Patent Application
20170136740
1. Field of the Invention
The present invention relates to a heat insulating window film, a heat insulating window glass, and a window. More specifically, the invention relates to a heat insulating window film having excellent heat insulating properties and radio-wave transmittance, a heat insulating window glass using this heat insulating window film, and a window using this heat insulating window film.
2. Description of the Related Art
In recent years, products with a lower environmental burden, which are so-called eco-friendly products have been required as one of energy saving measures for carbon dioxide reduction, and solar control window films for windows of vehicles or buildings have been required. A heat insulating window film is considered as such a product. The heat insulating window film is a film which delays transmission and reception of heat between an indoor side and an outdoor side by being attached to windows, and usage of heating and cooling is reduced by using this film, and therefore, energy saving can be expected. A degree of heat insulation is defined by using a coefficient of overall heat transmission. In the solar control window film procurement standard in the Law Concerning the Promotion of Procurement of Eco-Friendly Goods and Services by the State and Other Entities (so-called Green Purchasing Law), heat insulating properties are determined to be obtained when a coefficient of overall heat transmission is less than 5.9 W/(m2·K) measured by using a measurement method based on JIS A 5759 “Films for window glasses of buildings” (JIS stands for Japanese Industrial Standards). When the numerical value thereof is small, the transmission of heat is delayed and heat insulating properties are increased. According to JIS A 5759, a coefficient of overall heat transmission can be acquired from reflection spectra of far infrared rays at a wavelength of 5 μm to 50 μm. That is, it is preferable to increase reflectivity of far infrared rays at a wavelength of 5 μm to 50 μm, in order to decrease a coefficient of overall heat transmission.
Fibrous conductive particles are known as a material of a heat ray shielding film. JP2012-252172A, for example, discloses a heat ray shielding film including a transparent film and a heat ray reflecting layer provided on the surface thereof, in which the heat ray reflecting layer includes metal nanofibers. According to JP2012-252172A, the heat ray reflecting layer of the heat ray shielding film includes the metal nanofibers, and thus, excellent heat insulating properties are obtained in that heat rays of a heater or the like radiated from the indoor side are reflected to prevent radiation and outdoor heat does not enter the indoor side.
It is known that the fibrous conductive particles are used as a material of an electromagnetic wave shielding filter. JP2004-238503A, for example, discloses a metal nanofiber-containing composition including rod-like metal nanofibers (metal nanorods) having a long axis smaller than 400 nm and an aspect ratio greater than 1, and wire-like metal nanofibers (metal nanowires) having a long axis equal to or greater than 400 nm and a short axis equal to or smaller than 50 nm. According to JP2004-238503A, in a case of forming a resin film or a coating film, a composition including the metal nanorods and metal nanowires of JP2004-238503A has excellent absorption properties at a specific wavelength in a visible light region and a near infrared light region, a significantly small resistivity of the surface (high conductivity), and excellent electromagnetic wave shielding properties.
However, when the inventors further investigated properties of a layer prepared by using fibrous conductive particles and investigated properties of the heat insulating film disclosed in JP2012-252172A, it was found that radio-wave transmittance is low, and when the heat insulating film disclosed in JP2012-252172A is attached to a window, it is difficult to make a call using a mobile phone on the indoor side of the window. Accordingly, it is necessary the heat insulating film disclosed in JP2012-252172A has increased radio-wave transmittance of electric waves of a mobile phone.
It was well known for those skilled in the art that, in addition to the heat insulating film disclosed in JP2012-252172A, heat insulating films using reflection of far infrared rays in the related art generally have high conductivity (low resistivity or low surface resistivity) and have low radio-wave transmittance.
An object of the invention is to provide a heat insulating window film having excellent heat insulating properties and radio-wave transmittance.
When the inventors investigated properties of a layer prepared by using fibrous conductive particles, a layer having high heat insulating properties and radio-wave transmittance so as to easily transmit radio waves while having reflectivity for far infrared rays which was unknown in the related art was newly found. Specifically, when fibrous conductive particles-containing layers are prepared in various conditions and a relationship between a resistivity and a coefficient of overall heat transmission (excellent heat insulating properties are obtained, when a value of a coefficient of overall heat transmission is small) of each fibrous conductive particles-containing layer is plotted, a relationship between a common logarithm of the resistivity (log10(resistivity)) and a coefficient of overall heat transmission, when the resistivity is in a range of 5 to 500 Ω/□ (Ωper square) could be approximated as a directly proportional relation. That is, when the resistivity of the fibrous conductive particles-containing layer having the resistivity in a range of 5 to 500 Ω/□ in order to improve radio-wave transmittance, the coefficient of overall heat transmission is also increased, and thus, the heat insulating properties are deteriorated and a trade-off relationship between heat insulating properties and radio-wave transmittance was satisfied. Accordingly, since a heat insulating film having high heat insulating properties which is known in the related art has low resistivity and low radio-wave transmittance, it could be checked that both of heat insulating properties and radio-wave transmittance are not satisfied.
With respect to this, it was newly found that, when fibrous conductive particles are used, a low coefficient of overall heat transmission can be expected and a film having radio-wave transmittance is obtained, even when resistivity of a fibrous conductive particles-containing layer is set to be equal to or greater than 1,000 Ω/□. Accordingly, it was found that when the fibrous conductive particles are used, a directly proportional relationship between a common logarithm of the resistivity (log10(resistivity)) and a coefficient of overall heat transmission is not satisfied. That is, it was found that, when the resistivity is in a range of equal to or greater than 1,000 Ω/□, it is possible to break a trade-off relationship between heat insulating properties and radio-wave transmittance which was known in the related art and to obtain both of heat insulating properties and radio-wave transmittance.
As described above, the inventors newly found that, when a fibrous conductive particles-containing layer having excellent heat insulating properties is disposed on a surface of a support on a side opposite to a surface on a window side and a resistivity of the fibrous conductive particles-containing layer is equal to or greater than 1,000 Ω/□, unexpected effects of improving radio-wave transmittance while maintaining heat insulating properties are exhibited.
According to the finding described above, the inventors found that it is possible to provide a heat insulating window film having excellent heat insulating properties and radio-wave transmittance, by disposing a fibrous conductive particles-containing layer having excellent heat insulating properties on a surface of a support on a side opposite to a surface on a window side and setting a resistivity of the fibrous conductive particles-containing layer to be equal to or greater than 1,000 Ω/□.
The above-mentioned problems are solved with the invention having the following configurations.
[1] A heat insulating window film disposed on the inside of a window, comprising:
a support; and
a fibrous conductive particles-containing layer disposed on the support,
in which the fibrous conductive particles-containing layer contains fibrous conductive particles, and is disposed on a surface of the support on a side opposite to the surface of the window side, and
a resistivity of the fibrous conductive particles-containing layer is equal to or greater than 1,000 Ω/□.
[2] The heat insulating window film according to [1],
in which a content per unit area of the fibrous conductive particles of the fibrous conductive particles-containing layer is from 0.020 to 0.200 g/m2.
[3] The heat insulating window film according to [1] or [2],
in which an average long axis length of the fibrous conductive particles included in the fibrous conductive particles-containing layer is from 5 to 50 μm.
[4] The heat insulating window film according to any one of [1] to [3],
in which the fibrous conductive particles-containing layer of the heat insulating window film is the outermost layer or the second outermost layer on the indoor side.
[5] The heat insulating window film according to any one of [1] to [4],
in which visible light transmittance in a case where the heat insulating window film is bonded to a blue plate glass having a thickness of 3 mm is equal to or greater than 80%.
[6] A heat insulating window glass in which the heat insulating window film according to any one of [1] to [5] and a glass are laminated.
[7] A window comprising:
a transparent window support; and
the heat insulating window film according to any one of [1] to [5] bonded to the transparent window support.
According to the invention, it is possible to provide a heat insulating window film having excellent heat insulating properties and radio-wave transmittance.
Hereinafter, the invention will be described in detail. The description of the following constituent elements is based on representative embodiments and specific examples, but the invention is not limited to such embodiments. In this specification, a number range expressed using “to” means a range including the numerical numbers before and after the term “to” as a lower limit value and an upper limit value.
A heat insulating window film of the invention is a heat insulating window film disposed on the inner side of the window. The heat insulating window film at least includes a support, and a fibrous conductive particles-containing layer disposed on the support, the fibrous conductive particles-containing layer includes fibrous conductive particles, the fibrous conductive particles-containing layer is disposed on a surface of the support on a side opposite to a window side surface, and a resistivity of the fibrous conductive particles-containing layer is equal to or greater than 1,000 Ω/□.
With such a configuration, it is possible to provide a heat insulating window film having excellent heat insulating properties and radio-wave transmittance.
When a resistivity of the fibrous conductive particles-containing layer is in a range of equal to or greater than 1,000 Ω/□, a directly proportional relationship between a common logarithm of the resistivity (log10(resistivity)) and a coefficient of overall heat transmission is not satisfied, and a fibrous conductive particles-containing layer having a lower coefficient of overall heat transmission than a coefficient of overall heat transmission when the resistivity is 500 Ω/□, for example, is obtained. The reason of this phenomenon is not clearly found, but it is thought that, in a case where fibrous conductive particles do not come into contact with each other in the fibrous conductive particles-containing layer, it is possible to increase radio-wave transmittance of the entire fibrous conductive particles-containing layer due to a high resistivity, and to increase heat insulating properties of each fibrous conductive particle due to reflection of far infrared rays with high conductivity.
When the fibrous conductive particles-containing layer is disposed on a surface of the support on a side opposite to a window side surface (preferably, the fibrous conductive particles-containing layer is used as the outermost layer on the indoor side as possible), it is possible to reflect far infrared rays. When the heat insulating window film is not provided, far infrared rays in a room are adsorbed onto glass and the indoor heat escapes to the outside of the room due to heat conduction in the glass, but when the heat insulating window film is provided, far infrared rays are reflected in the room, and accordingly, the indoor heat hardly escapes to the outside of the room.
Since the resistivity of the fibrous conductive particles-containing layer is high, the heat insulating window film of the invention has excellent radio-wave transmittance.
The heat insulating window film having such a configuration can be manufactured particularly by applying the fibrous conductive particles-containing layer, and accordingly, the manufacturing cost thereof is low and an area of the film is easily enlarged, compared to a sputtering-metal laminate.
Hereinafter, the preferred aspect of the heat insulating window film of the invention will be described.
In the heat insulating window film of the invention, a resistivity of the fibrous conductive particles-containing layer is equal to or greater than 1,000 Ω/□. A resistivity of the fibrous conductive particles-containing layer is preferably equal to or greater than 1,500 Ω/□, more preferably equal to or greater than 2,000 Ω/□, and particularly preferably equal to or greater than 3,000 Ω/□.
