyl group-free unsaturated monomer such as a monomer.

The hydroxypolyol resin preferably has a hydroxyl value of 30 mgKOH / g or more and 200 mgKOH / g or less. If the hydroxyl value is less than 30 mgKOH / g, the hardness, salt water resistance (barrier property) and interlayer adhesion after curing of the coating film obtained by mixing with the fluororesin having a curable functional group may be inferior. be. If the hydroxyl value exceeds 200 mgKOH / g, the flexibility of the coating film obtained by mixing with the fluororesin having solvent solubility and the curable functional group after curing may be inferior.

The cross-linking agent (curing agent) that reacts with the curable functional group of the fluorine-containing resin is appropriately selected according to the curable functional group of the fluorine-containing resin. For example, for a hydroxyl group-containing fluorine-containing resin, Cross-linking agents such as polyisocyanate compounds, melamine resins, silicate compounds, and isocyanate group-containing silane compounds can be used, and among these, polyisocyanate compounds are preferable. Further, an amino-based cross-linking agent, an epoxy-based cross-linking agent, or the like can be used for the carboxyl group-containing fluororesin, and a carbonyl group-containing cross-linking agent or an epoxy-based cross-linking agent is used for the amino group-containing fluororesin. , An acid anhydride-based cross-linking agent and the like can be used.

Examples of the polyisocyanate compound include 2,4-tolylene diisocyanate, diphenylmethane-4,4'-diisocyanate, xylylene diisocyanate, isophorone diisocyanate, lysine methyl ester diisocyanate, methylcyclohexyldiisocyanate, trimethylhexamethylene diisocyanate, hexamethylene diisocyanate, and n. -Pentan-1,4-diisocyanates, trimerics thereof, adducts thereof, burettes and isocyanurates, polymers having two or more isocyanate groups, blocked isocyanates, etc. However, it is not limited to these. Among these, as the polyisocyanate compound, isocyanurate prepolymer which is a trimer of hexamethylene diisocyanate and isocyanurate prepolymer which is a trimer of isophorone diisocyanate are preferable from the viewpoint of weather resistance. Examples of such polyisocyanate compounds include "Coronate (registered trademark) HX" manufactured by Tosoh Corporation, "Destanato T1890" (trade name) manufactured by Evonik Degussa, and "Death Module" manufactured by Sumika Cobestrolethane. A registered trademark) Z4470 ”and the like can be exemplified.

The content of the cross-linking agent shall be 0.3 molar equivalents or more and 2.0 molar equivalents or less with respect to 1 equivalent of the curable functional group in the fluororesin having the curable functional group. Is more preferable, and more preferably 0.5 molar equivalent or more and 1.5 molar equivalent or less, still more preferably 0.8 molar equivalent or more and 1.2 molar equivalent or less. If the content of the cross-linking agent is less than 0.3 molar equivalent, the cross-linking of the obtained coating film may be insufficient, and the hardness and barrier properties may decrease. 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 coating film adhere to each other due to the influence of the low molecular weight cross-linking agent, and the coated raw material is adhered to. Blocking may occur when unwinding.

When the non-fluororesin resin has a curable functional group, the cross-linking agent that reacts with the curable functional group should be the same as the cross-linking agent used for the fluororesin having the curable functional group. It can be appropriately selected and used according to the curable functional group of the non-fluororesin-based resin.

The content of the fluororesin having a curable functional group is a resin composition of a layer containing the fluororesin having a curable functional group and a cross-linking agent that reacts with the curable functional group (including the cross-linking agent). ) Is preferably 34% by mass or more and 94% by mass or less with respect to the total mass. If the content of the fluororesin having a curable functional group is less than 34% by mass, the weather resistance and salt water resistance (barrier property) of the obtained coating film after curing may be inferior. When the content of the fluororesin having a curable functional group exceeds 94% by mass, the amount of the cross-linking agent that can be added decreases, so that the obtained coating film is not sufficiently cured and the salt water resistance (barrier property) is improved. It may be inferior or the recoatability may be inferior.

The layer containing the fluororesin having a curable functional group and the cross-linking agent that reacts with the curable functional group has fluorine with respect to carbon atom C (at%: atomic percent) in the cured resin composition of the layer. The ratio (F / C) of atomic F (at%: atomic percent) is preferably 0.08 or more and 0.30 or less. The at% of the carbon atom C and the fluorine atom F are values measured by elemental analysis by energy dispersive X-ray (EDX) analysis described later.

If the ratio (F / C) of the fluorine atom F (at%: atomic percent) to the carbon atom C (at%: atomic percent) is less than 0.08, the salt water resistance (barrier property) may be inferior. If the ratio (F / C) of the fluorine atom F (at%: atomic percent) to the carbon atom C (at%: atomic percent) exceeds 0.30, the interlayer adhesion and recoatability may be inferior.

The coating-type protective layer constituting the transparent heat-shielding and heat-insulating member of the present embodiment includes a plurality of layers, and among the above-mentioned coating-type protective layers, the layer located on the outermost surface side is used as a pre-curing resin component. It consists of a layer containing an ionizing radiation curable resin. This protects the layer containing the fluororesin having the curable functional group and the cross-linking agent that reacts with the curable functional group after ionizing radiation irradiation, and assists in improving the salt water resistance (barrier property). The scratch resistance of the entire coating type protective layer can be ensured.

As the ionizing radiation curable resin, for example, a polyfunctional (meth) acrylate monomer, a polyfunctional (meth) acrylate oligomer (prepolymer), or the like can be preferably used, and these can be used alone or in combination. .. Specifically, ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, 1,4-cyclohexanediacrylate, pentaerythritol tetra (meth) acrylate, pentaerythritol tri (meth). ) Acrylate, Trimethylol Propanetri (meth) Acrylate, Trimethylol Ethantri (Meta) Acrylate, Dipentaerythritol Tetra (Meta) Acrylate, Dipentaerythritol Penta (Meta) Acrylate, Dipentaerythritol Hexa (Meta) Acrylate, 1, Acrylate such as 2,3-cyclohexanetrimethacrylate; vinylbenzene such as 1,4-divinylbenzene, 4-vinylbenzoic acid-2-acryloylethyl ester, 1,4-divinylcyclohexanone and derivatives thereof; pentaerythritol triacrylate hexamethylene Urethane-based polyfunctional acrylate oligomers such as diisocyanate urethane prepolymer; ester-based polyfunctional acrylate oligomers produced 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 silicone compound, and the outermost surface layer of the above-mentioned coating type protective layer can be formed by adding a photopolymerization initiator as needed and irradiating with ionizing radiation.

As described above, the coating type protective layer is formed by 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 shield heat insulating member. In particular, the coating type protective layer is formed of, for example, two to four layers from the viewpoint of productivity. 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 reflective layer from the infrared reflective layer side. All you have to do is prepare in this order. In this case, the medium refractive index layer or the high refractive index layer in contact with the infrared reflective layer contains a fluorine-containing resin having the curable functional group and a cross-linking agent that reacts with the curable functional group, and is formed on the fluororesin. The ionized radiation curable resin may be contained in the medium refractive index layer or the low refractive index layer (outermost surface layer). 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 reflective layer from the infrared reflective layer side. It's fine. In this case, at least one of the medium refractive index layer and the high refractive index layer contains a fluororesin having a curable functional group and a cross-linking agent that reacts with the curable functional group, and at least the low refractive index layer. The rate layer may contain the above-mentioned ionizing radiation curable resin. When the coating type protective layer has a four-layer structure, the optical adjustment layer, the medium refractive index layer, the high refractive index layer, and the low refractive index layer are placed in this order on the infrared reflective layer from the infrared reflective layer side. You just have to be prepared. In this case, at least one of the optical adjustment layer, the medium refractive index layer, and the high refractive index layer contains a fluorine-containing resin having the curable functional group and a cross-linking agent that reacts with the curable functional group. At least, the low refractive index layer may contain the ionizing radiation curable resin.

Among the multi-layered configurations exemplified above, the coating type protective layer has the infrared rays from the viewpoint of the balance between the optical characteristics and the appearance (irid phenomenon, the change in the reflected color depending on the viewing angle) of the transparent heat insulating member. From the reflective layer side, it is preferable to have a two-layer structure including a high refractive index layer and a low refractive index layer in this order. Further, from the viewpoint of improving the visible light transmittance in addition to the above-mentioned balance, from the above-mentioned infrared reflecting layer side, from the three-layer structure including the medium refractive index layer, the high refractive index layer and the low refractive index layer in this order. It is more preferable to have 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 made of a normal acrylic ultraviolet (UV) curable hard coat resin (usually, the refractive index is around 1.50) is provided on the infrared reflective layer as a layer having a single layer structure. In the visible light reflection spectrum, especially from a wavelength of 500 nm to 780 nm, the fluctuation of the visible light reflectance tends to increase as the wavelength increases, and the fluctuation of the film thickness of the protective layer is also taken into consideration to generate an iris pattern. Or, the change in reflected color increases depending on the viewing angle. In particular, when the thickness of the protective layer is set thin in the range overlapping with the wavelength region of visible light of 380 to 780 nm in order to reduce the thermal transmission rate and improve the heat insulating performance, the influence of the interference of multiple reflections is obtained. So, 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 the wavelength region of visible light of 380 to 780 nm. Even if it is set, it is possible to reduce the vertical fluctuation of the visible light reflectance linked to the wavelength in the visible light reflection spectrum, and it is possible to suppress the generation of an iris pattern and the change in 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 thermal transmission rate, 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 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, medium refractive index layer, and high refractive index may be deteriorated. Influence of C = O group, CO group and aromatic group contained in the molecular skeleton of the resin used for the layer and the low refractive index layer, and the inorganic oxide fine particles used for adjusting the refractive index of each layer. As a result, the absorption and absorption of far infrared rays having a wavelength of 5.5 μm to 25.2 μm in the coating type protective layer becomes large, and the vertical radiation rate becomes large, and as a result, the heat insulating performance may deteriorate. When the total thickness is within the range of 200 nm or more and 980 nm or less, the thermal transmissivity can be 4.2 W / (m ² · K) or less, and the heat insulating performance can be sufficiently exhibited. Further, the total thickness is set to 300 nm or more from the viewpoint of further improving scratch resistance and corrosion resistance, and is set to 700 nm or less in the range of 300 nm or more and 700 nm or less from the viewpoint of further reducing the thermal transmission rate. It is most preferable to set it. If the total thickness is within the range of 300 nm or more and 700 nm or less, the thermal transmissivity can be 4.0 W / (m ² · K) or less, and heat insulation performance, scratch resistance, corrosion resistance and deterioration resistance can be obtained. It is possible to achieve both physical characteristics and physical characteristics at a higher level.

Hereinafter, each layer constituting the coating type protective layer will be described.

[Optical adjustment layer]
The optical adjustment layer is a layer for adjusting the optical characteristics of the infrared reflective layer of the transparent heat shield 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 or more and 2.00 or less. Is preferable, and more preferably, it is in the range of 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, as a preferred embodiment, when the protective layer is formed of four layers, the thickness of the optical adjustment layer is sequentially increased on the optical adjustment layer. Since the appropriate range differs depending on the refractive index and thickness of each of the stacked medium-refractive index layer, high-refractive index layer, and low-refractive index layer, it cannot be said unconditionally, but it is different from the above other layer configurations. It is preferable to set it in the range of 30 nm or more and 80 nm or less, and more preferably it is set in the range of 35 nm or more and 70 nm or less. By setting the thickness of the optical adjustment layer within the range of 30 nm or more and 80 nm or less, it is possible to achieve both the visible light transmittance and the near-infrared reflectance of the transparent heat-shielding heat insulating member of the present embodiment in a high balance. If the thickness of the optical adjustment layer is less than 30 nm, the coating itself becomes difficult. For example, "the metal layer is not completely covered with the second metal suboxide layer or the metal oxide layer, and the metal layer is not covered. There is a risk that the coating liquid will be easily repelled and coverage will not be possible at "a very small part where the metal of origin is exposed". In addition, the visible light transmittance may decrease, the transparency may be inferior, and the redness of the reflected color may increase. On the other hand, if the thickness of the optical adjustment layer exceeds 80 nm, the near-infrared reflectance may decrease and the heat shielding 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 becomes large, and the heat insulating performance may deteriorate.