A method of controlling the resistivity of the fibrous conductive particles-containing layer to be in the range described above is not particularly limited. For example, when preparing the fibrous conductive particles-containing layer, a method of preparing the layer by setting the amount of fibrous conductive particles to be smaller than the total amount of solid contents, that is, a method of decreasing the amount of fibrous conductive particles with respect to a fibrous conductive particles-containing layer can be used, as a result. This method is not limited to a certain theory, but it is considered that, it is possible to control a proportion of fibrous conductive particles coming into contact with each other in a fibrous conductive particles-containing layer and to control a resistivity of a fibrous conductive particles-containing layer.
In addition, the following method is used as the method of controlling the resistivity of the fibrous conductive particles-containing layer to be in the range described above.
A method of adding a material which is strongly adsorbed to fibrous conductive particles is used. It is thought that it is possible to control a proportion of fibrous conductive particles coming into contact with each other and to control a resistivity of a fibrous conductive particles-containing layer by using this method. Examples of the material which is strongly adsorbed to fibrous conductive particles include polymers including a hydrophilic group such as gelatin, polyvinyl alcohol, methyl cellulose, hydroxypropyl cellulose, polyalkylene amine, partial alkyl ester of polyacrylic acid, polyvinyl pyrrolidone, a copolymer having a polyvinyl pyrrolidone structure, and polyacrylic acid having an amino group or a thiol group. The material which is strongly adsorbed to fibrous conductive particles is preferably a material which is easily adsorbed to silver. A content per unit area of the material which is strongly adsorbed to fibrous conductive particles such as polyvinyl pyrrolidone is preferably in a range of 0.0001 to 10, more preferably in a range of 0.005 to 5, and particularly preferably in a range of 0.01 to 2, in terms of a mass ratio with respect to silver.
Since the heat insulating window film of the invention has excellent heat insulating properties and radio-wave transmittance, a coefficient of overall heat transmission is low and a radio attenuation rate is low. It is preferable that the heat insulating window film of the invention has excellent transparency. The preferable ranges of a coefficient of overall heat transmission, a radio attenuation rate, and transparency are the same as preferable ranges described as evaluation standard in the examples which will be described later.
A configuration of the heat insulating window film of the invention will be described.
The heat insulating window film 103 of the invention at least includes a support 10 and a fibrous conductive particles-containing layer 20 disposed on the support 10.
The fibrous conductive particles-containing layer 20 is disposed on a surface of the support 10 on a side opposite to a surface on the window (glass 61) side. In the invention, it is preferable that the fibrous conductive particles-containing layer 20 is the outermost layer or the second outermost layer on the indoor side, in a viewpoint of increasing heat insulating properties, and it is more preferable that the fibrous conductive particles-containing layer is the outermost layer on the indoor side.
A laminate obtained by bonding the support and the fibrous conductive particles-containing layer 20 provided on the support through an adhesive layer may be referred to as a heat insulating member 102. The adhesive layer may be a single layer or may be a laminate of two or more layers, and the adhesive layer in
In the heat insulating window film 103 of the invention, it is preferable that the pressure sensitive adhesive layer 51 is provided on a surface of the support 10 on the window (glass 61) side and it is preferable that the glass 61 and the pressure sensitive adhesive layer 51 are bonded to each other.
Hereinafter, preferred embodiments of each layer configuring the heat insulating window film of the invention will be described.
Various elements can be used as the support described above according to the purpose, as long as it can shoulder the fibrous conductive particles-containing layer. Generally, a plate-shaped or a sheet-shaped material is used.
The support may be transparent or may be opaque. Examples of a material configuring the support include transparent glass such as white plate glass, blue plate glass, or silica-coated blue plate glass; a synthetic resin such as polycarbonate, polyether sulfone, polyester, an acrylic resin, a vinyl chloride resin, an aromatic polyamide resin, polyamide imide, or polyimide; metal such as aluminum, copper, nickel, or stainless steel; ceramic; and a silicon wafer used in a semiconductor substrate. The surface of the support where the fibrous conductive particles-containing layer is formed may be previously treated by purification treatment using an alkaline aqueous solution, chemical treatment using a silane coupling agent, plasma treatment, ion plating, sputtering, a gas phase reaction method, and vacuum evaporation, if desired.
A thickness of the support is in a desired range according to the purpose. In general, the thickness thereof is selected from a range of 1 μm to 500 μm, is more preferably from 3 to 400 μm, and even more preferably from 5 μm to 300 μm.
Visible light transmittance of the support is preferably equal to or greater than 70%, more preferably equal to or greater than 85%, and even more preferably equal to or greater than 90%. The visible light transmittance of the support is measured based on ISO (ISO stands for International Organization for Standardization) 13468-1 (1996).
The fibrous conductive particles-containing layer contains fibrous conductive particles.
The fibrous conductive particles have a fibrous shape and the fibrous shape has the same meaning as a wire shape or a liner shape.
The fibrous conductive particles have conductivity.
As the fibrous conductive particles, metal nanowires, rod-shaped metal particles, or carbon nanotubes can be used. Metal nanowires are preferable as the fibrous conductive particles. Hereinafter, the metal nanowires will be described as a representative example of the fibrous conductive particles, but the description of the metal nanowires can be used as general description of the fibrous conductive particles.
The fibrous conductive particles-containing layer preferably contains metal nanowires having an average short axis length equal to or smaller than 150 nm as fibrous conductive particles. The average short axis length is preferably equal to or smaller than 150 nm, because heat insulating properties are improved and optical characteristics are hardly deteriorated due to light scattering. The fibrous conductive particles such as metal nanowires preferably have a solid structure.
In order to easily form more transparent fibrous conductive particles-containing layer, fibrous conductive particles having an average short axis length of 1 nm to 150 nm are preferable, for example, as the fibrous conductive particles such as metal nanowires.
From easiness of handling at the time of the manufacturing, an average short axis length (average diameter) of the fibrous conductive particles such as metal nanowires is preferably equal to or smaller than 100 nm, more preferably equal to or smaller than 60 nm, and even more preferably equal to or smaller than 50 nm, and the average short axis length thereof is particularly equal to or smaller than 25 nm, because more excellent properties with respect to haze are obtained. When the average short axis length thereof is equal to or greater than 1 nm, a fibrous conductive particles-containing layer having excellent oxidation resistance and excellent weather resistance. The average short axis length thereof is more preferably equal to or greater than 5 nm, even more preferably equal to or greater than 10 nm, and particularly preferably equal to or greater than 15 nm.
The average short axis length of the fibrous conductive particles such as metal nanowires is preferably from 1 nm to 100 nm, more preferably from 5 nm to 60 nm, even more preferably from 10 nm to 60 nm, and particularly preferably from 15 nm to 50 nm, from viewpoints of a haze value, oxidation resistance, and weather resistance.
The average long axis length of the fibrous conductive particles such as metal nanowires is preferably the same as a wavelength in a reflection band of far infrared rays desired to be reflected, in order to easily perform reflection in the reflection band of far infrared rays desired to be reflected. The average long axis length of the fibrous conductive particles such as metal nanowires is preferably from 5 μm to 50 μm, in order to easily reflect far infrared rays at a wavelength of 5 to 50 μm, more preferably from 10 μm to 40 μm, and even more preferably from 15 μm to 40 μm. When the average long axis length of the metal nanowires is equal to or smaller than 50 μm, synthesis of metal nanowires is easily performed without generating aggregates, and when the average long axis length thereof is equal to or greater than 5 μm, sufficient heat insulating properties are easily obtained.
The average short axis length (average diameter) and the average long axis length of fibrous conductive particles such as metal nanowires can be acquired by observing a transmission electron microscope (TEM) image or an optical microscope image by using a TEM and an optical microscope, for example. Specifically, regarding the average short axis length (average diameter) and the average long axis length of fibrous conductive particles such as metal nanowires, short axis lengths and long axis lengths of 300 metal nanowires randomly selected are measured by using a transmission electron microscope (JEOL, Ltd., product name: JEM-2000FX) and the average short axis length and the average long axis length of fibrous conductive particles such as metal nanowires can be acquired from the average values thereof. In this specification, the values obtained by using this method are used. Regarding the short axis length in a case where a cross section of the metal nanowires in a short axis direction does not have a circular shape, a length of the longest portion obtained by measuring a length in a short axis direction is set as the short axis length. In addition, in a case where the fibrous conductive particles such as metal nanowires are curved, a circle having the curved shape as an arc is considered, and a value calculated from the radius thereof and curvature is set as the long axis length.
In the embodiment, a content of fibrous conductive particles such as metal nanowires having a short axis length (diameter) equal to or smaller than 150 nm and a long axis length of 5 μm to 500 μm with respect to a content of fibrous conductive particles such as the entire metal nanowires of the fibrous conductive particles-containing layer is preferably equal to or greater than 50% by mass, more preferably equal to or greater than 60% by mass, and even more preferably equal to or greater than 75% by mass, in terms of the metal amount.
It is preferable that a rate of the fibrous conductive particles such as metal nanowires having a short axis length (diameter) equal to or smaller than 150 nm and a long axis length of 5 μm to 500 μm is equal to or greater than 50% by mass, because a percentage of metal nanowires which easily reflect far infrared rays at a wavelength of 5 μm to 50 μm is increased. In a configuration in which conductive particles other than the fibrous conductive particles are not substantially contained in the fibrous conductive particles-containing layer, a decrease in transparency can be avoided, even in a case of strong plasmon absorption.
A coefficient of variation of the short axis lengths (diameters) of the fibrous conductive particles such as metal nanowires used in the fibrous conductive particles-containing layer is preferably equal to or smaller than 40%, more preferably equal to or smaller than 35%, and even more preferably equal to or smaller than 30%.
The coefficient of variation is preferably equal to or smaller than 40%, from a viewpoint of transparency and heat insulating properties, because a proportion of metal nanowires which easily reflect far infrared rays at a wavelength of 5 to 50 μm is increased.
The coefficient of variation of the short axis lengths (diameters) of the fibrous conductive particles such as metal nanowires can be acquired by measuring short axis lengths (diameters) of 300 nanowires randomly selected from a transmission electron microscope (TEM), for example, calculating a standard deviation and an arithmetic mean value thereof, and dividing the standard deviation by the arithmetic mean value.
An aspect ratio of the fibrous conductive particles such as metal nanowires used in the invention is preferably equal to or greater than 10. Here, the aspect ratio means a ratio of the average long axis length to the average short axis length (average long axis length/average short axis length). The aspect ratio can be calculated from the average long axis length and the average short axis length calculated by using the method described above.
The aspect ratio of the fibrous conductive particles such as metal nanowires is not particularly limited, as long as it is equal to or greater than 10. The aspect ratio thereof can be suitably selected according to the purpose, and is preferably from 10 to 100,000, more preferably from 50 to 100,000, and even more preferably from 100 to 100,000.
When the aspect ratio is equal to or greater than 10, a network in which the fibrous conductive particles such as metal nanowires are in contact with each other is easily formed, and a fibrous conductive particles-containing layer having high heat insulating properties is easily obtained. When the aspect ratio is equal to or smaller than 100,000, formation of aggregates due to a tangle of the fibrous conductive particles such as metal nanowires in a coating solution used when providing the fibrous conductive particles-containing layer on the support by coating, for example, and a stable coating solution is obtained, and accordingly, the fibrous conductive particles-containing layer is easily manufactured.
The content of the fibrous conductive particles such as metal nanowires having an aspect ratio equal to or greater than 10 with respect to the mass of the fibrous conductive particles such as the entire metal nanowires contained in the fibrous conductive particles-containing layer is not particularly limited. The content is, for example, preferably equal to or greater than 70% by mass, more preferably equal to or greater than 75% by mass, and most preferably equal to or greater than 80% by mass.
A shape of the fibrous conductive particles such as metal nanowires may be arbitrary shapes such as a cylindrical shape, a rectangular parallelepiped shape, or a columnar shape having a polygonal cross section. When a high transparency is necessary, a cylindrical shape or a polygonal shape having a pentagonal or more polygonal cross section and having a cross sectional shape without a sharp-pointed angle is preferable.
The cross sectional shape of the fibrous conductive particles such as metal nanowires can be detected by applying a fibrous conductive particles aqueous dispersion such as metal nanowires on a support and observing a cross section with a transmission electron microscope (TEM).
The metal for forming the fibrous conductive particles such as metal nanowires is not particularly limited and any metal may be used. In addition to one kind of metal, a combination of two or more kinds of metal may be used and an alloy thereof can be used. Among these, the metal is preferably formed of a metal alone or a metal compound, and the metal is more preferably formed of a metal alone.
As the metal, at least one kind of metal selected from the group consisting metals of fourth, fifth, and sixth period in a long-form periodic table (IUPAC 1991) is preferable, at least one kind of metal selected from second to fourteenth groups is more preferable, at least one kind of metal selected from the second group, the eighth group, the ninth group, the tenth group, the eleventh group, the twelfth group, the thirteenth group, and the fourteenth group is even more preferable, and it is particularly preferable that these metals are contained as a main component.
Specific examples of the metal include copper, silver, gold, platinum, palladium, nickel, tin, cobalt, rhodium, iridium, iron, ruthenium, osmium, manganese, molybdenum, tungsten, niobium, tantalum, titanium, bismuth, antimony, lead, and an alloy containing any one of these. Among these, copper, silver, gold, platinum, palladium, nickel, tin, cobalt, rhodium, iridium, or an alloy thereof is preferable, palladium, copper, silver, gold, platinum, tin, or an alloy of any one of these is more preferable, and silver or an alloy containing silver is particularly preferable. Here, a content of silver in an alloy containing silver is preferably equal to or greater than 50 mol %, more preferably equal to or greater than 60 mol %, and even more preferably equal to or greater than 80 mol % with respect to the entire quantity of the alloy.
The fibrous conductive particles such as metal nanowires contained in the fibrous conductive particles-containing layer preferably contains silver nanowires, from a viewpoint of realizing high heat insulating properties. It is more preferable to contain silver nanowires having an average short axis length of 1 nm to 150 nm and an average long axis length of 1 μm and 100 μm and even more preferable to contain silver nanowires having an average short axis length of 5 nm to 30 nm and an average long axis length of 5 μm to 30 μm. The content of silver nanowires with respect to the mass of the fibrous conductive particles such as the entire metal nanowires contained in the fibrous conductive particles-containing layer is not particularly limited, as long as it does not disturb the effects of the invention. The content of silver nanowires with respect to the mass of the fibrous conductive particles such as the entire metal nanowires contained in the fibrous conductive particles-containing layer is, for example, preferably equal to or greater than 50% by mass and more preferably equal to or greater than 80% by mass, and it is even more preferable that the fibrous conductive particles such as the entire metal nanowires are substantially silver nanowires. Here, the term “substantially” means that inevitably mixed metal atoms other than silver are accepted.
The content of the fibrous conductive particles such as metal nanowires contained in the fibrous conductive particles-containing layer is preferably set as an amount so that resistivity, visible light transmittance, and a haze value of the fibrous conductive particles-containing layer are in desired ranges, in accordance of the type of the fibrous conductive particles such as metal nanowires.
At this time, the amount of fibrous conductive particles with respect to the fibrous conductive particles-containing layer is preferably small, from a viewpoint of controlling resistivity of the fibrous conductive particles-containing layer. In a case of setting the amount of fibrous conductive particles to be in the range described above, the mass per unit area of the fibrous conductive particles-containing layer (coating amount of entire solid contents of a coating solution at the time of preparing a film) is preferably in a range of 0.110 to 1.000 g/m2, more preferably in a range of 0.150 to 0.600 g/m2, and particularly preferably in a range of 0.200 to 0.500 g/m2.
The amount of fibrous conductive particles with respect to the fibrous conductive particles-containing layer is preferably 1% to 35% by mass, more preferably 3% to 30% by mass, and particularly preferably 5% to 25% by mass.
The fibrous conductive particles such as metal nanowires are not particularly limited and may be manufactured by any method. As will be described below, it is preferable that the fibrous conductive particles are manufactured by reducing metal ions in a solvent obtained by dissolving a halogen compound and a dispersing agent. After fibrous conductive particles such as metal nanowires are formed, desalinization treatment is performed in a routine procedure, and this operation is preferable from viewpoints of dispersibility and temporal stability of the fibrous conductive particles-containing layer.
As the manufacturing method of the fibrous conductive particles such as metal nanowires, methods disclosed in JP2009-215594A, JP2009-242880A, JP2009-299162A, JP2010-84173A, and JP2010-86714 can be used.
As a solvent used in the manufacturing of the fibrous conductive particles such as metal nanowires, a hydrophilic solvent is preferable, and examples thereof include water, an alcohol solvent, an ether solvent, and a ketone solvent. These may be used alone or in combination of two or more kinds thereof
Examples of the alcohol solvent include methanol, ethanol, propanol, isopropanol, butanol, and ethylene glycol.
Examples of the ether solvent include dioxane and tetrahydrofuran.
Examples of the ketone solvent include acetone and the like.
In a case of performing heating, a heating temperature thereof is preferably equal to or lower than 250° C., more preferably from 20° C. to 200° C., even more preferably from 30° C. to 180° C., and particularly preferably from 40° C. to 170° C. When the temperature is equal to or higher than 20° C., a length of the fibrous conductive particles such as metal nanowires formed is in a preferable range so as to ensure dispersion stability, and when the temperature is equal to or lower than 250° C., the periphery of the cross section of the metal nanowires has a smooth shape without acute angles, and accordingly, coloration due to surface plasmon absorption of the metal particles is prevented. Therefore, the range thereof is preferable from a viewpoint of transparency.
The temperature may be changed during a particle formation process, if necessary, and the temperature change during the process may have effects of control of nucleus formation or prevention of regeneration of nucleus, and improvement of monodispersity due to improvement of selective growth.
The heating process is preferably performed by adding a reducing agent.
The reducing agent is not particularly limited and can be suitably selected from elements normally used. Examples thereof include borohydride metal salt, aluminum hydride salt, alkanolamine, aliphatic amine, heterocyclic amine, aromatic amine, aralkyl amine, alcohols, organic acids, reducing sugars, sugar alcohols, sodium sulfite, hydrazine compounds, dextrin, hydroquinone, hydroxylamine, ethylene glycol, and glutathione. Among these, reducing sugars, sugar alcohols as a derivative thereof, and ethylene glycol are particularly preferable.
As a reducing agent, a compound having a function as both of a dispersing agent or a solvent can be preferably used, in the same manner.
The fibrous conductive particles such as metal nanowires are preferably manufactured by adding a dispersing agent and halogen compounds or metal halide fine particles.
The timing of adding a dispersing agent and halogen compounds may be before adding a reducing agent or after adding a reducing agent or may be before adding metal ions or metal halide fine particles or after adding metal ions or metal halide fine particles. In order to obtain fibrous conductive particles having better monodispersity, the adding of halogen compounds is preferably divided into two or more steps, because nucleus formation and growth can be controlled.
The step of adding a dispersing agent is not particularly limited. A dispersing agent may be added before preparing the fibrous conductive particles such as metal nanowires and the fibrous conductive particles such as metal nanowires may be added under the presence of the dispersing agent, or a dispersing agent may be added after preparing the fibrous conductive particles such as metal nanowires, in order to control a dispersion state.
Examples of the dispersing agent include an amino group-containing compound, a thiol group-containing compound, a sulfide group-containing compound, amino acid or a derivative thereof, a peptide compounds, polysaccharides, a polysaccharides-derived natural polymer, a synthetic polymer, and polymer compounds such as gel derived therefrom. Among these, various polymer compounds used as a dispersing agent are compounds contained in polymers which will be described below.
Preferable examples of polymers used as a dispersing agent include polymers including a hydrophilic group such as gelatin, polyvinyl alcohol, methyl cellulose, hydroxypropyl cellulose, polyalkylene amine, partial alkyl ester of polyacrylic acid, polyvinyl pyrrolidone, a copolymer having a polyvinyl pyrrolidone structure, and polyacrylic acid having an amino group or a thiol group which are protective colloid polymers.
A weight average molecular weight (Mw) of the polymer used as a dispersing agent measured by using gel permeation chromatography (GPC) is preferably from 3,000 to 300,000 and more preferably from 5,000 to 100,000.
The description in “Genryo No Jiten” (edited by Seijiro Ito, published by Asakura Publishing, 2000) can be referred for the structure of a compound capable of being used as a dispersing agent.
A shape of metal nanowires obtained can be changed depending on the kind of a dispersing agent used.
The halogen compound is not particularly limited, as long as it is a compound containing bromine, chlorine, and iodine, and can be suitably selected according to the purpose. Preferable examples thereof include alkali halide such as sodium bromide, sodium chloride, sodium iodide, potassium iodide, potassium bromide, or potassium chloride, or a compound capable of being used in combination with the following dispersion additive.
The halogen compound may function as a dispersion additive and the dispersion additive can be preferably used in the same manner.
Silver halide fine particles may be used as a substitute of the halogen compound, or a halogen compound and silver halide fine particles may be used in combination.
In addition, a single substance having both a function of a dispersing agent and a function of a halogen compound may be used. That is, both functions of a dispersing agent and a halogen compound are realized with one compound, by using a halogen compound having a function as a dispersing agent.