Further, the material constituting the optical adjusting layer may contain the same kind of material as the material constituting the second metal suboxide layer or the metal oxide layer of the infrared reflecting layer. It is preferable from the viewpoint of ensuring adhesion to the second metal suboxide layer or the metal oxide layer that is in direct contact with the metal oxide layer. For example, as the second metal suboxide layer or the metal oxide layer, partial oxidation of titanium metal When a physical layer, 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 adjustment layer contains titanium oxide fine particles, it is only possible to appropriately control the refractive index of the optical adjustment layer to a high refractive index within the range of 1.60 or more and 2.00 or less. It is possible to improve the adhesion to the partial oxide layer or oxide layer of the titanium metal or the metal suboxide layer or the metal oxide layer composed of the partial oxide layer or the oxide layer of the metal containing titanium as a main component. ..

The constituent material of the optical adjustment layer containing the inorganic fine particles represented 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 is not particularly limited, for example, a thermoplastic resin and a thermosetting layer. A material containing a resin such as a resin or an ionizing radiation curable resin and inorganic fine particles dispersed in the resin is preferably used. Among the constituent materials of the optical adjustment layer, the ionizing radiation curable resin and the ionizing radiation curable resin are dispersed in terms of optical properties such as transparency, physical properties such as scratch resistance, and productivity. A material containing inorganic fine particles is preferable. Further, a material containing inorganic fine particles in the ionization radiation curable resin is generally coated on the second metal suboxide layer or the metal oxide layer of the infrared reflective layer and then ionized radiation such as ultraviolet rays. It is cured by irradiation and formed as the optical adjustment layer. However, since the film is suppressed from shrinking during curing due to the inclusion of inorganic fine particles, the optical adjustment layer and the second metal suboxide layer are suppressed. Alternatively, the adhesion to the metal oxide layer can be improved.

Examples of the thermoplastic resin include modified polyolefin resin, vinyl chloride resin, acrylonitrile resin, polyamide resin, polyimide resin, polyacetal resin, polycarbonate resin, polyvinyl butyral resin, acrylic resin, and polyacetic acid. Examples thereof include vinyl-based resins, polyvinyl alcohol-based resins, cellulose-based resins, and the like, and examples of the thermosetting resin include phenol-based resins, melamine-based resins, urea-based resins, unsaturated polyester-based resins, epoxy-based resins, and polyurethanes. Examples thereof include based resins, silicone based resins, alkyd resins and the like, and these can be used alone or in combination, and the above optical adjustment layer can be formed by adding a cross-linking agent as necessary and thermosetting.

Examples of the ionized radiation curable resin include a polyfunctional (meth) acrylate monomer having two or more unsaturated groups, a polyfunctional (meth) acrylate oligomer (prepolymer), and the like, and these are 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-cyclohexanediacrylate, pentaerythritol tetra (meth) acrylate, pentaerythritol tri (meth). ) Acrylate, Trimethylol Propanetri (meth) Acrylate, Trimethylol Ethantri (Meta) Acrylate, Dipentaerythritol Tetra (Meta) Acrylate, Dipentaerythritol Penta (Meta) Acrylate, Dipentaerythritol Hexa (Meta) Acrylate, 1, Acrylate such as 2,3-cyclohexanetrimethacrylate; vinylbenzene such as 1,4-divinylbenzene, 4-vinylbenzoic acid-2-acryloylethyl ester, 1,4-divinylcyclohexanone and derivatives thereof; pentaerythritol triacrylate hexamethylene Urethane-based polyfunctional acrylate oligomers such as diisocyanate urethane prepolymer; ester-based polyfunctional acrylate oligomers produced from polyhydric alcohol and (meth) acrylic acid; epoxy-based polyfunctional acrylate oligomers and the like can be mentioned. The optical adjustment layer can be formed by adding a photopolymerization initiator as needed and curing the acrylate by irradiating it with ionizing radiation.

Further, in order to further improve the adhesion between the optical adjustment layer containing the ionization radiation curable resin and the second metal suboxide layer or the metal oxide layer of the infrared reflective layer, the ionization radiation curable type is used. Used by adding a (meth) acrylic acid derivative having a polar group such as a phosphoric acid group, a sulfonic acid group or an amide group, a silane coupling agent having an unsaturated group such as a (meth) acrylic group or a vinyl group to the resin. May be.

Further, 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 ), zinc oxide (ZrO ₂ ), zinc oxide (ZnO), indium tin oxide (ITO), niobium oxide (Nb ₂ O ₅ ), and yttrium oxide (Y ₂ O ₃ ). , Yttrium oxide (In ₂ O ₃ ), tin oxide (SnO ₂ ), antimony oxide (Sb ₂ O ₃ ), tantalum pentoxide (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, which can increase the refractive index with a small amount of addition as compared with other materials, are preferable, and the absorption of light in the far-infrared region is relatively small, and the above-mentioned metal suboxide layer. Titanium oxide is more preferable from the viewpoint of ensuring adhesion to the TiO _X layer, which is suitable for the above.

The particle size of the inorganic fine particles is preferably in the range of 5 nm or more and 100 nm or less, and more preferably in the range of 10 nm or more and 80 nm or less from the viewpoint of transparency of the optical adjustment layer. If the average particle size exceeds 100 nm, the haze value may increase when the optical adjustment layer is formed, and the transparency may decrease. If the average particle size is less than 5 nm, the optical adjustment layer may increase. When used as a paint, it may be difficult to maintain the dispersion stability of the inorganic fine particles.

When the optical adjustment layer is a layer containing a fluororesin having a curable functional group and a cross-linking agent that reacts with the curable functional group, the thermoplastic resin, the thermosetting resin, and the ionizing radiation curable resin are used. Instead, the above-mentioned inorganic fine particles for adjusting the refractive index are dispersed using a fluorine-containing resin having the above-mentioned curable functional group or a mixture of the fluorine-containing resin and a non-fluorine-based resin, and then the curable functional group. The coating material for the optical adjustment layer to which a cross-linking agent that reacts with the above is added may be adjusted to form and cure a coating film.

[Medium refractive index layer]
In the medium refractive index layer, the refractive index of light having a wavelength of 550 nm is preferably in the range of 1.45 or more and 1.55 or less, and the refractive index is more preferably in the range of 1.47 or more and 1.53 or less. preferable. When the coating type protective layer is formed of a plurality of layers, for example, as a preferred embodiment, when it is formed of four layers or three layers, the thickness of the medium refractive index layer is higher than that of the medium refractive index layer. The appropriate range differs depending on the refractive index and thickness of each of the lower refractive index layer, the upper refractive index layer and the lower refractive index layer in order with respect to the medium refractive index layer. However, in consideration of the composition of the other layers, it is preferable to set the thickness in the range of 35 nm or more and 200 nm or less, and the thickness is set in the range of 50 nm or more and 150 nm or less. Is more preferable. If 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 shield heat insulating member, the greenish color becomes stronger in the transmitted color, and the total light transmittance decreases. On the other hand, if the thickness of the medium refractive index layer exceeds 200 nm, the absorption of light in the infrared region becomes large and the heat insulating property may deteriorate, which is not preferable. In addition, the magnitude of ripple in the visible light reflection spectrum of the transparent heat shield and heat insulating member, that is, the fluctuation of the reflectance with respect to the wavelength in the visible light region cannot be sufficiently reduced, and not only the iris pattern becomes conspicuous, but also The change in the reflected color becomes large depending on the viewing angle, which may cause a problem in appearance, which is not preferable. For example, the reddish color may become stronger or the visible light transmittance may decrease in the reflected color of the transparent heat shield / heat insulating member. In addition, the absorption of light in the infrared region is increased, and the heat insulating property may be deteriorated.

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, and is, for example, thermal. A plastic resin, a thermosetting resin, an ionized radiation curable resin and the like are preferably used. As the resin such as the thermoplastic resin, the thermosetting resin, and the ionizing radiation curable resin, the same resin that can be used for the optical adjustment layer can be used, and the medium refraction can be used with the same formulation. A rate layer can be formed. Further, in order to adjust the refractive index, inorganic fine particles may be dispersed and added in the resin as needed. Among the constituent materials of the medium refractive index layer, a material containing an ionizing radiation curable resin is preferable from the viewpoint of optical characteristics such as transparency, physical characteristics such as scratch resistance, and productivity.

Among the above-mentioned ionizing radiation curable resins, resins and acryloyl groups containing urethane-based, ester-based, and epoxy-based polyfunctional (meth) acrylate oligomers (prepolymers) that have relatively little curing shrinkage when irradiated with ionizing radiation such as ultraviolet rays. A super-polyfunctional acrylic polymer resin having a large number of the above 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.

Further, in order to further improve the adhesion between the medium refractive index layer containing the ionization radiation curable resin and the optical adjustment layer or the second metal suboxide layer or the metal oxide layer, the ionization radiation curable type is used. Used by adding a (meth) acrylic acid derivative having a polar group such as a phosphoric acid group, a sulfonic acid group or an amide group, a silane coupling agent having an unsaturated group such as a (meth) acrylic group or a vinyl group to the resin. May be.

When the medium refractive index layer is a layer containing a fluororesin having a curable functional group and a cross-linking agent that reacts with the curable functional group, the thermoplastic resin, the thermosetting resin, and the ionizing radiation curable type are used. A medium refractive index layer to which a cross-linking agent that reacts with the curable functional group is added by using the above-mentioned fluororesin having a curable functional group or a mixture of the fluororesin and a non-fluorine-based resin instead of the resin. The paint for use may be prepared, a coating film may be formed, and the coating film may be cured. If necessary, inorganic fine particles for adjusting the refractive index may be dispersed.

The coating-type protective layer of the present embodiment contains, in particular, a fluororesin having a curable functional group and a cross-linking agent that reacts with the curable functional group, with the medium refractive index layer as a pre-curing resin component. Most preferably, it is a layer. This is due to the following reasons. That is, the coating type protective layer is formed of a plurality of layers for the purpose of achieving a good balance between the optical characteristics and the appearance (iris phenomenon, reflection color change depending on the viewing angle) of the transparent heat shield 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, but in many cases, the refractive index in this range is resin alone. Alternatively, it can be obtained with a resin to which a very small amount of inorganic fine particles for adjusting the refractive index is added, and such a medium refractive index layer can be obtained by adjusting the refractive index like the above-mentioned optical adjustment layer and the high refractive index layer described later. Compared to a layer containing a large amount of inorganic fine particles for use, the layer has extremely few fine voids and is a denser layer. Therefore, when the layer containing the fluorine-containing resin having the curable functional group and the cross-linking agent that reacts with the curable functional group is applied to the medium refractive index layer, it is applied to the optical adjustment layer and the high refractive index layer. Compared to the above-mentioned case, the above-mentioned "metal layer is not completely covered by the second metal suboxide layer and the metal derived from the metal layer is exposed. The function (barrier function) of protecting "small parts" and the infrared reflective layer from external environmental factors such as oxygen, water, and chloride ions can be further enhanced.

[High refractive index layer]
In the high refractive index layer, the refractive index of light having a wavelength of 550 nm is preferably in the range of 1.65 or more and 1.95 or less, and the refractive index is preferably in the range of 1.70 or more and 1.90 or less. preferable. Further, when the coating type protective layer is formed of a plurality of layers, for example, as a preferred embodiment, when the protective layer is formed of four layers, three layers or two layers, the thickness of the high refractive index layer is high refraction. The appropriate range differs depending on the refractive index and thickness of each of the medium refractive index layer, the optical adjustment layer, and the low refractive index layer, which is the upper layer for the high refractive index layer. Therefore, although it cannot be said unconditionally, it is preferable to set it in the range of 60 nm or more and 550 nm or less, and the thickness is set in the range of 65 nm or more and 400 nm or less in consideration of the composition of the other layers. It is more preferable to be done. If the thickness of the high-refractive index layer is less than 60 nm, there is a concern that the 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 may be formed. When a large amount of inorganic fine particles is contained, the absorption of light in the infrared region becomes large, which may lead to a decrease in 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 for example, a resin such as a thermoplastic resin, a thermosetting resin, or an ionizing radiation curable resin. A material containing the above-mentioned inorganic fine particles dispersed in the resin is preferably used. As the resin such as the thermoplastic resin, the thermosetting resin, the ionizing radiation curable resin, and the inorganic fine particles, the same resin and inorganic fine particles that can be used for the optical adjustment layer can be used. The high refractive index layer can be formed with the same formulation. Among the constituent materials of the high refractive index layer, the ionizing radiation curable resin and the ionizing radiation curable resin are included in the ionizing radiation curable resin and the ionizing radiation curable resin in terms of optical characteristics such as transparency, physical characteristics such as scratch resistance, and productivity. A material containing dispersed inorganic fine particles is preferable. Further, a material containing inorganic fine particles in the ionizing radiation curable resin is generally formed as the high refractive index layer by being coated on the medium refractive index layer and then cured by irradiation with ionizing radiation such as ultraviolet rays. However, since the shrinkage of the film at the time of curing is suppressed by containing the inorganic fine particles, the adhesion between the high refractive index layer and the medium refractive index layer can be improved.