Examples of the halogen compound having a function as a dispersing agent include hexadecyl-trimethyl ammonium bromide containing an amino group and bromide ions, hexadecyl-trimethyl ammonium chloride containing an amino group and chloride ions, dodecyltrimethylammonium bromide containing an amino group and bromide ions or chloride ions, dodecyltrimethylammonium chloride, stearyltrimethylammonium bromide, stearyltrimethylammonium chloride, decyltrimethylammonium bromide, decyltrimethylammonium chloride, dimethyldistearylammonium bromide, dimethyldistearylammonium chloride, dilauryldimethylammonium bromide, dilauryldimethylammonium chloride, dimethyldipalmitylammonium bromide, and dimethyldipalmitylammonium chloride. In the manufacturing method of the metal nanowires, it is preferable to perform desalinization treatment after forming the metal nanowires. The desalinization treatment after forming the metal nanowires can be performed by using methods such as ultrafiltration, dialysis, gel filtration, decantation, and centrifugal separation.
It is preferable that the fibrous conductive particles such as metal nanowires do not contain inorganic ions such as alkali metal ions, alkali earth metal ions, and halide ions, if possible. Electric conductivity of a dispersed material obtained by dispersing metal nanowires in an aqueous solvent is preferably equal to or smaller than 1 mS/cm, more preferably equal to or smaller than 0.1 mS/cm, and even more preferably equal to or smaller than 0.05 mS/cm.
Viscosity of the aqueous dispersed material of the fibrous conductive particles such as metal nanowires at 25° C. is preferably from 0.5 mPa·s to 100 mPa·s and more preferably from 1 mPa·s to 50 mPa·s.
The electric conductivity and the viscosity are measured by setting concentration of the fibrous conductive particles such as metal nanowires in the aqueous dispersed material as 0.45% by mass. In a case where the concentration of the fibrous conductive particles such as metal nanowires in the aqueous dispersed material is higher than the above-mentioned concentration, the measurement is performed by diluting the aqueous dispersed material with a distilled water.
An average film thickness of the fibrous conductive particles-containing layer is normally selected from a range of 0.005 μm to 2 μm. For example, when the average film thickness thereof is from 0.001 μm to 0.5 μm, sufficient durability and film hardness are obtained. Particularly, the average film thickness thereof is preferably in a range of 0.01 μm to 0.1 μm, because the allowable range in the manufacturing can be ensured.
In the invention, it is preferable that, by providing a fibrous conductive particles-containing layer satisfying at least one of the following condition (i) or (ii), high heat insulating properties and transparency are maintained, fibrous conductive particles such as metal nanowires are stably solidified due to a sol-gel hardened material, and high strength and durability are realized. Even when the fibrous conductive particles-containing layer is a thin layer having a film thickness of 0.005 μm to 0.5 μm, for example, it is possible to obtain a fibrous conductive particles-containing layer having abrasion resistance, heat resistance, moist heat resistance, and bending resistance without practical problems. Accordingly, the heat insulating window film of the embodiment of the invention is suitably used for various purposes. When it is necessary to provide a thin layer, a film thickness thereof may be from 0.005 μm to 0.5 μm, preferably from 0.007 μm to 0.3 μm, more preferably from 0.008 μm to 0.2 μm, and particularly preferably from 0.01 μm to 0.1 μm. By setting the fibrous conductive particles-containing layer to be a thinner layer as described above, transparency of the fibrous conductive particles-containing layer is further improved.
Regarding an average film thickness of the fibrous conductive particles-containing layer, film thicknesses of five spots of the fibrous conductive particles-containing layer are measured by directly observing the cross section of the fibrous conductive particles-containing layer using an electron microscope, and an arithmetic average value thereof is calculated. In addition, the film thickness of the fibrous conductive particles-containing layer can also be measured as a level difference between a portion where the fibrous conductive particles-containing layer is formed and a portion where the fibrous conductive particles-containing layer is removed, by using a stylus type surface shape measurement device (Dektak (registered trademark) 150, manufactured by Bruker AXS K.K). However, some parts of the support may be removed when removing the fibrous conductive particles-containing layer and an error regarding the fibrous conductive particles-containing layer formed easily occurs, because the fibrous conductive particles-containing layer is a thin film. Therefore, in the following examples, the average film thickness measured by using an electron microscope is shown.
It is preferable that the fibrous conductive particles-containing layer has excellent abrasion resistance. This abrasion resistance can be evaluated, for example, by using a method of (1) or (2) disclosed in paragraph “0067” of JP2013-225461A.
The fibrous conductive particles-containing layer may contain a matrix. Here, a “matrix” is a general term of substances forming a layer including fibrous conductive particles such as metal nanowires. By containing a matrix, a dispersion state of fibrous conductive particles such as metal nanowires of the fibrous conductive particles-containing layer is stably maintained, and even in a case where the fibrous conductive particles-containing layer is formed on the surface of the support without using the adhesive layers, strong adhesion between the support and the fibrous conductive particles-containing layer tends to be ensured.
The fibrous conductive particles-containing layer preferably contains a sol-gel hardened material having a function as a matrix, and more preferably contains a sol-gel hardened material obtained by hydrolysis and polycondensation of an alkoxide compound of an element (b) selected from the group consisting of Si, Ti, Zr, and Al.
The fibrous conductive particles-containing layer more preferably contains at least a metal element (a), metal nanowires having an average short axis length equal to or smaller than 150 nm, and a sol-gel hardened material obtained by hydrolysis and polycondensation of an alkoxide compound of an element (b) selected from the group consisting of Si, Ti, Zr, and Al.
The fibrous conductive particles-containing layer preferably satisfies at least one of the following condition (i) or (ii), more preferably satisfies at least the following conditions (ii), and particularly preferably satisfies the following conditions (i) and (ii).
(i) A ratio of substance quantity of the element (b) contained in the fibrous conductive particles-containing layer and substance quantity of the metal element (a) contained in the fibrous conductive particles-containing layer [molar number of (element (b))/molar number of (metal element (a))] is in a range of 0.10/1 to 22/1.
(ii) A ratio of a mass of the alkoxide compound used for forming the sol-gel hardened material in the fibrous conductive particles-containing layer to a mass of metal nanowires contained in the fibrous conductive particles-containing layer [(content of alkoxide compound)/(content of metal nanowires)] is in a range of 0.25/1 to 30/1.
It is preferable that the fibrous conductive particles-containing layer is formed so that a ratio of a usage amount of a specified alkoxide compound with respect to a usage amount of metal nanowires, that is, a ratio of [(mass of specified alkoxide compound)/(mass of metal nanowires)] is in a range of 0.25/1 to 30/1. In a case where the mass ratio is equal to or greater than 0.25/1, it is possible to obtain a fibrous conductive particles-containing layer having excellent heat insulating properties (this may be due to high conductivity of the fibrous conductive particles) and transparency, and excellent abrasion resistance, heat resistance, moist heat resistance, and bending resistance. In a case where the mass ratio is equal to or smaller than 30/1, it is possible to obtain a fibrous conductive particles-containing layer having excellent conductivity and bending resistance.
The mass ratio is more preferably in a range of 0.5/1 to 25/1, even more preferably in a range of 1/1 to 20/1, and most preferably in a range of 2/1 to 15/1. By setting the mass ratio to be in the preferable range, the fibrous conductive particles-containing layer obtained has high heat insulating properties and high transparency (visible light transmittance and haze), and excellent abrasion resistance, heat resistance, moist heat resistance, and bending resistance, and accordingly, it is possible to stably obtain a heat insulating window film having suitable physical properties.
As an optimal state, in the fibrous conductive particles-containing layer, the ratio of substance quantity of the element (b) and substance quantity of the metal element (a) [molar number of (element (b))/molar number of (metal element (a))] is in a range of 0.10/1 to 22/1. The molar ratio is more preferably from 0.20/1 to 18/1, particularly preferably from 0.45/1 to 15/1, more particularly preferably from 0.90/1 to 11/1, and even more particularly preferably from 1.5/1 to 10/1.
When the molar ratio is in the range described above, the fibrous conductive particles-containing layer has both of heat insulating properties and transparency, and has excellent abrasion resistance, heat resistance, moist heat resistance, and bending resistance, from a viewpoint of physical properties.
The specified alkoxide compound used when forming the fibrous conductive particles-containing layer is used up due to hydrolysis and polycondensation and substantially no alkoxide compound is present in the fibrous conductive particles-containing layer, but the fibrous conductive particles-containing layer obtained contains the element (b) such as Si or the like derived from the specified alkoxide compound. By adjusting the ratio of the substance quantity of the element (b) such as Si contained and the metal element (a) derived from metal nanowires, the fibrous conductive particles-containing layer having excellent properties is formed.
A component of the element (b) selected from the group consisting of Si, Ti, Zr, and Al derived from the specified alkoxide compound of the fibrous conductive particles-containing layer and a component of the metal element (a) derived from metal nanowires can be analyzed by the following method.
That is, the ratio of the substance quantity, that is, the value of (component molar number of (element (b))/component molar number of (metal element (a)) can be calculated by performing X ray photoelectron analysis (Electron Spectroscopy FOR Chemical Analysis (ESCA)) with respect to the fibrous conductive particles-containing layer. However, since measurement sensitivity is different depending on an element in the analysis method using ESCA, a value obtained does not necessarily directly show a molar ratio of the element components. Accordingly, a calibration curve is drawn by using a fibrous conductive particles-containing layer having a well-known molar ratio of element components in advance, and a ratio of substance quantity of the actual fibrous conductive particles-containing layer can be calculated from the calibration curve. As the molar ratio of each element in this specification, a value calculated by using the following method is used.
The heat insulating window film preferably exhibits effects of obtaining high heat insulating properties and transparency and excellent abrasion resistance, heat resistance, moist heat resistance, and bending resistance. The reason of exhibiting such effects is not clear, but the following reasons are assumed.
That is, since the fibrous conductive particles-containing layer contains metal nanowires, and a matrix which is a sol-gel hardened material obtained by hydrolysis and polycondensation of the specified alkoxide compound, a dense fibrous conductive particles-containing layer having less voids and high crosslinking density is formed, even when the rate of the matrix contained in the fibrous conductive particles-containing layer is small, compared to a fibrous conductive particles-containing layer containing a general organic polymer resin (for example, an acrylic resin, a vinyl polymerization resin, or the like) as a matrix, and accordingly, a heat insulating window film having excellent abrasion resistance, heat resistance, and moist heat resistance is obtained. It is assumed that, by satisfying any one of setting the content molar ratio of the element (b) derived from the specified alkoxide compound/metal element (a) derived from metal nanowires in a range of 0.10/1 to 22/1 and setting the mass ratio of the specified alkoxide compound/metal nanowires in a range of 0.25/1 to 30/1, in relation to the above-mentioned content molar ratio which is in a range of 0.10/1 to 22/1, the operation is improved with good balance, heat insulating properties and transparency are maintained, and excellent abrasion resistance, heat resistance, and moist heat resistance, and excellent bending resistance are exhibited.
The sol-gel hardened material contained in the fibrous conductive particles-containing layer has a function as a matrix, but the fibrous conductive particles-containing layer may further contain matrix other than the sol-gel hardened material (hereinafter, referred to as other matrix). The fibrous conductive particles-containing layer containing other matrix contains a material capable of forming other matrix in a liquid composition which will be described later, and may be formed by applying this on the support.