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 smaller amount than other materials. And zirconium oxide are preferable, and titanium oxide is more preferable in that light absorption in the infrared region is relatively small.

Further, in order to further improve the adhesion between the high refractive acid layer containing the ionizing radiation curable resin and the medium refractive acid layer or the second metal suboxide layer or the metal oxide layer, the ionizing radiation curing is performed. A (meth) acrylic acid derivative having a polar group such as a phosphoric acid group, a sulfonic acid group or an amide group, a silane coupling agent having an unsaturated group such as a (meth) acrylic group or a vinyl group is added to the mold resin. You may use it.

When the high refractive index layer is a layer containing a fluororesin having a curable functional group and a cross-linking agent that reacts with the curable functional group, the thermoplastic resin, the thermosetting resin, and the ionizing radiation curable type are used. Instead of the resin, a fluorine-containing resin having the above-mentioned curable functional group or a mixture of the fluorine-containing resin and a non-fluorine-based resin is used to disperse the inorganic fine particles for adjusting the refractive index, and then the curable functional property is used. A coating material for a high refractive index layer to which a cross-linking agent that reacts with a group is added may be prepared, and a coating film may be formed and cured.

[Low refractive index layer]
In the low refractive index layer, the refractive index of light having a wavelength of 550 nm is preferably in the range of 1.30 or more and less than 1.45, and the refractive index is more preferably in the range of 1.35 or more and 1.43 or less. preferable. Further, when the protective layer is formed of a plurality of layers, for example, as a preferred embodiment, when the protective layer is formed of four layers, three layers or two layers, the thickness of the low refractive index layer is set to the low refractive index layer. On the other hand, since the appropriate range differs depending on the refractive index and thickness of each of the lower refractive index layer, medium refractive index layer, and optical adjustment layer in order, it cannot be said unconditionally, but the above other layers In consideration of the configuration, it is preferable to set it in the range of 70 nm or more and 150 nm or less, and it is more preferable to set the thickness in the range of 80 nm or more and 130 nm or less. When the thickness of the low refractive light layer is out of the range of 70 nm or more and 150 nm or less, the magnitude of the ripple of the reflection spectrum in the visible light region of the transparent heat-shielding heat insulating member of the present embodiment, that is, the reflectance with respect to the wavelength in the visible light region. The fluctuation of the light cannot be sufficiently reduced, and not only the iris pattern becomes conspicuous, but also the change in the reflected color becomes large 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 ionizing radiation curable resin as the pre-curing resin component. As the ionizing radiation curable resin, for example, a polyfunctional (meth) acrylate monomer, a polyfunctional (meth) acrylate oligomer (prepolymer), or the like can be preferably used, and these can be used alone or in combination. .. Specifically, ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, 1,4-cyclohexanediacrylate, pentaerythritol tetra (meth) acrylate, pentaerythritol tri (meth). ) Acrylate, Trimethylol Propanetri (meth) Acrylate, Trimethylol Ethantri (Meta) Acrylate, Dipentaerythritol Tetra (Meta) Acrylate, Dipentaerythritol Penta (Meta) Acrylate, Dipentaerythritol Hexa (Meta) Acrylate, 1, Acrylate such as 2,3-cyclohexanetrimethacrylate; vinylbenzene such as 1,4-divinylbenzene, 4-vinylbenzoic acid-2-acryloylethyl ester, 1,4-divinylcyclohexanone and derivatives thereof; pentaerythritol triacrylate hexamethylene Urethane-based polyfunctional acrylate oligomers such as diisocyanate urethane prepolymer; ester-based polyfunctional acrylate oligomers produced 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 silicone compound, and the outermost surface layer of the above-mentioned coating type protective layer can be formed by adding a photopolymerization initiator as needed and irradiating with ionizing radiation. Further, in order to adjust the refractive index, inorganic fine particles may be dispersed and added in the ionizing radiation curable resin as needed. For example, a material containing the ionizing radiation curable resin and the low refractive index inorganic fine particles dispersed in the ionizing radiation curable resin, and the ionizing radiation curable resin and the low refractive index inorganic fine particles are chemically bonded. Materials containing organic / inorganic hybrid materials are preferred.

The inorganic fine particles are dispersed and added in the resin in order to adjust the refractive index of the low refractive index layer. As the inorganic fine particles having a low refractive index, for example, silicon oxide, magnesium fluoride, aluminum fluoride and 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. Therefore, a silicon oxide-based material is preferable, and a hollow type silicon oxide (hollow silica) -based material having voids inside in order to exhibit a low refractive index is particularly preferable.

Further, a material containing inorganic fine particles in the ionizing radiation curable resin is generally formed as the low refractive index layer by being coated on the high refractive index layer and then cured by irradiation with ionizing radiation such as ultraviolet rays. However, since the film contains the inorganic fine particles, the shrinkage of the film during curing is suppressed, so that the adhesion to the high refractive index layer can be improved.

Further, in order to further improve the adhesion between the low refractive acid layer containing the ionization radiation curable resin and the high refractive acid layer or the second metal suboxide layer or the metal oxide layer, the ionization radiation curable type is used. Used by adding a (meth) acrylic acid derivative having a polar group such as a phosphoric acid group, a sulfonic acid group or an amide group, a silane coupling agent having an unsaturated group such as a (meth) acrylic group or a vinyl group to the resin. May be.

The constituent material of the low refractive index layer may contain additives such as a leveling agent, a lubricant, an antistatic agent, and a haze-imparting agent in addition to the constituent materials, and the content of these additives may be contained. Is appropriately adjusted as long as the object of the present embodiment is not impaired.

As described above, as the coating type protective layer formed from the multi-layered layer, (1) a laminated structure including the high refraction rate layer and the low refraction rate layer from the infrared reflective layer side in this order, (2). A laminated structure including the medium refraction layer, the high refraction layer and the low refraction layer in this order from the infrared reflective layer side, or (3) the optical adjustment layer, the medium refraction layer, and the high refraction from the infrared reflective layer side. A laminated structure including a rate layer and a low refractive index layer in this order is a preferable embodiment of the present embodiment, but in any of the configurations, the total thickness of the coating type protective layer made of each layer is high. The thickness of the optical adjustment layer having a refractive index of 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 can be adjusted from the range of 30 nm or more and 80 nm or less. The thickness of the medium refraction layer having a refractive index of 1.45 or more and 1.55 or less for light at 550 nm is within the range of 40 nm or more and 200 nm or less, and the refractive index for light with a wavelength of 550 nm is 1.65 or more. The thickness of the high refractive index layer of 1.95 or less is within 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. By appropriately setting the thickness from the range of 70 nm or more and 150 nm or less, scratch resistance while maintaining heat insulating properties (the value of heat transmission coefficient is 4.2 W / (m ² · K) or less), It is possible to provide a transparent heat-shielding and heat-insulating member having excellent physical properties such as corrosion resistance and deterioration resistance, a low solar radiation absorption rate, and a good appearance that suppresses an iris phenomenon and a change in reflected color depending on a viewing angle. In particular, in order to maintain high visible light transmittance and lower solar absorption rate, the above-mentioned plurality of reflectances are generally set to be high in the wavelength band of 800 to 1500 nm, which is a wavelength band having a large energy value coefficient. It is preferable to set a layer 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 within the range of 300 nm or more and 700 nm or less, the thermal transmissivity value becomes 4.0 W / (m ² · K) or less. Moreover, since the mechanical properties of the protective layer can be sufficiently ensured, it is possible to achieve both heat insulating performance and physical properties such as scratch resistance and corrosion resistance at a higher level.

When the coating type protective layer is composed of two layers including the medium refractive index layer (bottom) and the medium refractive index layer (top) from the infrared reflective layer side in this order, the medium refractive index layer Each thickness does not have 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. And set it.

In the transparent heat-shielding and heat-insulating member of the present embodiment, at least the layer in contact with the (second) metal suboxide layer or the metal oxide layer of the infrared reflective layer among the coating type protective layers is corroded against metal. It is preferable to include an inhibitor. The above (second) metal suboxide layer or the layer in contact with the metal oxide layer contains the corrosion inhibitor for the metal to reduce the solar absorption rate of the low radiation film. Even if the metal suboxide layer or the metal oxide layer (2) is formed thinly, the corrosion inhibitor for the metal is "the metal layer is completely formed by the (second) metal suboxide layer or the metal oxide layer. By adsorbing to "a very small part where the metal derived from the metal layer is exposed without being covered" to form a corrosion prevention layer, the minute metal part can be treated with oxygen, water, and chloride ions. In addition to the barrier effect of the layer containing the fluorine-containing resin having the curable functional group and the cross-linking agent that reacts with the curable functional group, it can be protected from external environmental factors such as corrosion deterioration of the metal layer. Progression can be further suppressed.

The type of the corrosion inhibitor for the metal is not particularly limited, and any compound capable of suppressing the corrosion of the metal may be used. Among them, those capable of suppressing the corrosion of silver are preferable, and compounds having a functional group easily adsorbed on 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, silicone-modified resins and the like. Among them, a compound having a nitrogen-containing group and a compound having a sulfur-containing group are particularly preferable, and it is preferable to select from at least one of these or a mixture thereof.

Examples of the compound having a nitrogen-containing group include alkyl alcohol amine derivatives such as aminoalcohol, methylethanolamine, dimethylaminoethanol, N, N-dimethylethanolamine; and phenylamine derivatives such as diphenylamine, alkylated diphenylamine, and phenylenediamine. Guanidin derivatives such as guanidine, 1-o-tolylbiguanide, 1-phenylguanidine, aminoguanidine; triazoles such as 1,2,3-triazole, 1,2,4-triazole, benzotriazole, 1-hydroxybenzotriazole. And its derivatives; pyrrol derivatives such as N-butyl-2,5-dimethylpyrrole, N-phenyl-2,5-dimethylpyrrole; pyrazole, pyrazoline, pyrazolone, pyrazolidine, pyrazoridone, 3,5-dimethylpyrazole, 3-methyl Pyrazoles and derivatives thereof such as -5-hydroxypyrazole and 4-aminopyrazole; imidazoles such as imidazole, histidine, 2-heptadecylimidazole, 2-methylimidazole and derivatives thereof; 4-chloroindazole, 4-nitroindazole, Examples thereof include indazoles such as 5-nitroindazole and 4-chloro-5-nitroindazole and their derivatives.

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. Thiol benzoic acids and their derivatives; pentaerythritol-tetrakis (3-mercaptobutyrate), 1,4-bis (3-mercaptobutylyloxy) butane, trimethylolpropane-tris (3-mercaptobutyrate), trimethylolethane Polyfunctional thiol monomers such as ethane-tris (3-mercaptobutyrate); examples thereof include thiophenol, glycol dimercaptoacetate, 3-mercaptopropyltrimethoxysilane and the like.

Further, examples of the compound having both a nitrogen-containing group and a sulfur-containing group include mercaptotriazoles such as 3-mercapto-1,2,4-triazole and 1-methyl-3-mercapto-1,2,4-triazole. And its derivatives; mercaptotriazoles such as 2-mercaptobenzothiazole and its derivatives; mercaptoimidazoles such as 2-mercaptobenzoimidazole and its derivatives; mercaptotriazines such as 2,4-dimercaptotriazine and its derivatives; 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 can be mentioned. ..

The content of the corrosion inhibitor for the metal is preferably 1% by mass or more and 20% by mass or less with respect to 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 and the protective layer in contact with the second metal suboxide layer or the metal oxide layer There is a risk that the strength of the layer containing the corrosion inhibitor against the other metals will decrease, and the adhesion at the interface in contact with the layer will decrease.

The corrosion inhibitor for the metal is contained in at least the (second) metal suboxide layer or the layer in contact with the metal oxide layer of the infrared reflective layer in the coating type protective layer composed of a plurality of layers. On the surface of the infrared reflective layer, "the metal layer is not completely covered with the (second) metal suboxide layer or the metal oxide layer, and the metal derived from the metal layer is exposed. This is because the corrosion inhibitor for the metal can be adsorbed to the "small portion" most efficiently to form the corrosion inhibitor layer. As a result, when the above-mentioned (second) metal suboxide layer or metal oxide layer is thinly formed for the purpose of reducing the solar radiation absorption rate of the low-emission film, the "metal layer becomes (second)". Even if a "microscopic part" that is not completely covered by the metal suboxide layer or the metal oxide layer and the metal derived from the metal layer is exposed is generated, the corrosion inhibitor for the metal is used. The corrosion prevention layer formed by adsorbing to extremely small metal parts serves as a barrier layer against external environmental factors such as oxygen, water, and chloride ions that have diffused and permeated the protective layer, and is an external environmental factor. In order to protect from the conventional problem, "the metal layer is not completely covered with the (second) metal suboxide layer or the metal oxide layer, and the metal derived from the metal layer is exposed. It is possible to remarkably suppress the progress of corrosion deterioration of the metal layer starting from "a very small part".

As described above, when the coating type protective layer is formed by 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 contact with the (second) metal suboxide layer or the metal oxide layer in the infrared reflective layer contains a corrosion inhibitor for the metal, but in addition, other layers are also included. 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 coating type protective layer, the wet coating liquid may be used as the above-mentioned "metal layer is a (second) metal sub-layer". It is repelled by "a very small part where the metal derived from the metal layer is exposed because it is not completely covered by the oxide layer or the metal oxide layer", and the surface cannot be covered to prevent corrosion of the metal. Even if the agent cannot be adsorbed to a very small metal portion well, if the protective layer for the next second layer contains a corrosion inhibitor for the metal, the above 2 can be placed on the first layer of the protective layer. When the protective layer of the layer is formed by the wet coating, there is an opportunity to adsorb the anticorrosion agent for the metal again to the extremely minute metal part where the anticorrosion agent for the metal could not be adsorbed due to the inability to cover the metal. Because it can be given. As a result, the above-mentioned "metal layer is not completely covered with the (second) metal suboxide layer or the metal oxide layer, and the metal derived from the metal layer is exposed." It is possible to significantly reduce the residual rate of "microscopic parts that are in a state".

<Adhesive layer>
In the transparent heat-shielding and heat-insulating member of the present embodiment, it is preferable to arrange the pressure-sensitive adhesive layer on the surface opposite to the surface on which the coating-type protective layer of the transparent substrate is formed. As a result, the transparent heat-shielding and heat-insulating member of the present embodiment can be easily attached to a transparent substrate such as a window glass. As the material of the pressure-sensitive adhesive layer, a material having a high visible light transmittance and a small difference in refractive index from the transparent substrate is preferably used. For example, acrylic, polyester, urethane, rubber, silicone and other resins 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 cost.

The acrylic resin (adhesive) includes a homopolymer of an acrylic monomer such as acrylic acid and its ester, methacrylic acid and its ester, acrylamide, and acrylonitrile, or a copolymer thereof, and at least one of the acrylic monomers. And a copolymer with a vinyl monomer such as vinyl acetate, maleic anhydride, styrene and the like. In particular, suitable acrylic pressure-sensitive adhesives include alkyl acrylate-based main monomers such as methyl acrylate, ethyl acrylate, butyl acrylate, and 2-ethylhexyl acrylate, which are components for developing tackiness, and for improving the cohesive force. Monomers such as vinyl acetate, acrylamide, acrylonitrile, styrene, and methacrylate, which are components, and acrylic acid, methacrylic acid, itaconic acid, crotonic acid, and anhydrous, which are components for improving adhesive strength and imparting cross-linking points. Examples thereof include those obtained by appropriately copolymerizing a monomer having a functional group such as maleic acid, hydroxylethyl methacrylate, hydroxylpropyl methacrylate, dimethylaminoethyl methacrylate, methylolacrylamide, and glycidyl methacrylate. The Tg (glass transition temperature) of the acrylic pressure-sensitive adhesive is preferably in the range of -60 ° C or higher and -10 ° C or lower, and the weight average molecular weight is preferably in the range of 100,000 or higher and 2,000,000 or lower, particularly 500. Those in the range of 000 or more and 1,000,000 or less are more preferable. As the acrylic pressure-sensitive adhesive, one or a mixture of two or more cross-linking agents such as isocyanate-based, epoxy-based, and metal chelate-based adhesives can be used, if necessary.

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

The pressure-sensitive adhesive layer preferably contains an ultraviolet absorber such as a benzophenone-based, benzotriazole-based or triazine-based agent in order to suppress deterioration of the transparent heat-shielding heat insulating member due to ultraviolet 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-shielding and heat-insulating member is attached to the transparent substrate and used.

<Transparent heat shield and heat insulating member>
Since the transparent heat-shielding and 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 proper design combination of the infrared reflecting layer and the coating type protective layer. Hereinafter, the thermal transmittance 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-emissivity film having high transparency and excellent heat-shielding and heat-insulating properties, in which the risk of heat cracking of the glass when the film is attached to the window glass is reduced.

Further, since the transparent heat-shielding and heat-insulating member has the above-mentioned structure, 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 by properly designing the infrared reflective layer and the coating type protective layer. When the salt water resistance test is performed, the transmittance of light having a transmittance of 1100 nm in the transmission spectrum (initial) in the wavelength range of 300 to 1500 nm of the transparent heat shield heat insulating member measured before the salt water resistance test is _TB %. When the transmittance of light having a transmittance 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 shield and heat insulating member measured after the salt water resistance test is _TA %, the value of TA _{- TB} . Can be less than 10 points. That is, the above aspect means that deterioration of the function of the infrared reflective layer under a harsh test environment is remarkably suppressed, and it is possible to provide a low emissivity film having excellent corrosion resistance deterioration.

Further, since the transparent heat-shielding heat insulating member has the above-mentioned structure, the reflection spectrum measured according to JIS R3106-1998 by a proper design combination of the infrared reflecting layer and the coating type protective layer. The point corresponding to the wavelength 535 nm on the virtual line a showing the average value of the maximum reflectance and the minimum reflectance in the wavelength range of 500 to 570 nm is set as a point A, and the maximum reflectance in the wavelength range of 620 to 780 nm of the reflection spectrum. The point corresponding to the wavelength of 700 nm on the virtual line b showing the average value of the minimum reflectance is defined as the point B, and the straight line passing through the point A and the point B is extended in the range of the wavelength of 500 to 780 nm to be the reference straight line AB. When comparing the reflectance value of the reflectance spectrum and the reflectance value of the reference straight line AB in the range of 500 to 570 nm, the reflectance at the wavelength where the difference between the respective reflectance values is 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 range of the wavelength 620 to 780 nm. When comparing the value of the above and the value of the reflectance of the reference straight line AB, the absolute value of the difference of the reflectance value at the wavelength where the difference of the respective reflectance values is maximum is defined as the maximum fluctuation difference ΔB. Occasionally, the value of the maximum fluctuation 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 to the wavelength in the reflection spectrum is reduced, and the appearance that suppresses the generation of the iris pattern and the change in the reflected color depending on the viewing angle. It is also possible to provide an excellent low radiation film.

Next, an example of the transparent heat-shielding and heat-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 a transparent heat-shielding and heat-insulating member of the present embodiment. In FIG. 1, the transparent heat-shielding and heat-insulating member 10 includes a transparent base material 11, a functional layer 23 composed of an infrared reflective layer 21 and a coating-type protective layer 22, and an adhesive layer 19. The infrared reflective 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 is formed of 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, the medium refractive index layer 16 is a pre-curing resin component, a layer containing a fluorine-containing resin having a curable functional group and a cross-linking agent that reacts with the curable functional group, and the low refractive index layer 18 is a pre-curing resin component. , Can be a layer containing an ionized radiation curable resin.

FIG. 2 is a diagram showing an example of the transmission spectrum of the transparent heat shield heat insulating member of the present embodiment before and after the salt water resistance test. When the transparent heat-shielding and heat-insulating member is immersed in a sodium chloride aqueous solution having a temperature of 50 ° C. and a concentration of 5% by mass for 30 days, the wavelength 300 of the transparent heat-shielding and heat-insulating member measured before the salt-water resistance test. The transmittance of light having a transmittance of 1100 nm in the transmission spectrum (initial) in the range of ~ 1500 nm is _TB %, and the transmittance of the transparent heat-shielding heat insulating member measured after the salt water resistance test in the range of 300 to 1500 nm (immersion for 30 days). Assuming that the transmittance of light having a wavelength of 1100 nm in (later) is _TA %, the value of TA _{- TB} can be less than 10 points.

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

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

As described above, the transparent heat-shielding and heat-insulating member of the above-described embodiment can exhibit a heat-insulating function and a heat-shielding function while lowering the solar absorption rate by the infrared-reflecting layer, and also has scratch resistance by the coating-type protective layer. Corrosion resistance and deterioration resistance are improved, and the heat insulating function can be maintained.

(Manufacturing method of transparent heat shield and heat insulating member)
Next, an embodiment of the method for manufacturing a transparent heat-shielding and heat-insulating member of the present invention will be described. An embodiment of the method for manufacturing a transparent heat-shielding and heat-insulating member of the present invention includes 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 provided with a step of forming by a wet coating method.

Hereinafter, an example of the method for manufacturing the transparent heat-shielding and heat-insulating member of the present embodiment will be described with reference to FIG.

First, the infrared reflective layer 21 is formed on one surface of the transparent base material 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 it may be formed by another method. The infrared reflective layer 21 has a three-layer structure consisting of a first metal suboxide layer or a metal oxide layer 12, a metal layer 13, and a second metal suboxide layer or a metal oxide layer 14. , Preferable in terms of heat insulation / insulation function, corrosion deterioration resistance, and productivity. In particular, when the first metal suboxide layer 12 and the second metal suboxide layer 14 are formed, it is preferable to form them by various sputtering methods as described above. This makes it possible to reliably form a metal suboxide layer in which the metal is partially oxidized.

Next, an optical adjustment layer 15 containing a corrosion inhibitor for metal is formed on the infrared reflective layer 21. Subsequently, a medium refractive index layer 16 containing a fluorine-containing resin having a curable functional group and a cross-linking agent that reacts with the curable functional 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 high refractive index layer 17, and a low refractive index layer 18 containing a radiation-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 in this way can prevent the infrared reflective layer 21 from being damaged by window cleaning or the like even if the infrared reflective layer 21 is arranged indoors, and is resistant to damage. It has excellent corrosion deterioration resistance, can suppress angle dependence such as iris phenomenon and change in reflected color depending on viewing angle, and can maintain the heat insulating function of the infrared reflective layer while lowering the solar absorption rate. ..

Finally, the pressure-sensitive adhesive layer 19 is formed on the other surface of the transparent base material 11. The method for 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 base material 11, or a separately prepared pressure-sensitive adhesive sheet may be attached.

By the above steps, an example of the transparent heat-shielding and heat-insulating member of the present embodiment is obtained, and then, if necessary, it is used by being bonded to a glass substrate or the like.

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

(Measurement of refractive index)
The refractive indexes 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 / Comparative Examples were measured by the methods shown below.

First, a paint for forming each layer was applied to a thickness of 500 nm on the surface of the polyethylene terephthalate (PET) film "A4100" (trade name, thickness: 50 μm) manufactured by Toyobo Co., Ltd., which had one side easily adhered. It is applied so as to be, and dried to prepare a sample for measuring the refractive index. When an ultraviolet curable paint is used as the paint for forming each layer, it is dried and then cured by irradiating it with an ultraviolet ray having a light amount of 300 mJ / cm ² with a high-pressure mercury lamp to prepare a sample for refractive index measurement. ..

Next, a black tape was attached to the back side of the coated surface of the prepared sample for measuring the refractive index, and the reflection spectrum was measured with a reflection spectroscopic 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 equation of n-Cauchy, and the refractive index of light having a wavelength of 550 nm for each layer was determined.