The other matrix may be nonphotosensitive such as an organic polymer or may be photosensitive such as a photoresist composition.
In a case where the fibrous conductive particles-containing layer contains other matrix, the content thereof is from 0.10% by mass to 20% by mass, preferably from 0.15% by mass to 10% by mass, and even more preferably from 0.20% by mass to 5% by mass, with respect to the content of the sol-gel hardened material derived from the specified alkoxide compound contained in the fibrous conductive particles-containing layer, because a fibrous conductive particles-containing layer having excellent heat insulating properties, transparency, film hardness, abrasion resistance, and bending resistance is obtained.
The other matrix may be nonphotosensitive or may be photosensitive as described above. A nonphotosensitive matrix is preferable.
The preferable nonphotosensitive matrix contains an organic polymer. Specific examples of the organic polymer include polyacrylic acid such as polymethacrylic acid, polymethacrylate (for example, poly (methyl methacrylate)), polyacrylate, or polyacrylonitrile, a highly aromatic polymer such as polyvinyl alcohol, polyesters (e.g., polyethylene terephthalate (PET), polyester naphthalate, and polycarbonate), phenol or cresol formaldehyde (Novolacs (registered trademark)), polystyrene, polyvinyl toluene, polyvinyl xylene, polyimide, polyamide, polyamideimide, polyetherimide, polysulfide, polysulfone, polyphenylene, or polyphenylether, polyurethane, epoxy, polyolefin (e.g., polypropylene, polymethylpentene, and cyclic olefins), acrylonitrile-butadiene-styrene copolymer, cellulose, silicone, and other silicon-containing polymer (for example, polysilsesquioxane and polysilane), polyvinyl chloride, polyvinyl acetate, polynorbornene, synthetic rubber, (for example, ethylene propylene rubber (EPR), styrene-butadiene rubber (SBR), ethylene propylene diene monomer rubber (EPDM)), and a fuorocarbon-based polymer (for example, polyvinylidene fluoride, polytetrafluoroethylene, or polyhexafluoropropylene), a fluoro-olefin copolymer, hydrocarbon olefin (for example, “LUMIFLON” (registered trademark) manufactured by Asahi Glass Co., Ltd.), an amorphous fluorocarbon polymer or copolymer (for example, “CYTOP” (registered trademark) manufactured by Asahi Glass Co., Ltd., and “Teflon” (registered trademark) AF manufactured by Dupont), and there is no limitation.
A crosslinking agent is a compound which forms a chemical bond by free radicals or acids and heat and hardens a conductive layer, and examples thereof include a melamine-based compound substituted with at least one selected from a methylol group, an alkoxymethyl group, and an acyloxymethyl group, a guanamine-based compound, a glycoluril-based compound, a urea-based compound, a phenol-based compound or an ether compound of phenol, an epoxy-based compound, an oxetane-based compound, a thioepoxy-based compound, an isocyanate-based compound, or an amide-based compound, and a compound having an ethylenically unsaturated group containing a methacryloyl group or an acryloyl group. Among these, an epoxy-based compound, an oxetane-based compound, and a compound having an ethylenically unsaturated group are particularly preferable, from viewpoints of film properties, heat resistance, and solvent resistance.
An oxetane-based compound can be used alone or in a mixture with an epoxy resin. Particularly, it is preferable to use an oxetane-based compound together with an epoxy resin, from viewpoints of high reactivity and improvement of film properties.
When the total mass of a solid content of the fibrous conductive particles such as metal nanowires described above is 100 parts by mass, the content of the crosslinking agent in the fibrous conductive particles-containing layer is preferably from 1 part by mass to 250 parts by mass and more preferably from 3 part by mass to 200 parts by mass.
A dispersing agent is used for dispersing the fibrous conductive particles such as metal nanowires in the photopolymerizable composition while preventing aggregation thereof. The dispersing agent is not particularly limited as long as it can disperse metal nanowires and can be suitably selected according to the purpose. For example, a dispersing agent which is commercially available as a pigment dispersing agent can be used, and it is preferable to use particularly a polymer dispersing agent having properties of being adsorbed to metal wires. Examples of such a polymer dispersing agent include polyvinylpyrrolidone, BYK SERIES (registered trademark, manufactured by BYK Additives & Instruments), SOLSPERSE SERIES (manufactured by The Lubrizol Corporation), and AJISPER SERIES (manufactured by Ajinomoto Co., Inc.).
The content of the dispersing agent in the fibrous conductive particles-containing layer is preferably from 0.1 parts by mass to 50 parts by mass, more preferably from 0.5 parts by mass to 40 parts by mass, and particularly preferably from 1 part by mass to 30 parts by mass, with respect to 100 parts by mass of a binder in a case of using a binder disclosed in paragraphs “0086” to “0095” of JP2013-225461A.
When the content of the dispersing agent with respect to the binder is equal to or greater than 0.1 parts by mass, aggregation of the fibrous conductive particles such as metal nanowires in a dispersion is effectively prevented, and when the content thereof is equal to or smaller than 50 parts by mass, a stable liquid film is formed in a coating step and generation of coating unevenness is prevented, and thus, the ranges described above are preferable. cl Solvent
A solvent is a component used for preparing a coating solution for forming a composition containing the fibrous conductive particles such as metal nanowires, the specified alkoxide compound, and the photopolymerizable composition on the surface of the support or a surface of an adhesive layer of an adhesive layer-attached support to have a film shape, and can be suitably selected according to the purpose. Examples thereof include propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, ethyl 3-ethoxypropionate, methyl 3-methoxypropionate, ethyl lactate, 3-methoxy butanol, water, 1-methoxy-2-propanol, isopropyl acetate, methyl lactate, N-methylpyrrolidone, γ-butyrolactone, and propylene carbonate. This solvent may serve as at least some of the solvent of the dispersion of the metal nanowires described above. These may be used alone or in combination of two or more kinds thereof.
A solid content concentration of the coating solution containing the solvent is preferably in a range of 0.1% by mass to 20% by mass.
The fibrous conductive particles-containing layer preferably contains a metal corrosion inhibitor of the fibrous conductive particles such as metal nanowires. The metal corrosion inhibitor is not particularly limited and can be suitably selected according to the purposes. Thiols or azoles are suitable, for example.
When the metal corrosion inhibitor is contained, it is possible to exhibit an antirust effect and to prevent a decrease in heat insulating properties and transparency of the fibrous conductive particles-containing layer over time. The metal corrosion inhibitor can be applied by being added into a composition for forming the fibrous conductive particles-containing layer in a state of being suitably dissolved with a solvent or in a state of powder, or manufacturing a conductive film using a coating solution for a conductive layer which will be described later and then dipping the conductive film in a metal corrosion inhibitor bath.
In a case of adding the metal corrosion inhibitor, the content thereof in the fibrous conductive particles-containing layer is preferably from 0.5% by mass to 10% by mass with respect to the content of the fibrous conductive particles such as metal nanowires.
As the other matrix, the polymer compound of the dispersing agent used when preparing the fibrous conductive particles such as metal nanowires described above can be used as at least a part of components configuring the matrix.
The fibrous conductive particles-containing layer may include other conductive materials, for example, conductive fine particles, in addition to the fibrous conductive particles such as metal nanowires, within a range not degrading the effects of the invention. From a viewpoint of the effect, a content of the fibrous conductive particles such as metal nanowires (preferably, metal nanowires having an aspect ratio equal to or greater than 10) is preferably equal to or greater than 50%, more preferably equal to or greater than 60%, and particularly preferably equal to or greater than 75%, based on volume, with respect to the total amount of the conductive material containing the fibrous conductive particles such as metal nanowires. When the content of the fibrous conductive particles such as metal nanowires is 50%, a fine network of the fibrous conductive particles such as metal nanowires is formed and a fibrous conductive particles-containing layer having high conductivity can be easily formed.
The conductive particles other than the fibrous conductive particles such as metal nanowires may not significantly contribute to conductivity of the fibrous conductive particles-containing layer and may have absorption in a visible light region. It is particularly preferable that the conductive particles are metal and do not have a shape with strong plasmon absorption such as a spherical shape, from a viewpoint of not deteriorating transparency of the fibrous conductive particles-containing layer.
Here, a percentage of the fibrous conductive particles such as metal nanowires can be acquired as follows. For example, in a case where the fibrous conductive particles are silver nanowires and the conductive particles are silver particles, a silver nanowires aqueous dispersion is filtered to separate silver nanowires and other conductive particles, each of an amount of silver remaining on the filter paper and an amount of silver transmitted through the filter paper are measured by using a inductively coupled plasma (ICP) emission analysis device, and the percentage of the metal nanowires can be calculated. The aspect ratio of the fibrous conductive particles such as metal nanowires is calculated by observing the fibrous conductive particles such as metal nanowires remaining on the filter paper using a TEM and measuring each of short axis lengths and long axis lengths of the fibrous conductive particles such as 300 metal nanowires.
The measurement method of the average long axis length and the average short axis length of the fibrous conductive particles such as metal nanowires are as described above.
(Manufacturing Method of Fibrous Conductive Particles-Containing Layer)
A manufacturing method of the fibrous conductive particles-containing layer is not particularly limited, as long as the preparation can be performed so that resistivity of the fibrous conductive particles-containing layer becomes equal to or greater than 1,000 Ω/□. When preparing the fibrous conductive particles-containing layer, a method of preparing the layer by setting the amount of fibrous conductive particles to be smaller than the total amount of solid contents is preferably used. In other preferred embodiments, as a method of forming the fibrous conductive particles-containing layer on a support, the fibrous conductive particles-containing layer can be manufactured by a method at least containing: forming a liquid film by applying a liquid composition (hereinafter, also referred to as a “sol-gel coating solution) containing the fibrous conductive particles such as metal nanowires having an average short axis length equal to or smaller than 150 nm and the specified alkoxide compound so that the mass ratio thereof (that is, (content of specified alkoxide compound)/(content of metal nanowires)) is in a range of 0.25/1 to 30/1 or the content molar ratio of the element (b) derived from the specified alkoxide compound and the metal element (a) derived from the metal nanowires is in a range of 0.10/1 to 22/1, on a support; and forming a fibrous conductive particles-containing layer by allowing a reaction such as hydrolysis and polycondensation of the specified alkoxide compound in the liquid film (hereinafter, this reaction such as hydrolysis and polycondensation is also referred to as a “sol-gel reaction”). This method may or may not further include evaporating (drying) performed by heating water contained in the liquid composition as a solvent, if necessary.
In the embodiment, by using the sol-gel coating solution, an aqueous dispersion of metal nanowires is prepared or the metal nanowires and the specified alkoxide compound may be mixed to prepare an aqueous dispersion. In the embodiment, an aqueous solution containing the specified alkoxide compound is prepared, this aqueous solution is heated, at least some parts of the specified alkoxide compound are subjected to hydrolysis and polycondensation to set a sol state, and the aqueous solution in the sol state and the aqueous dispersion of metal nanowires may be mixed to prepare a sol-gel coating solution.
In order to promote a sol-gel reaction, it is practically preferable to use an acid catalyst or a basic catalyst together, in order to improve reaction efficiency.
The liquid composition may contain water and/or an organic solvent, if necessary. By containing an organic solvent, a more uniform liquid film can be formed on the support.
Examples of such an organic solvent include a ketone-based solvent such as acetone, methyl ethyl ketone, or diethyl ketone, an alcohol-based solvent such as methanol, ethanol, 2-propanol, 1-propanol, 1-butanol, or tert-butanol, a chlorine-based solvent such as chloroform or methylene chloride, an aromatic solvent such as benzene or toluene, an ester-based solvent such as ethyl acetate, butyl acetate, or isopropyl acetate, an ether-based solvent such as diethyl ether, tetrahydrofuran, or dioxane, and a glycol ether-based solvent such as ethylene glycol monomethyl ether or ethylene glycol dimethyl ether. In a case where the liquid composition contains the organic solvent, the content thereof is preferably in a range of equal to or smaller than 50% by mass and more preferably in a range of equal to or smaller than 30% by mass, with respect to the total mass of the liquid composition.
A reaction such as hydrolysis and polycondensation of the specified alkoxide compound occurs in the coating liquid film of the sol-gel coating solution formed on the support, and in order to promote the reaction, it is preferable that the coating liquid film is heated and dried. A heating temperature for promoting the sol-gel reaction is suitably in a range of 30° C. to 200° C. and more preferably in a range of 50° C. to 180° C. The heating and drying time is preferably from 10 seconds to 300 minutes and more preferably from 1 minute to 120 minutes.
A method of forming the fibrous conductive particles-containing layer described above on the support is not particularly limited. General coating methods can be used and any method can be suitably selected according to the purpose. Examples thereof include a roll coating method, a bar coating method, a dip coating method, a spin coating method, a casting method, a die coating method, a blade coating method, a gravure coating method, a curtain coating method, a spray coating method, and doctor coating method.
It is preferable that the heat insulating window film includes at least one interlayer between the support and the fibrous conductive particles-containing layer. When the interlayer is provided between the support and the fibrous conductive particles-containing layer, at least one of adhesiveness between the support and the fibrous conductive particles-containing layer, visible light transmittance of the fibrous conductive particles-containing layer, the haze of the fibrous conductive particles-containing layer, or film hardness of the fibrous conductive particles-containing layer can be improved.
As the interlayer, an adhesive layer for improving adhesiveness between the support and the fibrous conductive particles-containing layer or a functional layer for improving functionality with interaction with a component contained in the fibrous conductive particles-containing layer is used, and the interlayer is suitably selected according to the purpose.
A configuration of the heat insulating window film further including the interlayer will be described with reference to the drawing.
In
An interlayer having a configuration other than that of
A material used for the interlayer is not particularly limited and materials for improving at least any one of the properties described above may be used.
For example, in a case of including the adhesive layer as the interlayer, materials selected from a polymer used in an adhesive, a silane coupling agent, a titanium coupling agent, and a sol-gel film obtained by allowing hydrolysis and polycondensation of the alkoxide compound of Si are contained in the adhesive layer.
It is preferable that the interlayer adjacent to the fibrous conductive particles-containing layer (that is, in a case where the interlayer is a single layer, the interlayer adjacent to the fibrous conductive particles-containing layer, and in a case where the interlayer includes a plurality of sub-interlayers, the sub-interlayer adjacent to the fibrous conductive particles-containing layer) is a functional layer including a compound including a functional group (hereinafter, referred to as “interaction-capable functional group”) capable of allowing electrostatic interaction with the fibrous conductive particles such as metal nanowires contained in the fibrous conductive particles-containing layer 20, because a fibrous conductive particles-containing layer having excellent visible light transmittance, haze, and film hardness is obtained. In a case of including such an interlayer, even when the fibrous conductive particles-containing layer 20 includes the fibrous conductive particles such as metal nanowires and the organic polymer, a fibrous conductive particles-containing layer having excellent film hardness is obtained.
Although the reason is not clear, when the interlayer including a compound including the interaction-capable functional group with the fibrous conductive particles such as metal nanowires contained in the fibrous conductive particles-containing layer 20 is provided, aggregation of the conductive materials of the fibrous conductive particles-containing layer is prevented, even dispersibility is improved, a decrease in transparency haze caused by the aggregation of the conductive materials of the fibrous conductive particles-containing layer is prevented, and the improvement of film hardness due to adhesiveness is achieved, due to the interaction between the fibrous conductive particles such as metal nanowires contained in the fibrous conductive particles-containing layer and the compound including functional group described above contained in the interlayer. The interlayer which can exhibit such interaction may be referred to as a functional layer, hereinafter. The functional layer exhibits the effects described above by allowing the interaction with the fibrous conductive particles such as metal nanowires. Accordingly, when the fibrous conductive particles-containing layer contains the fibrous conductive particles such as metal nanowires, the effects described above are realized without depending on the matrix contained in the fibrous conductive particles-containing layer.
In a case where the fibrous conductive particles such as metal nanowires are silver nanowires, for example, examples of the interaction-capable functional group with the fibrous conductive particles such as metal nanowires include an amido group, an amino group, a mercapto group, a carboxylic acid group, a sulfonic acid group, a phosphoric acid group, and a phosphonic acid group or salt thereof, and a compound containing one or a plurality of functional groups selected from these is more preferable. As the functional group, an amino group, a mercapto group, a phosphoric acid group, and a phosphonic acid group or salt thereof are more preferable and an amino group is even more preferable.
Examples of the compound including the functional group include compounds including an amido group such as ureidopropyltriethoxysilane, polyacrylamide, or polymethacrylamide, compounds including an amino group such as N-β3(aminoethyl) γ-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, bis(hexamethylene)triamine, N,N′-bis(3-aminopropyl)-1,4-butanediamine tetrahydrochloride, spermine, diethylenetriamine, meta-xylenediamine, or metaphenylene diamine, compounds including a mercapto group such as 3-mercaptopropyltrimethoxysilane, 2-mercaptobenzothiazole, or toluene-3,4-dithiol, compounds including a group of sulfonic acid or salt thereof such as poly(sodium para-styrene sulfonate), or poly(2-acrylamido-2-methylpropane sulfonate), compounds including a carboxylic acid group such as polyacrylic acid, polymethacrylic acid, polyaspartic acid, terephthalic acid, cinnamic acid, fumaric acid, or succinic acid, compounds including a phosphoric acid group such as PHOSMER PE, PHOSMER CL, PHOSMER M, and PHOSMER MH (product name, manufactured by Uni-Chemical Co., Ltd.) and polymers thereof, POLYPHOSMER M-101, POLYPHOSMER PE-201, and POLYPHOSMER MH-301 (product name, manufactured by DAP Co., Ltd.), and compounds including a phosphonic acid group such as phenylphosphonic acid, decylphosphonic acid, methylene diphosphonic acid, vinylphosphonic acid, or allylphosphonic acid.
By selecting these functional groups, aggregation of the fibrous conductive particles such as metal nanowires is prevented when applying a coating solution for forming a fibrous conductive particles-containing layer and allowing interaction between the fibrous conductive particles such as metal nanowires and the functional groups contained in the interlayer and drying, and a fibrous conductive particles-containing layer in which the fibrous conductive particles such as metal nanowires are uniformly dispersed can be formed.
The interlayer can be formed by applying liquid obtained by dissolving, dispersing, or emulsifying compounds configuring the interlayer on the support and drying the liquid, and general methods can be used as the application method. The method thereof is not particularly limited and can be suitably selected according to the purpose. Examples thereof include a roll coating method, a bar coating method, a dip coating method, a spin coating method, a casting method, a die coating method, a blade coating method, a gravure coating method, a curtain coating method, a spray coating method, and doctor coating method.
As shown in
The composition of the protective layer is not particularly limited, and cycloolefin polymer (COP), cycloolefin copolymer (COC), a sol-gel hardened material, and a silica sputter is preferable and a sol-gel hardened material is more preferable. As a material for forming a sol-gel hardened material used in a protective layer, a material for forming a sol-gel hardened material included in the fibrous conductive particles-containing layer can be used.
The heat insulating window film of the invention preferably includes a pressure sensitive adhesive layer. The pressure sensitive adhesive layer can contain an ultraviolet absorbing agent.
A material capable of being used for forming the pressure sensitive adhesive layer is not particularly limited and can be suitably selected according to the purpose. Examples thereof include a polyvinyl butyral resin, an acrylic resin, a styrene/acrylic resin, a urethane resin, a polyester resin, and silicone resin. These may be used alone or in combination of two or more kinds thereof. The pressure sensitive adhesive layer formed of these materials can be formed by coating.
As the ultraviolet absorbing agent, a material disclosed in paragraphs “0041” to “0046” of JP2012-215811A can be preferably used and the description in this document is incorporated in this specification.
In addition, an antistatic agent, a lubricant, or an antiblocking agent may be added to the pressure sensitive adhesive layer.
A thickness of the pressure sensitive adhesive layer is preferably from 0.1 μm to 10 μm.
The heat insulating window glass of the invention is a heat insulating window glass obtained by laminating the heat insulating window film of the invention and a glass.
The window of the invention is a window including a transparent window support and the heat insulating window film of the invention bonded to the transparent window support.
As the transparent window support, a transparent window support having a thickness equal to or greater than 0.5 mm is preferable, a transparent window support having a thickness equal to or greater than 1 mm is more preferable, and from a viewpoint of preventing thermal conduction due to the thickness of the transparent window support and increasing warmth, a transparent window support having a thickness equal to or greater than 2 mm is particularly preferable.
In general, a plate-shaped or a sheet-shaped material is used as the transparent window support.
Examples of the transparent window support include transparent glass such as white plate glass, blue plate glass, or silica-coated blue plate glass; a synthetic resin such as polycarbonate, polyether sulfone, polyester, an acrylic resin, a vinyl chloride resin, an aromatic polyamide resin, polyamide imide, or polyimide; metal such as aluminum, copper, nickel, or stainless steel; ceramic; and a silicon wafer used in a semiconductor substrate. Among these, the transparent window support is preferably glass or a resin plate and more preferably glass. Components configuring glass or window glass are not particularly limited, and transparent glass such as white plate glass, blue plate glass, or silica-coated blue plate glass can be used as the glass or the window glass, for example.
The glass used in the invention preferably has a smooth surface and is preferably float glass.
When acquiring visible light transmittance of the heat insulating window glass of the invention, it is preferable to perform the measurement by bonding the heat insulating window film of the invention to a blue plate glass having a thickness of 3 mm. As the blue plate glass having a thickness of 3 mm, a glass disclosed in JIS A 5759 is preferably used.