(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 / 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, the reflection spectrum is measured for each layer by the instantaneous multi-measurement system "MCPD-3000" (trade name, manufactured by Otsuka Electronics Co., Ltd.), and the obtained refractive index is measured by the above-mentioned refractive index. Using the obtained refractive index, fitting by the optimization method was performed to determine the film thickness of each layer.

(Measurement of ratio (F / C) of fluorine atom F (at%) to carbon atom C (at%))
Fluorine atom F (at%) with respect to carbon atom C (at%) in the resin composition of the layer containing the fluorine-containing resin having a curable functional group and the cross-linking agent that reacts with the curable functional group described in the following examples. The ratio (F / C) of (at%) is the energy dispersive type attached to the scanning electron microscope "S-3400N" (trade name, manufactured by Hitachi High-Technology Co., Ltd.) by using a separately prepared small piece of the same resin composition as a sample. SEM-EDX analysis using X-rays (acceleration voltage 15 kV, low vacuum mode 30 Pa, surface analysis) shows that the total of the four elements carbon atom C, fluorine atom F, oxygen atom O, and chlorine Cl is 100%. The atomic% of the element was calculated and calculated. The sample pieces were prepared by pouring a solution of the resin composition into an aluminum cup, sufficiently drying the solvent, and then aging at 120 ° C. for 2 minutes.

(Example 1)
<Manufacturing a transparent substrate with an infrared reflective layer>
First, a polyethylene terephthalate (PET) film "U483" (trade name, thickness: 50 μm) manufactured by Toray Industries, Inc., which was easily bonded on both sides, was used as a transparent base material, and the PET film was placed on one side of the PET film from the PET film side. The metal suboxide layer, the metal layer, and the second metal suboxide layer of No. 1 were formed as follows. First, using a titanium target, a first metal suboxide layer (TiO _X layer) having a thickness of 2 nm was formed by a reactive sputtering method. As the sputtering gas in the above reactive sputtering method, a mixed gas of Ar / O ₂ was used, and the gas flow rate / _volume ratio was Ar 97% / O 23%. Subsequently, a metal layer (Ag layer) having a thickness of 12 nm was formed on the first metal suboxide layer by a sputtering method using a silver target. As the sputtering gas in the above sputtering method, 100% Ar gas was used. Further, a second 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 above reactive sputtering method, a mixed gas of Ar / O ₂ was used, and the gas flow rate / _volume ratio was Ar 97% / O 23%. As a result, an infrared reflective layer having a three-layer structure consisting of a first metal suboxide layer (TiO _X layer) / metal layer (Ag layer) / second metal suboxide layer (TiO _X layer) from the PET film side. A PET film with a metal was prepared. 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>
Titanium oxide hard coating agent "Riodurus TYT80-01" manufactured by Toyo Ink Co., Ltd. (trade name, solid content concentration 25% by mass, refractive index 1.80 [nominal value]) 96.00 parts by mass and corrosion inhibitor for metals 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 methylisobutylketone as a diluting solvent are added to the disper. To prepare an optical adjustment paint A. Next, the optical adjustment paint A is applied onto the infrared reflective layer using a microgravure coater (manufactured by Yasui Seiki Co., Ltd.) so that the thickness after drying is 50 nm, dried, and then subjected to high pressure. An optical adjustment layer having a thickness of 50 nm was formed by irradiating with an ultraviolet ray having a light amount of 300 mJ / cm ² with a mercury lamp and curing the mixture. When the refractive index of the produced optical adjustment layer was measured by the above-mentioned method, it was 1.79.

<Formation of medium refractive index layer>
Fluororesin "Zeffle GK-570" manufactured by Daikin Industries, Ltd. (trade name, solid content concentration 65.0% by mass, hydroxyl group-containing TFE-based copolymer, hydroxyl value 64 mgKOH / g, acid value 4 mgKOH / g) 25.11 By mass, 3.68 parts by mass (NCO / OH = 1.0) of isocyanate-based curing agent "Coronate HX" (trade name, cross-linking agent, solid content concentration 100% by mass) manufactured by Toso Co., Ltd., and methyl as a diluting solvent. A medium refractive index coating material A was prepared by blending 971.21 parts by mass of an isobutyl ketone with a disper. Next, the medium refractive index paint A is applied onto the optical adjustment layer using the microgravure coater so that the thickness after drying is 60 nm, dried at 120 ° C. for 2 minutes, and thermoset. As a result, a medium refractive index layer having a thickness of 60 nm was formed. The refractive index of the produced medium refractive index layer was measured by the above-mentioned method and found to be 1.46. The content of the fluororesin in the medium refractive index layer was 82% by mass with respect to the total mass of the resin composition of the medium refractive index layer. Further, when elemental analysis was performed only on this medium refractive index layer by SEM-EDX analysis, the ratio (F / C) of the fluorine atom F (at%) to the carbon atom C (at%) in the layer was 0.23. Met.

<Formation of high refractive index layer>
Titanium oxide hard coat agent "Riodurus TYT80-01" manufactured by Toyo Ink Co., Ltd. (trade name, solid content concentration 25% by mass, refractive index 1.80 [nominal value]) 200.00 parts by mass and methyl isobutyl as a diluting solvent A high refractive index coating material A was prepared by blending 800.00 parts by mass of ketone with a diluent. Next, the high-refractive index paint A is applied onto the medium-refractive index layer using the microgravia coater so that the thickness after drying is 90 nm, dried, and then 300 mJ with a high-pressure mercury lamp. A high refractive index layer having a thickness of 90 nm was formed by irradiating with ultraviolet rays having a light amount of / cm ² and curing. The refractive index of the produced high refractive index layer was measured by the above-mentioned method and found to be 1.80.

<Formation of low refractive index layer>
The 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 and Chemicals Co., Ltd. was used as the low refractive index paint A as described above. The low refractive index paint A is applied onto the high refractive index layer using the microgravia coater so that the thickness after drying is 100 nm, dried, and then 300 mJ / cm ² with a high-pressure mercury lamp. A low refractive index layer having a thickness of 100 nm was formed by irradiating and curing a light amount of ultraviolet rays. When the refractive index of the produced low refractive index layer was measured by the above-mentioned method, it was 1.37.

As described above, an infrared reflective film (transparent heat shield heat insulating member) having a protective layer composed of an optical adjustment layer, a medium refractive index layer, a high refractive index layer and a low refractive index layer was produced. The thickness of the obtained protective layer was 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 side of which was treated with silicone, was prepared. In addition, an ultraviolet absorber (benzophenone) manufactured by Wako Pure Chemical Industries, Ltd. was used for 1000.00 parts by mass of the acrylic pressure-sensitive adhesive "SK Dyne 2094" (trade name, solid content: 25% by mass) manufactured by Soken Kagaku Co., 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 Kagaku Co., Ltd. were added and mixed with a disper to prepare an adhesive paint.

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

<Lasting with glass substrate>
First, as a glass substrate, float glass (manufactured 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 the adhesive layer is pressed. It was bonded to the central part of the float glass.

(Example 2)
Except for changing the amount of the isocyanate-based curing agent "Coronate HX" (trade name, cross-linking agent, solid content concentration 100% by mass) manufactured by Toso Co., Ltd. to 7.36 parts by mass (NCO / OH = 2.0). A medium refractive index paint B was produced in the same manner as in the medium refractive index paint A of Example 1, and a protective layer composed of four layers was provided in the same manner as in Example 1 except that the medium refractive index paint B was used. An infrared reflective film with an adhesive layer was prepared and attached to a glass substrate. The refractive index of the produced medium refractive index layer was measured by the above-mentioned method and found to be 1.46. The content of the fluororesin in the medium refractive index layer was 69% by mass with respect to the total mass of the resin composition of the medium refractive index layer. Further, when elemental analysis was performed only on this medium refractive index layer by SEM-EDX analysis, the ratio (F / C) of the fluorine atom F (at%) to the carbon atom C (at%) in the layer was 0.20. Met.

(Example 3)
Except for changing the amount of the isocyanate-based curing agent "Coronate HX" (trade name, cross-linking agent, solid content concentration 100% by mass) manufactured by Toso Co., Ltd. to 1.84 parts by mass (NCO / OH = 0.5). A medium refractive index paint C was produced in the same manner as in the medium refractive index paint A of Example 1, and a protective layer composed of four layers was provided in the same manner as in Example 1 except that the medium refractive index paint C was used. An infrared reflective film with an adhesive layer was prepared and attached to a glass substrate. The refractive index of the produced medium refractive index layer was measured by the above-mentioned method and found to be 1.46. The content of the fluororesin in the medium refractive index layer was 90% by mass with respect to the total mass of the resin composition of the medium refractive index layer. Further, when elemental analysis was performed only on this medium refractive index layer by SEM-EDX analysis, the ratio (F / C) of the fluorine atom F (at%) to the carbon atom C (at%) in the layer was 0.25. Met.

(Example 4)
<Making medium refractive index paint>
First, 45.06 parts by mass of the fluororesin "Obligard SS0057 main agent" (trade name, solid content concentration 38% by mass, hydroxyl group-containing CTFE-based copolymer) manufactured by AGC Cortec, and isocyanate-based curing manufactured by AGC Cortec. 3.47 parts by mass of the agent "Obligard SS0057 curing agent" (trade name, cross-linking agent, solid content concentration 83% by mass) and 951.47 parts by mass of methylisobutylketone as a diluting solvent are blended with a disper and medium refraction. A fluoropolymer D was produced.

An infrared reflective film with an adhesive layer having a protective layer consisting of four layers was prepared and bonded to a glass substrate in the same manner as in Example 1 except that the medium refractive index paint D was used. The refractive index of the produced medium refractive index layer was measured by the above-mentioned method and found to be 1.50. The content of the fluororesin in the medium refractive index layer was 86% by mass with respect to the total mass of the resin composition of the medium refractive index layer. Further, when elemental analysis was performed only on this medium refractive index layer by SEM-EDX analysis, the ratio (F / C) of the fluorine atom F (at%) to the carbon atom C (at%) in the layer was 0.19. Met.

(Example 5)
<Making medium refractive index paint>
First, AGC Asahi Glass Co., Ltd. fluororesin "Lumiflon LF-400" (trade name, solid content concentration 50% by mass, hydroxyl group-containing CTFE copolymer, hydroxyl value 47 mgKOH / g, acid value 5 mgKOH / g) 34.32 By mass, 2.84 parts by mass (NCO / OH = 1.0) of isocyanate-based curing agent "Coronate HX" (trade name, cross-linking agent, solid content concentration 100% by mass) manufactured by Toso Co., Ltd., and methyl as a diluting solvent. 962.84 parts by mass of the isocyanate-butyl ketone was blended with a diluent to prepare a medium refractive index coating material E.

An infrared reflective film with an adhesive layer having a protective layer consisting of four layers was prepared and bonded to a glass substrate in the same manner as in Example 1 except that the medium refractive index paint E was used. The refractive index of the produced medium refractive index layer was measured by the above-mentioned method and found to be 1.50. The content of the fluororesin in the medium refractive index layer was 86% by mass with respect to the total mass of the resin composition of the medium refractive index layer. Further, when elemental analysis was performed only on this medium refractive index layer by SEM-EDX analysis, the ratio (F / C) of the fluorine atom F (at%) to the carbon atom C (at%) in the layer was 0.19. Met.

(Example 6)
First, the fluororesin "Zeffle GK-510" manufactured by Daikin Industries, Ltd. (trade name, solid content concentration 50.0% by mass, hydroxyl group-containing TFE-based copolymer, hydroxyl value 60 mgKOH / g, acid value 11 mgKOH / g) 35 .33 parts by mass, 0.47 parts by mass (epoxide group / COOH = 1.0) of epoxy cross-linking agent "TEPIC-VL" (trade name, solid content concentration 100% by mass) manufactured by Nissan Chemical Industry Co., Ltd., and Toso Isocyanate-based curing agent "Coronate HX" (trade name, cross-linking agent, solid content concentration 100% by mass) manufactured by 1.87 parts by mass (NCO / OH = 0.5) and methylisobutylketone 962.33 as a diluting solvent. The parts by mass were blended with a disper to prepare a medium refractive index coating film F.