The heat insulating window film of the invention is bonded to the inner side of the window, that is, the indoor side of the window glass.
In the heat insulating window glass of the invention or the window of the invention, the fibrous conductive particles-containing layer of the heat insulating window film of the invention is disposed on the surface of the support on a side opposite to the surface of the window (glass or transparent window support) side. In the invention, although the heat insulating properties are dependent on the thickness of the fibrous conductive particles-containing layer, a distance between the fibrous conductive particles-containing layer and the outermost surface on the indoor side is preferably within 1 μm, from a viewpoint of increasing heat insulating properties, and more preferably within 0.5 μm.
In addition, the fibrous conductive particles-containing layer is preferably the outermost layer or the second outermost layer on the indoor side, from a viewpoint of increasing heat insulating properties, and more preferably the outermost layer on the indoor side.
An evaluation method of the distance between the fibrous conductive particles-containing layer and the outermost surface on the indoor side is not particularly limited and can be suitably selected according to the purpose. For example, a method of preparing an appropriate sectional piece and performing the evaluation by observing the fibrous conductive particles-containing layer and the outermost surface on the indoor side of this piece may be used. Specifically, a method of preparing a cross section sample or a cross section piece sample of the heat insulating window film by using a microtome or a focused ion beam (FIB) and performing an evaluation from an image obtained by observing the cross section sample or the cross section piece sample by using various microscope (for example, field emission scanning electron microscope (FE-SEM)) is used.
When bonding the heat insulating window film of the invention to the window glass, the heat insulating window film of the invention in which the pressure sensitive adhesive layer is provided by coating or laminating is prepared, an aqueous solution containing a surfactant (mainly anionic) is sprayed to the surface of the window glass or the surface of the pressure sensitive adhesive layer of the heat insulating window film of the invention in advance, and the heat insulating window film of the invention may be installed on the window glass through the pressure sensitive adhesive layer. The pressure sensitive adhesiveness of the pressure sensitive adhesive layer decreases while moisture is evaporated, and accordingly, the position of the heat insulating window film of the invention can be adjusted on the glass surface. After determining the bonding position of the heat insulating window film of the invention to the window glass, the moisture remaining between the window glass and the heat insulating window film of the invention is swept from the center to the edge of the glass by using a squeegee or the like, and accordingly, the heat insulating window film of the invention can be fixed to the surface of the window glass. By doing so, the heat insulating window film of the invention can be installed on the window glass.
The usage of the heat insulating window film, the heat insulating window glass, and the window of the invention is not particularly limited and can be suitably selected according to the purposes. For example, the heat insulating window film, the heat insulating window glass, and the window are used for vehicles, for building materials or buildings, and for agriculture. Among these, the heat insulating window film, the heat insulating window glass, and the window are preferably used in building materials, buildings, and vehicles, from a viewpoint of energy saving effects.
The building material is a building material including the heat insulating window film of the invention or the heat insulating window glass of the invention.
The building is a building including the heat insulating window film of the invention, the heat insulating window glass of the invention, the building material of the invention, or the window of the invention. Examples of the building include a house, an office building, and a warehouse.
The vehicle is a vehicle including the heat insulating window film of the invention, the heat insulating window glass of the invention, or the window of the invention. Examples of the vehicle include a car, a railway vehicle, and a ship.
Hereinafter, the embodiments of the invention will be described more specifically with reference to the examples and comparative examples. The materials, the usage amount, the ratio, the process content, and the process procedure shown in the following examples can be suitably changed within a range not departing from the gist of the invention. Therefore, the ranges of the invention is not narrowly interpreted based on the specific examples shown below.
Short axis lengths (diameters) and long axis lengths of 300 metal nanowires randomly selected from the metal nanowires which were enlarged and observed by using a transmission electron microscope (TEM; product name: JEM-2000FX manufactured by JEOL, Ltd.) were measured, and an average short axis length (average diameter) and an average long axis length of the metal nanowires were acquired from the average value thereof.
The short axis lengths (diameters) of 300 nanowires randomly selected from the transmission electron microscope (TEM) image were measured and a standard deviation and an average value of 300 nanowires were calculated to acquire a coefficient of variation. The coefficient of variation was acquired by dividing the value of the standard deviation by the average value.
The following liquid additives A, G, and H were prepared in advance.
(Liquid Additive A)
5.1 g of silver nitrate powder was dissolved in 500 mL of pure water. After that, 1 mol/L of ammonia water was added thereto until a transparent material was obtained. Pure water was added so that the total amount of the mixture becomes 100 mL.
(Liquid Additive G)
1 g of glucose powder was dissolved in 280 mL of pure water to prepare a liquid additive G
(Liquid Additive H)
4 g of hexadecyl-trimethylammoniumbromide (HTAB) powder was dissolved in 220 mL of pure water to prepare a liquid additive H.
Next, a silver nanowire aqueous dispersion (1) was prepared as follows.
410 mL of pure water was put in a three-necked flask, and 82.5 mL of the liquid additive H and 206 mL of the liquid additive G were added through a funnel while stirring the solution at 20° C. (first stage). 206 mL of the liquid additive A was added to this solution at a flow rate of 2.0 mL/min and a stirring rotation rate of 800 rpm (round per minute) (second stage). After 10 minutes, 82.5 mL of the liquid additive H was added (third stage). Then, the internal temperature was increased to 73° C. at a rate of 3° C./min. After that, the stirring rotation rate was decreased to 200 rpm and the solution was heated for 4 hours. The obtained aqueous dispersion was cooled.
An ultrafiltration module SIP 1013 (product name, manufactured by Asahi Kasei Corporation, molecular weight cutoff: 6,000), a magnet pump, and a stainless steel cup were connected to each other through silicone tubes to prepare an ultrafiltration device.
The cooled aqueous dispersion described above was put into the stainless steel cup of the ultrafiltration device and the pump was operated to perform ultrafiltration. 950 mL of distilled water was added into the stainless steel cup and washing was performed, when the amount of a filtrate from the ultrafiltration module has become 50 mL. The washing described above was repeatedly performed until electric conductivity (measured by CM-25R manufactured by DKK-TOA Corporation) has become equal to or smaller than 50 μS/cm, and then, the concentration was performed to obtain 0.84% silver nanowire aqueous dispersion (1). The obtained silver nanowire aqueous dispersion (1) was set as a silver nanowire aqueous dispersion of Preparation Example 1. An average short axis length and an average long axis length of silver nanowires contained in the silver nanowire aqueous dispersion of Preparation Example 1 obtained and a coefficient of variation of short axis lengths of the silver nanowires were measured as described above. As a result, it was found that the silver nanowires having an average short axis length of 17.1 nm, an average long axis length of 25.1 μm, and a coefficient of variation of 17.9% were obtained. Hereinafter, the “silver nanowire aqueous dispersion (1)” indicates the silver nanowire aqueous dispersion obtained by the method described above.
A solution for adhesion 1 was prepared with the following combination.
(Solution for Adhesion 1)
TAKELAC (registered trademark) WS-4000: 5.0 parts by mass (polyurethane for coating, solid content concentration of 30%, manufactured by Mitsui Chemicals)
Surfactant: 0.3 parts by mass
(product name: NAROACTY HN-100 manufactured by Sanyo Chemical Industries)
Surfactant: 0.3 parts by mass
(SANDET (registered trademark) BL, solid content concentration of 43%, manufactured by Sanyo Chemical Industries)
Water: 94.4 parts by mass
Corona discharge treatment was performed with respect to one surface of a PET film (reference numeral 10 in
A solution for adhesion 2 was prepared with the following combination.
(Solution for Adhesion 2)
Tetraethoxysilane: 5.0 parts by mass
(product name: KBE-04 manufactured by Shin-Etsu Chemical Co., Ltd.)
3-glycidoxypropyltrimethoxysilane: 3.2 parts by mass
(product name: KBM-403 manufactured by Shin-Etsu Chemical Co., Ltd.)
2-(3,4-epoxycyclohexyl) ethyl trimethoxysilane: 1.8 parts by mass
(product name: KBM-303 manufactured by Shin-Etsu Chemical Co., Ltd.)
Acetic acid aqueous solution (acetic acid concentration=0.05%, power of Hydrogen (pH)=5.2): 10.0 parts by mass
Hardener: 0.8 parts by mass
(boric acid manufactured by Wako Pure Chemical Industries, Ltd.)
Colloidal silica: 60.0 parts by mass
(SNOWTEX (registered trademark) 0, average particle diameter of 10 nm to 20 nm, solid content concentration of 20%, pH=2.6, manufactured by Nissan Chemical Industries, Ltd.)
Surfactant: 0.2 parts by mass
(product name: NAROACTY HN-100 manufactured by Sanyo Chemical Industries)
Surfactant: 0.2 parts by mass
(SANDET (registered trademark) BL, solid content concentration of 43%, manufactured by Sanyo Chemical Industries)
The solution for adhesion 2 was prepared by the following method. While vigorously stirring the acetic acid aqueous solution, 3-glycidoxypropyltrimethoxysilane was added dropwise into this acetic acid aqueous solution for 3 minutes. Next, 2-(3,4-epoxycyclohexyl) ethyl trimethoxysilane was added for 3 minutes while strongly stirring the acetic acid aqueous solution. Then, tetraethoxysilane was added for 5 minutes while strongly stirring the acetic acid aqueous solution, and stirring was continued for 2 hours. Next, colloidal silica, the hardener, and the surfactant were sequentially added to prepare the solution for adhesion 2.
The surface of the first adhesive layer (reference numeral 31 in
A solution of an alkoxide compound having the following composition was stirred at 60° C. for 1 hour and a uniform state was confirmed. The prepared solution was set as a sol-gel solution.
Tetraethoxysilane: 5.0 parts by mass
(product name: KBE-04 manufactured by Shin-Etsu Chemical Co., Ltd.)
1% Acetic acid aqueous solution: 10.0 parts by mass
Distilled water: 4.0 parts by mass
8.1 parts by mass of the obtained sol-gel solution and 32.70 parts by mass of the silver nanowire aqueous dispersion (1) obtained in Preparation Example 1 were mixed with each other and diluted using the distilled water to obtain a sol-gel coating solution.
Corona discharge treatment was performed with respect to the surface of the second adhesive layer (reference numeral 32 in
An average film thickness of the fibrous conductive particles-containing layer measured by using an electron microscope as described below was 0.20 μm.