An infrared reflective film with an adhesive layer having a protective layer consisting of four layers was prepared and bonded to a glass substrate in the same manner as in Example 1 except that the medium refractive index paint F was used. The refractive index of the produced medium refractive index layer was measured by the above-mentioned method and found to be 1.46. The content of the fluororesin in the medium refractive index layer was 88% by mass with respect to the total mass of the resin composition of the medium refractive index layer. Furthermore, when elemental analysis was performed only on this medium refractive index layer by SEM-EDX analysis, the ratio (F / C) of the fluorine atom F (at%) to the carbon atom C (at%) in the layer was 0.21. Met.

(Example 7)
An infrared reflective film with an adhesive layer having a protective layer consisting of four layers was produced and bonded to a glass substrate 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. rice field.

<Formation of optical adjustment layer>
First, the titanium oxide ultrafine particles "TTO-55 (A)" (trade name) manufactured by Ishihara Sangyo Co., Ltd. (trade name) 13.92 parts by mass and the fluororesin "Zeffle GK-570" (trade name, solid content) manufactured by Daikin Kogyo Co., Ltd. A mixed solution is prepared by mixing 12.67 parts by mass of a TFE-based copolymer containing 65.0% by mass, a hydroxyl value of 64 mgKOH / g, and an acid value of 4 mgKOH / g) and 47.27 parts by mass of methylisobutylketone. Prepared. Zirconia beads having a diameter of 0.3 mm were added to this mixed solution and subjected to dispersion treatment 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, 1.86 parts by mass (NCO / OH = 1.0) of an isocyanate-based curing agent "Coronate HX" (trade name, cross-linking agent, solid content concentration 100% by mass) manufactured by Tosoh Corporation was added. , 924.28 parts by mass of methylisobutylketone as a diluting solvent was blended with a disper to prepare an optically adjusting paint B. Next, the optical adjustment paint B was applied onto the infrared reflective layer used in Example 1 using a microgravure coater (manufactured by Yasui Seiki Co., Ltd.) so that the thickness after drying was 50 nm. An optical adjustment layer having a thickness of 50 nm was formed by drying at 120 ° C. for 2 minutes and thermosetting. When the refractive index of the produced optical adjustment layer was measured by the above-mentioned method, it was 1.79. The content of the fluororesin in the resin composition of the optical adjustment layer was 82% by mass with respect to the total mass of the resin composition of the optical adjustment layer. Further, when only the resin composition of this optical adjustment layer was subjected to elemental analysis by SEM-EDX analysis, the ratio of fluorine atom F (at%) to carbon atom C (at%) in the resin composition (F / C). ) Was 0.23.

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

(Example 8)
Medium in the same manner as in Example 1 except that the thickness of the medium refractive index layer after drying was changed to 150 nm and the thickness of the high refractive index layer after drying was changed to 290 nm without providing the optical adjustment layer. An infrared reflective film with an adhesive layer provided with a protective layer composed of a refractive index layer, a high refractive index layer, and a low refractive index layer was prepared and attached to a glass substrate. The thickness of the obtained protective layer was 540 nm.

(Example 9)
The same as in Example 1 except that the formation of the high refractive index layer was changed to the following and the thickness of the low refractive index layer after drying was changed to 95 nm without providing the optical adjustment layer and the medium refractive index layer. An infrared reflective film with an adhesive layer provided with a protective layer composed of two layers, a high refractive index layer and a low refractive index layer, was produced and bonded to a glass substrate. The thickness of the obtained 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 fluororesin "Zeffle GK-570" (trade name, solid content) manufactured by Daikin Kogyo Co., Ltd. A mixed solution is prepared by mixing 26.40 parts by mass of a TFE-based copolymer containing 65.0% by mass, a hydroxyl value of 64 mgKOH / g, and an acid value of 4 mgKOH / g) and 98.47 parts by mass of methylisobutylketone. Prepared. Zirconia beads having a diameter of 0.3 mm were added to this mixed solution and subjected to dispersion treatment 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, an isocyanate-based curing agent "Coronate HX" (trade name, cross-linking agent, solid content concentration 100% by mass) manufactured by Tosoh Corporation was added to 3.87 parts by mass (NCO / OH = 1.0). , Methylisobutylketone 842.30 parts by mass as a diluting solvent was blended with a disper to prepare a high refractive index coating material B. Next, the high-refractive index paint B was applied onto the infrared reflective layer used in Example 1 using a microgravure coater (manufactured by Yasui 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. When the refractive index of the produced high refractive index layer was measured by the above-mentioned method, it was 1.79. The content of the fluororesin in the resin composition of the high refractive index layer was 82% by mass with respect to the total mass of the resin composition of the high refractive index layer. Further, when only the resin composition of this high refractive index layer was subjected to elemental analysis by SEM-EDX analysis, the ratio of the fluorine atom F (at%) to the carbon atom C (at%) in the resin composition (F / C) was 0.23.

(Example 10)
<Making medium refractive index paint>
First, the fluororesin "Zeffle GK-570" manufactured by Daikin Industries, Ltd. (trade name, solid content concentration 65.0% by mass, hydroxyl group-containing TFE-based copolymer, hydroxyl value 64 mgKOH / g, acid value 4 mgKOH / g) 20 .27 parts by mass and 7.40 parts by mass of acrylic polyol resin "Acryt 6AN-6000" (trade name, solid content concentration 44.5% by mass, hydroxyl value 48 mgKOH / g, acid value 6 mgKOH / g) manufactured by Taisei Fine Chemicals Co., Ltd. And 3.53 parts by mass (NCO / OH = 1.0) of the isocyanate-based curing agent "Coronate HX" (trade name, cross-linking agent, solid content concentration 100% by mass) manufactured by Toso Co., Ltd., and methylisobutylketone as a diluting solvent. 968.80 parts by mass was blended with a disper to prepare a medium refractive index coating material H.

An infrared reflective film with an adhesive layer having a protective layer consisting of four layers was prepared and bonded to a glass substrate in the same manner as in Example 1 except that the medium refractive index paint H was used. When the refractive index of the produced medium refractive index layer was measured by the above-mentioned method, it was 1.47. The content of the fluororesin in the medium refractive index layer was 66% by mass with respect to the total mass of the resin composition of the medium refractive index layer. Furthermore, when elemental analysis was performed only on this medium refractive index layer by SEM-EDX analysis, the ratio (F / C) of the fluorine atom F (at%) to the carbon atom C (at%) in the layer was 0.18. Met.

(Example 11)
Except for changing the amount of the isocyanate-based curing agent "Coronate HX" (trade name, cross-linking agent, solid content concentration 100% by mass) manufactured by Toso Co., Ltd. to 6.00 parts by mass (NCO / OH = 2.0). A medium refractive index paint I was produced in the same manner as in the medium refractive index paint H of Example 10, and a protective layer composed of four layers was provided in the same manner as in Example 1 except that the medium refractive index paint I was used. An infrared reflective film with an adhesive layer was prepared and attached to a glass substrate. When the refractive index of the produced medium refractive index layer was measured by the above-mentioned method, it was 1.47. The content of the fluororesin in the medium refractive index layer was 56% by mass with respect to the total mass of the resin composition of the medium refractive index layer. Further, when elemental analysis was performed only on this medium refractive index layer by SEM-EDX analysis, the ratio (F / C) of the fluorine atom F (at%) to the carbon atom C (at%) in the layer was 0.15. Met.

(Example 12)
<Making medium refractive index paint>
First, the fluororesin "Zeffle GK-570" manufactured by Daikin Industries, Ltd. (trade name, solid content concentration 65.0% by mass, hydroxyl group-containing TFE-based copolymer, hydroxyl value 64 mgKOH / g, acid value 4 mgKOH / g) 12 .56 parts by mass and 12.23 parts by mass of acrylic polyol resin "Acryt 6AN-6000" (trade name, solid content concentration 44.5% by mass, hydroxyl value 48 mgKOH / g, acid value 6 mgKOH / g) manufactured by Taisei Fine Chemicals Co., Ltd. 4.14 parts by mass (NCO / OH = 1.5) of the isocyanate-based curing agent "Coronate HX" (trade name, cross-linking agent, solid content concentration 100% by mass) manufactured by Toso Co., Ltd., and the isocyanate-based curing agent manufactured by Toso Co., Ltd. Hardener "Coronate HL" (trade name, cross-linking agent, solid content concentration 75% by mass) 3.01 parts by mass (NCO / OH = 0.5), and methylisobutylketone 968.06 parts by mass as a diluting solvent as a disper To prepare a medium refractive index paint J.

An infrared reflective film with an adhesive layer having a protective layer consisting of four layers was prepared and bonded to a glass substrate in the same manner as in Example 1 except that the medium refractive index paint J was used. The refractive index of the produced medium refractive index layer was measured by the above-mentioned method and found to be 1.49. The content of the fluororesin in the medium refractive index layer was 41% by mass with respect to the total mass of the resin composition of the medium refractive index layer. Further, when elemental analysis was performed only on this medium refractive index layer by SEM-EDX analysis, the ratio (F / C) of the fluorine atom F (at%) to the carbon atom C (at%) in the layer was 0.11. Met.

(Example 13)
<Making medium refractive index paint>
First, AGC Asahi Glass Co., Ltd.'s fluororesin "Lumiflon LF-400" (trade name, solid content concentration 50% by mass, hydroxyl group-containing CTFE copolymer, hydroxyl value 47 mgKOH / g, acid value 5 mgKOH / g) 13.31 12.96 parts by mass and 12.96 parts by mass of acrylic polyol resin "Acryt 6AN-6000" (trade name, solid content concentration 44.5% by mass, hydroxyl value 48 mgKOH / g, acid value 6 mgKOH / g) manufactured by Taisei Fine Chemicals Co., Ltd. Isocyanate-based curing agent "Coronate HX" manufactured by Toso Co., Ltd. (trade name, cross-linking agent, solid content concentration 100% by mass) 3.61 parts by mass (NCO / OH = 1.5) and isocyanate-based curing agent manufactured by Toso Co., Ltd. "Coronate HL" (trade name, cross-linking agent, solid content concentration 75% by mass) 2.63 parts by mass (NCO / OH = 0.5), and 967.49 parts by mass of methyl isocyanate butyl ketone as a diluting solvent are mixed with a disper. Then, the medium refractive index coating material K was produced.

An infrared reflective film with an adhesive layer having a protective layer consisting of four layers was prepared and bonded to a glass substrate in the same manner as in Example 1 except that the medium refractive index paint K was used. The refractive index of the produced medium refractive index layer was measured by the above-mentioned method and found to be 1.51. The content of the fluororesin in the medium refractive index layer was 41% by mass with respect to the total mass of the resin composition of the medium refractive index layer. Furthermore, when elemental analysis was performed only on this medium refractive index layer by SEM-EDX analysis, the ratio (F / C) of the fluorine atom F (at%) to the carbon atom C (at%) in the layer was 0.08. Met.

(Example 14)
An optical adjustment paint similar to the optical adjustment paint A of Example 1 except that 2-mercaptobenzothiazole having a sulfur-containing group was changed to 1-o-tolylbiguanide having a nitrogen-containing group as a corrosion inhibitor for metals. C was prepared, and an infrared reflective film with an adhesive layer having a protective layer consisting of four layers was prepared and bonded to a glass substrate in the same manner as in Example 1 except that the optical adjusting paint C was used. When the refractive index of the produced optical adjustment layer was measured by the above-mentioned method, it was 1.79.

(Example 15)
An optical adjustment paint D was prepared in the same manner as the optical adjustment paint A of Example 1 except that 2-mercaptobenzothiazole having a sulfur-containing group was not added as a corrosion inhibitor for metals, and the optical adjustment paint D was used. An infrared reflective film with an adhesive layer having a protective layer consisting of four layers was prepared and bonded to a glass substrate in the same manner as in Example 1 except that it was used. The refractive index of the produced optical adjustment layer was measured by the above-mentioned method and found to be 1.80.

(Example 16)
An 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 after drying was changed to 500 nm. An infrared reflective film with a refraction was prepared and attached to a glass substrate. The thickness of the obtained protective layer was 780 nm.

(Example 17)
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. An infrared reflective film with an adhesive layer having a protective layer consisting of four layers was produced in the same manner as in Example 1 except that the thickness was changed to 550 nm and the thickness of the low refractive index layer after drying was changed to 120 nm. 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)] is 12 nm. The ratio of the thickness of the second metal suboxide layer (TiO _X layer) to the total thickness was 16.7%. The thickness of the obtained protective layer was 930 nm.

(Example 18)
The same as in Example 1 except that the thickness of the medium refractive index layer after drying was changed to 150 nm, the thickness of the high refractive index layer after drying was changed to 700 nm, and the thickness of the low refractive index layer after drying was changed to 110 nm. An infrared reflective film with an adhesive layer having a protective layer composed of four layers was prepared and attached to a glass substrate. The thickness of the obtained protective layer was 1010 nm.

(Example 19)
Infrared reflection with an 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 second metal suboxide layer (TiO _X layer) of the infrared reflective layer was changed to 4 nm. A film was prepared and 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 suboxide layer (TiO _X layer)] is 18 nm. The ratio of the thickness of the second metal suboxide layer (TiO _X layer) to the total thickness was 22.2%.

(Example 20)
<Manufacturing a transparent substrate with an infrared reflective layer>
First, the above-mentioned PET film "U483" (thickness: 50 μm) having both sides easily adhered was used as a transparent base material, and the first metal suboxide layer and metal from the PET film side were used on one side of the PET film. The layer and the second metal oxide layer were formed as follows. First, using a titanium target, a first metal suboxide layer (TiO _X layer) having a thickness of 2 nm was formed by a reactive sputtering method. As the sputtering gas in the above reactive sputtering method, a mixed gas of Ar / O ₂ was used, and the gas flow rate / _volume ratio was Ar 97% / O 23%. Subsequently, a metal layer (Ag layer) having a thickness of 13 nm was formed on the metal suboxide layer by a sputtering method using a silver target. As the sputtering gas in the above sputtering method, 100% Ar gas was used. Further, a second metal oxide layer (TiO ₂ layer) having a thickness of 5 nm was formed on the metal layer by a sputtering method using a titanium oxide target. As the sputtering gas in the above sputtering method, 100% Ar gas was used. As a result, an infrared reflective layer having a three-layer structure consisting 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. A PET film with a metal was prepared. The x of the TiO _X layer was 1.5.

An infrared reflective film with an adhesive layer having a protective layer consisting of four layers was prepared and bonded to a glass substrate in the same manner as in Example 1 except that the PET film with an infrared reflective layer was used. 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)] is 20 nm. The ratio of the thickness of the second metal oxide layer (TIO ₂ layer) to the total thickness was 25.0%.

(Example 21)
An infrared reflective film with an adhesive layer provided with a protective layer consisting of four layers in the same manner as in Example 20 except that the thickness of the second metal oxide layer (TIO ₂ layer) of the infrared reflective layer is changed to 7 nm. Was prepared and 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)] is 22 nm. The ratio of the thickness of the second metal oxide layer (TIO ₂ layer) to the total thickness was 31.8%.

(Example 22)
<Manufacturing a transparent substrate with an infrared reflective layer>
First, the above-mentioned PET film "U483" (thickness: 50 μm) having both sides easily adhered was used as a transparent base material, and a first metal oxide layer and a metal layer from the PET film side were used on one side of the PET film. , The second metal suboxide layer was formed as follows. First, using a titanium oxide target, a first metal oxide layer (TiO ₂ layer) having a thickness of 2 nm was formed by a sputtering method. As the sputtering gas in the above sputtering method, 100% Ar gas was used. Subsequently, a metal layer (Ag layer) having a thickness of 12 nm was formed on the metal oxide layer by a sputtering method using a silver target. As the sputtering gas in the above sputtering method, 100% Ar gas was used. Further, a second 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 above reactive sputtering method, a mixed gas of Ar / O ₂ was used, and the gas flow rate / _volume ratio was Ar 97% / O 23%. As a result, an infrared reflective layer having a three-layer structure consisting 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. A PET film with a metal was prepared. The x of the TiO _X layer was 1.5.

An infrared reflective film with an adhesive layer having a protective layer consisting of four layers was prepared and bonded to a glass substrate in the same manner as in Example 1 except that the PET film with an infrared reflective layer was used. 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)] is 16 nm. The ratio of the thickness of the second metal suboxide layer (TIO _X layer) to the total thickness was 12.5%.

(Example 23)
<Formation of medium refractive index layer (lower layer)>
First, the medium refractive index paint D used in Example 4 was applied to the infrared reflective layer used in Example 1 using the above microgravure coater so that the thickness after drying was 60 nm, and the temperature was 120 ° C. A medium refractive index layer (lower layer) having a thickness of 60 nm was formed by drying and heat-curing the mixture for 2 minutes. The refractive index of the produced medium refractive index layer (lower layer) was measured by the above-mentioned method and found to be 1.50. The content of the fluororesin in the medium refractive index layer (lower layer) was 86% by mass with respect to the total mass of the resin composition of the medium refractive index layer (lower layer). Furthermore, when elemental analysis was performed on only this middle refractive index layer (lower layer) by SEM-EDX analysis, the ratio (F / C) of the fluorine atom F (at%) to the carbon atom C (at%) in the layer was found. It was 0.19.

<Formation of medium refractive index layer (upper layer)>
165.40 parts by mass of ionizing radiation curable acrylic polymer solution "SMP-250A" (trade name, solid content concentration 50% by mass) manufactured by Kyoeisha Chemical Co., Ltd. and a phosphate group-containing methacrylic acid derivative "light ester" manufactured by Kyoeisha Chemical Co., Ltd. 8.30 parts by mass of P-2M "(trade name) and 8.30 parts by mass of solvent-containing urethane (meth) acrylate monomer" Fomblin MT70 "(trade name, solid content concentration 80% by mass) manufactured by Solvay Specialty Polymers Japan. 1.30 parts by mass of the silicone-modified acrylate "TEGO Rad 2650" manufactured by Ebonic Degusa Japan, 4.80 parts by mass of the photopolymerization initiator "Irgacure 819" (trade name) manufactured by BASF, and a diluting solvent. As a result, 815.40 parts by mass of methyl isobutyl ketone was blended with a disper to prepare a medium refractive index coating material L. Next, the medium refractive index paint L is applied onto the medium refractive index layer (lower layer) using the microgravia coater so that the thickness after drying is 920 nm, dried, and then a high-pressure mercury lamp. A medium refractive index layer (upper layer) having a thickness of 920 nm was formed by irradiating with ultraviolet rays having a light amount of 300 mJ / cm ² and curing the mixture. The refractive index of the produced medium refractive index layer (upper layer) was measured by the above-mentioned method and found to be 1.49.

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 composed of two layers, 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 an infrared reflective layer provided with the protective layer was used. An infrared reflective film with an adhesive layer was prepared and attached to a glass substrate. The thickness of the obtained protective layer was 980 nm.

(Example 24)
A protective layer composed of two layers, a middle refractive index layer (lower layer) and a middle refractive index layer (upper layer), was provided in the same manner as in Example 23 except that the thickness of the middle refractive index layer (upper layer) was changed to 620 nm. An infrared reflective film with an adhesive layer was prepared and attached to a glass substrate. The thickness of the obtained protective layer was 680 nm.

(Comparative Example 1)
An infrared reflective film with an adhesive layer having a protective layer consisting of four layers was prepared and attached to a glass substrate in the same manner as in Example 15 except that the formation of the medium refractive index layer was changed to the following.

<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 903.53 parts of butyl acetate as a diluting solvent. And were blended with a dispersion to prepare a medium refractive index paint M. The medium refractive index paint M is applied onto the optical adjustment layer using the microgravia coater so that the thickness after drying is 60 nm, and after drying, the amount of light is 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 the medium refractive index layer. The refractive index of the produced medium refractive index layer was measured by the above-mentioned method and found to be 1.52.

(Comparative Example 2)
<Manufacturing a transparent substrate with an infrared reflective layer>
First, the above-mentioned PET film "U483" (thickness: 50 μm) having both sides easily adhered was used as a transparent base material, and a first metal oxide layer and a metal layer from the PET film side were used on one side of the PET film. , The second metal oxide layer was formed as follows. First, a first metal oxide layer (ZTO layer) having a thickness of 10 nm was formed by a reactive sputtering method using a target having a metal composition of tin / zinc = 90% by mass / 10% by mass. As the sputtering gas in the above reactive sputtering method, a mixed gas of Ar / O ₂ was used, and the gas flow rate / _volume ratio was Ar 97% / O 23%. Subsequently, a metal layer (Ag layer) having a thickness of 12 nm was formed on the metal oxide layer by a sputtering method using a silver target. As the sputtering gas in the above sputtering method, 100% Ar gas was used. 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. bottom. As the sputtering gas in the above reactive sputtering method, a mixed gas of Ar / O ₂ was used, and the gas flow rate / _volume ratio was Ar 97% / O 23%. As a result, 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 paint A used in Example 1 is coated on the infrared reflective layer using the microgravia coater (manufactured by Yasui Seiki Co., Ltd.) so that the thickness after drying is 60 nm, and dried. After that, a low refractive index layer having a thickness of 60 nm was formed by irradiating with an ultraviolet ray having a light amount of 300 mJ / cm ² with a high-pressure mercury lamp and curing the mixture. When the refractive index of the produced low refractive index layer was measured by the above-mentioned method, it was 1.37.

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

(Comparative Example 3)
<Formation of medium refractive index layer>
The medium refractive index paint L used in Example 23 was coated on the infrared reflective layer used in Comparative Example 2 using the above microgravia coater (manufactured by Yasui 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 with an ultraviolet ray having a light amount of 300 mJ / cm ² with a high-pressure mercury lamp and curing the mixture. The refractive index of the produced medium refractive index layer was measured by the above-mentioned method and found to be 1.49.

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

(Comparative Example 4)
Instead of the low refractive index layer which is a layer located on the outermost surface side of the protective layer of Comparative Example 1, the medium refractive index layer of Example 1 is a layer (thickness 100 nm) located on the outermost surface side of the protective layer. An infrared reflective film with an adhesive layer having a protective layer consisting of four layers was produced in the same manner as in Comparative Example 1 except that the film was coated and formed (dried at 120 ° C. for 2 minutes and heat-cured). I pasted it on.

<Evaluation of transparent heat shield and heat insulating material>
Regarding Examples 1 to 24 and Comparative Examples 1 to 4, the visible light transmittance, the visible light reflectance, and the visible light reflectance of the infrared reflective film (transparent heat-shielding and heat insulating member) in a state of being attached to the glass substrate. The maximum fluctuation difference, solar radiation absorption rate, shielding coefficient, and heat transmittance were measured as follows, and the salt water resistance, scratch resistance, and appearance of the infrared reflective film were evaluated.

[Visible Light Transmittance]
The visible light transmittance is measured by using an ultraviolet visible near-infrared spectrophotometer "Ubest V-570" (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 based on JIS A5759-2008.

[Visible light reflectance]
The visible light reflectance is measured by measuring the spectral reflectance using the ultraviolet-visible near-infrared spectrophotometer "Ubest V-570" in the wavelength range of 380 to 780 nm with the glass substrate side as the incident light side, and JIS. Calculated according to R3106-1998.

[Maximum variation difference in reflectance]
With the glass substrate side as the incident light side, the spectral reflectance is measured in the range of 300 to 800 nm using the ultraviolet-visible near-infrared spectrophotometer "Ubest V-570" (trade name) manufactured by JASCO Corporation. It was measured based on. From the measured visible light reflection spectrum, the "maximum fluctuation difference ΔA" and the "maximum fluctuation difference ΔB" of the reflectance were obtained by the above-mentioned method.

[Solar absorption rate]
For the solar radiation absorption rate, the spectral transmittance and the spectral reflectance are measured using the ultraviolet-visible near-infrared spectrophotometer "Ubest V-570" 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 transmittance and the solar reflectance obtained in accordance with JIS A5759-2008.

[Shielding coefficient]
The shielding coefficient is measured by measuring the spectral transmittance and the spectral reflectance using the ultraviolet-visible near-infrared spectrophotometer "Ubest V-570" in the wavelength range of 300 to 2500 nm with the glass substrate side as the incident light side. , JIS A5759 was used to determine the solar transmittance and reflectance, and JIS R3106-2008 was used to determine the vertical emissivity, which was determined from the values of the solar transmittance, solar reflectance and vertical emissivity.

[Thermal transmission rate]
For the heat transmission coefficient, an attachment for positive reflection measurement is attached to the infrared spectrophotometer "IR Pressige21" (trade name) manufactured by Shimadzu Corporation, and the spectral normal reflectance on the protective layer side and the glass substrate side of the infrared reflective film is set to a wavelength of 5. Measured in the range of .5 to 25.2 μm, determine the vertical emissivity of the protective layer side and glass substrate side of the infrared reflective film according to JIS R3106-2008, and based on this, heat according to JIS A5759-2008. The emissivity was calculated.

[Salt water resistance]
First, using the ultraviolet-visible near-infrared spectrophotometer "Ubest V-570", the spectral transmittance of the infrared reflective film attached to the glass substrate in the wavelength range of 300 to 1500 nm was measured, and the light having a wavelength of 1100 nm was measured. Transmittance _TB (in% units) was measured. Then, the infrared reflective film attached to the glass substrate was immersed in a 5% by mass sodium chloride aqueous solution, placed in a constant temperature and humidity chamber at 50 ° C. in this state, and stored for 30 days for a salt water resistance test. After the completion of the salt water resistance test, the infrared reflective film attached to the glass substrate was washed with pure water and naturally dried. Subsequently, in the same manner as described above, the transmittance _TA (in% units) 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. From the above measurement results, the point value of TA _{- TB} was calculated as the difference in the 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 shield and heat insulating member is within a constant field of view after the white flannel cloth is placed on the protective layer and the white flannel cloth is reciprocated 1000 times with a load of 1000 g / cm ² applied. The state of the surface of the protective layer was visually observed and evaluated in the following three stages.
Excellent: When no scratches are made Good: When several scratches (5 or less) are confirmed Defective: When many scratches (6 or more) are confirmed

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

The above results are shown in Tables 1 to 7 together with the layer structure of the infrared reflective film (transparent heat shield and heat insulating member).

As shown in Tables 1 to 6, the infrared reflective films (transparent heat-shielding and heat-insulating members) of all the examples except Examples 7 and 9 are also good in the salt water resistance test assuming a harsh external environment. The results are shown, and even if dew condensation water, human sebum, sweat, etc. adhere to the film surface, the metal layer of the infrared reflective layer does not corrode and deteriorate in a short period of time. Further, since the visible light transmittance is large and the fluctuation difference of the visible light reflectance is small, the transparency and appearance are not impaired even when the visible light is attached to the window glass. In addition, the shielding coefficient and thermal transmission rate 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 level where there is no problem in practical use. Furthermore, since the solar absorption rate is small, it is unlikely that the glass will be thermally cracked after being applied to the window glass. That is, it can be seen that a well-balanced transparent heat-shielding and heat-insulating member is practically obtained.

In Examples 7 and 9, respectively, an optical adjustment layer containing a large amount of inorganic fine particles and a high refractive index layer are used as a layer containing a fluorine-containing resin having a curable functional group and a cross-linking agent that reacts with the curable functional group. Therefore, as compared with other examples in which the medium refractive index layer containing no inorganic fine particles is a layer containing a fluororesin having a curable functional group and a cross-linking agent that reacts with the curable functional group, it is salt resistant. It was slightly inferior in the aqueous test.

In Example 15, since the layer in contact with the metal suboxide layer does not contain a corrosion inhibitor for metal, the layer in contact with the metal suboxide layer contains a corrosion inhibitor for metal. It was slightly inferior in the salt water resistance test as compared with Example 14.

Example 18 showed good results in the salt water resistance test, but since the total thickness of the protective layer was slightly thick at 1010 nm, the thermal transmissivity was slightly large at 4.3 W / (m ² · K), and protection was achieved. The thermal insulation performance was slightly inferior as compared with other examples in which the total thickness of the layer was 980 nm or less.

Example 21 showed good results in the salt water resistance test, but the thickness of the second metal oxide layer (TIO ₂ layer) of the infrared reflective layer was 7 nm, which was the total thickness of the infrared reflective layer. Since it corresponds to 31.8%, which exceeds 25%, the solar absorption rate is as large as 22.2%, and compared with other examples in which the solar absorption rate is 20% or less, when it is applied to the window glass. The risk of thermal cracking of the glass became high.

Although Examples 23 and 24 showed good results in the salt water resistance test, since the protective layer is composed of two layers having a medium refractive index layer, the protective layer is composed of a laminated structure having a different refractive index range. Compared with the example, the visible light transmittance and the appearance were slightly inferior.

On the other hand, as shown in Table 7, Comparative Example 1 is a fluororesin having a curable functional group in any of the layers other than the layer located on the outermost surface side of the protective layer composed of a plurality of layers. Since it does not contain a cross-linking agent that reacts with the curable functional group, the protective layer is peeled off in the salt water resistance test, the infrared reflective layer causes corrosion deterioration, and the TA _{- TB} value is also 50. It became as large as 0 points. That is, it has almost no heat-shielding and heat-insulating function.

Further, in Comparative Examples 2 and 3, the protective layer is composed of one layer of low refractive index layer and one layer of medium refractive index layer, respectively, and the fluororesin having a curable functional group in the layer and the curable functional group. Since it does not contain a cross-linking agent that reacts with, in the salt water resistance test, the protective layer peels off and the infrared reflective layer causes corrosion deterioration, and the TA _{- TB} values are also 35.0 points, respectively. , 29.5 points. That is, it has almost no heat-shielding and heat-insulating function. Further, 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 31. Since it corresponds to 3%, the solar absorption rate increased to 20.9% and 21.5%, respectively, and the risk of thermal cracking of the glass when applied to the window glass became high. Further, in Comparative Example 2, since the thickness of the protective layer was as thin as 60 nm, the scratch resistance was inferior. Further, in Comparative Example 3, the protective layer was one layer of the medium refractive index layer, and the thickness was 680 nm, which overlapped with the wavelength region of visible light, so that the appearance was inferior.

Further, in Comparative Example 4, among the protective layers composed of multiple layers, the layer located on the outermost surface side contains a fluororesin having a curable functional group and a cross-linking agent that reacts with the curable functional group. Since the refractive index layer was applied, good results were shown in the salt water resistance test, but the medium refractive index layer located on the outermost surface side does not contain an ionizing radiation curable resin, and therefore is inferior in scratch resistance. It was a thing.

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

10 Transparent heat shield and heat insulating member 11 Transparent base material 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 refraction rate layer 17 High refraction layer 18 Low refraction layer 19 Adhesive layer 21 Infrared reflective layer 22 Coating type protective layer 23 Functional layer

Claims (17)

A transparent heat-shielding and heat-insulating member including a transparent base material and a functional layer formed on the transparent base material.
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 includes at least a metal layer and a metal suboxide layer or a metal oxide layer in this order from the transparent substrate side.
The coating type protective layer is composed of a plurality of layers.
Of the coating type protective layers, at least one layer other than the layer located on the outermost surface side reacts with the fluororesin having a curable functional group and the curable functional group as a pre-curing resin component. It consists of a layer containing a cross-linking agent and
A transparent heat-shielding and heat-insulating member characterized in that the layer located on the outermost surface side of the coating-type protective layer is composed of a layer containing an ionizing radiation-curable resin as a pre-curing resin component. The content of the fluororesin having a curable functional group is based on the total mass of the resin composition of the layer containing the fluororesin having the curable functional group and the cross-linking agent that reacts with the curable functional group. , The transparent heat-shielding and heat-insulating member according to claim 1, which is 34% by mass or more and 94% by mass or less. The layer containing the fluororesin having a curable functional group and the cross-linking agent that reacts with the curable functional group is a resin after curing of the layer as measured by elemental analysis by energy dispersive X-ray (EDX) analysis. Claim 1 or 2 in which the ratio (F / C) of the fluorine atom F (at%: atomic percent) to the carbon atom C (at%: atomic percent) in the composition is 0.08 or more and 0.30 or less. The transparent heat shield and heat insulating member described. The transparent heat-shielding heat insulating member according to any one of claims 1 to 3, wherein the curable functional group of the fluororesin having a curable functional group is a hydroxyl group, and the cross-linking agent is a polyisocyanate compound. The fluororesin having a curable functional group is composed of a group consisting of a hydroxyl group-containing perfluoroolefin polymer mainly composed of a perfluoroolefin unit and a hydroxyl group-containing chlorotrifluoroethylene polymer mainly composed of a chlorotrifluoroethylene unit. The transparent heat-shielding and heat-insulating member according to any one of claims 1 to 4, which is at least one selected copolymer polymer. The coating type protective layer includes a medium refractive index layer, a high refractive index layer, and a low refractive index layer in this order from the infrared reflective layer side, and the medium refractive index layer is the curable as a pre-curing resin component. The transparent heat-shielding heat insulating member according to any one of claims 1 to 5, which comprises a fluororesin having a functional group and a cross-linking agent that reacts with the curable functional 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 reflective layer side, and the medium refractive index layer is used as a resin component before curing. The transparent heat-shielding heat insulating member according to any one of claims 1 to 6, which comprises a fluororesin having a curable functional group and a cross-linking agent that reacts with the curable functional group. The transparent heat-shielding and heat-insulating member according to any one of claims 1 to 7, wherein the total thickness of the coating type protective layer is 200 nm or more and 980 nm or less. The transparent heat-shielding heat insulating layer according to any one of claims 1 to 8, wherein at least the layer in contact with the metal suboxide layer or the metal oxide layer among the coating type protective layers contains a corrosion inhibitor for metal. Element. The transparent heat-shielding and heat-insulating member according to claim 9, 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 reflective layer includes a first metal suboxide layer or a metal oxide layer, a metal layer, a second metal suboxide layer or a metal oxide layer in this order from the transparent substrate side, and the infrared rays. The claim that 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. The transparent heat-shielding and heat-insulating member according to any one of 1 to 10. The transparent heat-shielding heat insulating member according to claim 11, wherein the metal suboxide or metal oxide contained in the second metal suboxide layer or metal oxide layer of the infrared reflective layer contains a titanium component. The transparent heat-shielding heat insulating member according to any one of claims 1 to 12, wherein 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. The transparent heat-shielding and heat-insulating member has a visible light transmittance of 60% or more, a shielding coefficient of 0.69 or less, a thermal transmission rate of 4.0 W / (m ² · K) or less, and a solar radiation absorption rate of 20. The transparent heat-shielding and heat-insulating member according to any one of claims 1 to 13, which is% or less. When the transparent heat-shielding and heat-insulating member is immersed in a sodium chloride aqueous solution having a temperature of 50 ° C. and a concentration of 5% by mass for 30 days, the wavelength 300 of the transparent heat-shielding and heat-insulating member measured before the salt-water resistance test. The transmission of light with a wavelength of 1100 nm in the transmission spectrum in the range of ~ 1500 nm is _TB %, and the transmission of light with a wavelength of 1100 nm in the transmission spectrum in the range of wavelength of 300 to 1500 nm of the transparent heat shield and heat insulating member measured after the salt water resistance test. The transparent heat-shielding and heat-insulating member according to any one of claims 1 to 14, wherein the value of TA _{- TB} is less than 10 points, where the rate is _TA %. In the reflection spectrum measured according to JIS R3106-1998,
A point corresponding to the wavelength 535 nm on the virtual line a showing 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 a point A, and the wavelength range of the reflection spectrum is 620 to 780 nm. The point corresponding to the wavelength of 700 nm on the virtual line b showing the average value of the maximum reflectance and the minimum reflectance is set as a point B, and the straight line passing through the point A and the point B is extended in the wavelength range of 500 to 780 nm. The reference straight line AB is used.
When the value of the reflectance of the reflection spectrum in the wavelength range of 500 to 570 nm and the value of the reflectance of the reference straight line AB are compared, the value of the reflectance at the wavelength at which the difference between the values of the respective reflectances is maximum. When the absolute value of the difference is defined as the maximum fluctuation difference ΔA, the value of the maximum fluctuation difference ΔA is 7% or less in% of the reflectance.
When the value of the reflectance of the reflection spectrum in the wavelength range of 620 to 780 nm and the value of the reflectance of the reference straight line AB are compared, the value of the reflectance at the wavelength at which the difference between the values of the respective reflectances is maximum. The transparent heat shield according to any one of claims 1 to 15, 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 the reflectance. Insulation member. The method for manufacturing a transparent heat-shielding and heat-insulating member according to any one of claims 1 to 16.
The process of forming an infrared reflective layer on a transparent substrate by the dry coating method,
A method for manufacturing a transparent heat-shielding and heat-insulating member, which comprises a step of forming a protective layer composed of a plurality of layers on the infrared reflective layer by a wet coating method.

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