The protective layer (reference numeral 21 in
Then, a slice having a width of approximately 10 μm and a thickness of approximately 100 nm was prepared in a focusing ion beam device (product name: FB-2100) manufactured by Hitachi, Ltd., the cross section of the fibrous conductive particles-containing layer was observed with a scanning transmission electron microscope (product name: HD-2300, applying voltage: 200 kV) manufactured by Hitachi, Ltd., film thicknesses of five portions of the fibrous conductive particles-containing layer were measured, and an average film thickness was calculated as the arithmetic average value thereof. The average film thickness was calculated by measuring only the thickness of the matrix portion not present in the metal nanowires. A distance between the five portions of the fibrous conductive particles-containing layer and the outermost surface on the indoor side was measured and an interlayer distance as was calculated as the arithmetic average value thereof. The obtained results were shown in the following Table 1.
An electron micrograph which is for observing the cross section of the fibrous conductive particles-containing layer with a scanning transmission electron microscope (product name: HD-2300, applying voltage: 200 kV) manufactured by Hitachi, Ltd. and which shows the state of the arrangement of the fibrous conductive particles is shown in
A pressure sensitive adhesive material was bonded onto a rear surface of a surface the adhesive layer-attached support (PET substrate; reference numeral 101 in
The obtained laminate was set as a heat insulating window film of Example 1.
Regarding the heat insulating window film of Example 1, a radio attenuation rate was measured by using a method which will be described later and radio-wave transmittance was evaluated.
The other peelable separator (silicone coat PET) of the pressure sensitive adhesive material PD-S1 was peeled off from the pressure sensitive adhesive layer formed by the method described above, the pressure sensitive adhesive layer was bonded to a plate glass (thickness of plate glass: blue plate glass having a thickness of 3 mm; reference numeral 61 in
Regarding the heat insulating window glass of Example 1, the evaluation regarding properties other than radio-wave transmittance (radio attenuation rate), that is, the evaluation of resistivity, visible light transmittance, and heat insulating properties (coefficient of overall heat transmission) was performed by a method which will be described later. As the plate glass, glass which is obtained by wiping dirt by isopropyl alcohol and naturally drying was used, and at the time of bonding, pressure welding was performed at surface pressure of 0.5 kg/cm2 by using a rubber roller in the environment of 25° C. and relative humidity of 65%.
A heat insulating window film and a heat insulating window glass of Example 2 were prepared in the same manner as in Example 1, except for applying the sol-gel coating solution so that the silver amount of the fibrous conductive particles-containing layer is 0.020 g/m2 and the total solid content coating amount is 0.140 g/m2.
A heat insulating window film and a heat insulating window glass of Example 3 were prepared in the same manner as in Example 1, except for applying the sol-gel coating solution so that the silver amount of the fibrous conductive particles-containing layer is 0.080 g/m2 and the total solid content coating amount is 0.560 g/m2.
A heat insulating window film and a heat insulating window glass of Example 4 were prepared in the same manner as in Example 1, except for preparing a sol-gel coating solution for Example 4 in which a mixing ratio of the sol-gel solution to silver nanowire aqueous dispersion (1) is changed so that the silver amount of the fibrous conductive particles-containing layer is 0.040 g/m2 and the total solid content coating amount is 0.160 g/m2, and applying the sol-gel coating solution for Example 4 instead of the sol-gel coating solution for Example 1.
A heat insulating window film and a heat insulating window glass of Example 5 were prepared in the same manner as in Example 1, except for applying the sol-gel coating solution so that the silver amount of the fibrous conductive particles-containing layer is 0.040 g/m2, the amount of polyvinylpyrrolidone is 0.005 g/m2, and the total solid content coating amount is 0.120 g/m2.
A heat insulating window film and a heat insulating window glass of Example 6 were prepared in the same manner as in Example 1, except for applying the solution for adhesion 2 prepared in Preparation Example 2 onto the fibrous conductive particles-containing layer 20 and further providing the protective layer having a thickness of 0.5 μm.
A heat insulating window film and a heat insulating window glass of Comparative Example 1 were prepared in the same manner as in Example 1, except for preparing a sol-gel coating solution for Comparative Example 1 in which a mixing ratio of the sol-gel solution to silver nanowire aqueous dispersion (1) is changed so that the silver amount of the fibrous conductive particles-containing layer is 0.040 g/m2 and the total solid content coating amount is 0.100 g/m2, and applying the sol-gel coating solution for Comparative Example 1 instead of the sol-gel coating solution for Example 1.
A PET film having a thickness of 75 μm (reference numeral 10 in
The glass (reference numeral 61 in
A heat insulating window film and a heat insulating window glass of Comparative Example 3 were prepared in the same manner as in Example 1, except for providing the pressure sensitive adhesive layer (reference numeral 51 in
A heat ray shielding film disclosed in JP2012-252172A prepared in the same manner as in Example 1 was set as a heat insulating window film of Comparative Example 4.
A heat insulating window glass of Comparative Example 4 was prepared in the same manner as in Example 1, except for using the heat insulating window film of Comparative Example 4 instead of the heat insulating window film of Example 1.
Transmission spectra of heat insulating window glass materials prepared in Examples and Comparative Examples were measured by using a ultraviolet-visible near infrared spectroscope (manufactured by JASCO Corporation, V-670, integrating sphere unit ISN-723) and visible light transmittance was calculated based on JIS R 3106 and JIS A 5759.
In the heat insulating window film of the invention, it is practically necessary that the visible light transmittance in a case of bonding the heat insulating window film to the blue plate glass having a thickness of 3 mm (heat insulating window glass material of Examples and Comparative Examples) is equal to or greater than 70%, and the visible light transmittance of the heat insulating window film of the invention is preferably in a case of bonding the heat insulating window film to the blue plate glass having a thickness of 3 mm is preferably equal to or greater than 80% and more preferably equal to or greater than 85%.
Reflection spectra of heat insulating window glass materials prepared in Examples and Comparative Examples were measured in a wavelength range of 5 μm to 25 μm by using a near infrared spectroscope IFS66v/S (manufactured by Bruker Optics K.K.). The coefficient of overall heat transmission was calculated based on JIS A 5759. The reflectivity at a wavelength of 25 μm to 50 μm was extrapolated from the reflectivity at 25 μm based on JIS A 5759.
AAA: less than 4.5 W/m2·K
AA: equal to or greater than 4.5 W/m2·K and less than 5.0 W/m2·K
A: equal to or greater than 5.0 W/m2·K and less than 5.5 W/m2·K
B: equal to or greater than 5.5 W/m2·K
Radio attenuation rates [dB] at 0.1 MHz and 2 GHz regarding the heat insulating window films of the examples and comparative examples were measured based on the following equation by using a KEC measurement method defined by KEC Electronic Industry Development Center and the radio-wave transmittance was evaluated based on the following standard.
Radio attenuation rates [dB]=20×Log10(Ei/Et)
(In the above equation, Ei represents an incident field intensity [V/m] and Et represents a conductive field intensity [V/m])
AA: radio attenuation rate is less than 1 dB at any frequencies
A: radio attenuation rate is equal to or greater than 1 dB and less than 10 dB at any one frequency
B: radio attenuation rate is equal to or greater than 10 dB at any one frequency
When the radio attenuation rate is small, the radio-wave transmittance is high.
The resistivity of the fibrous conductive particles-containing layer was measured by using a non-contact resistance meter (EC-80: manufactured by Napson Corporation).
The resistivity “OV” means overrange and means high resistance (equal to or greater than 3,000 Ω/□) which cannot be measured in a device.
Measurement results or evaluation results are shown in the following Table 1.
(*1)In Comparative Example 2, resistivity of a silver layer having conductivity was measured.
From Table 1, it was found that the heat insulating window glass of the invention using the heat insulating window film of the invention has excellent heat insulating properties and radio-wave transmittance. Since the heat insulating window film of the invention can be manufactured by a coating method, it is possible to reduce the manufacturing cost and the large area is easily achieved. In the preferred aspect of the heat insulating window glass of the invention using the heat insulating window film of the invention, excellent transparent is obtained.
Meanwhile, it was found that the heat insulating window glass material using the heat insulating window film of the Comparative Example 1 having high conductivity has poor radio-wave transmittance.
It was found that the heat insulating window glass material using the heat insulating window film of the Comparative Example 2 using the metal multilayer film provided by sputtering as a heat insulating material, instead of the fibrous conductive particles-containing layer, has poor radio-wave transmittance. In addition, since the heat insulating window glass material using the heat insulating window film of the Comparative Example 2 is manufactured by a method of providing the metal multilayer film by sputtering, the manufacturing cost was high and it was difficult to have a large area.
It was found that, in a case of the heat insulating window glass using the heat insulating window film of the Comparative Example 3 in which the fibrous conductive particles-containing layer is disposed on the surface of the support on a side opposite to the surface of the glass (window) side, that is, in a case where the fibrous conductive particles-containing layer is between the support and the glass (window), poor heat insulating properties are obtained.
The heat insulating window glass material using the heat insulating window film of the Comparative Example 4 having high conductivity which was prepared in the same manner as in Example 1 of JP2012-252172A has poor radio-wave transmittance.
When the heat insulating window film of Example 1 was bonded to a window of a building material, the consumption of an air conditioner was averagely decreased by 10% during the winter, compared to a case where the heat insulating window film was not used.
In addition, when the heat insulating window film of Example 1 was bonded to a window of a vehicle, the consumption of an air conditioner was averagely decreased by 15% during the winter.
The heat insulating window glass of the invention using the heat insulating window film of the invention has excellent heat insulating properties and radio-wave transmittance, and accordingly, when the heat insulating window film of the invention is disposed on the inner side of the window, it is possible to provide a window having excellent heat insulating properties and radio-wave transmittance. When the heat insulating window film of the invention is used as a building material, it is possible to provide a building or a vehicle including windows having excellent heat insulating properties and radio-wave transmittance. The building provided with such windows can allow light on the outdoor side of the window to emit the indoor side thereof and can prevent heat exchange from the indoor side to the outdoor side. Accordingly, the indoor side (the inside of a room or the inside of a vehicle) of a building or a vehicle provided with such windows can be maintained in a desired environment.
Even when the heat insulating window film of the invention is bonded to the inside of a well-known window (for example, window of a building or a vehicle), it is possible to provide a window having excellent heat insulating properties and radio-wave transmittance.
10: support
20: fibrous conductive particles-containing layer
21: protective layer
31: first adhesive layer
32: second adhesive layer
51: pressure sensitive adhesive layer
61: glass
71: titanium oxide layer
72: silver layer
73: titanium oxide layer
101: adhesive layer-attached support
102: heat insulating member
103: heat insulating window film
111: heat insulating window glass
IN: indoor side
OUT: outdoor side
| Number | Date | Country | Kind |
|---|---|---|---|
| 2014-157163 | Jul 2014 | JP | national |
This application is a Continuation of PCT International Application No. PCT/JP2015/071428, filed on Jul. 29, 2015, which claims priority under 35 U.S.C. Section 119(a) to Japanese Patent Application No. 2014-157163 filed on Jul. 31, 2014. Each of the above applications is hereby expressly incorporated by reference, in its entirety, into the present application.
| Number | Date | Country | |
|---|---|---|---|
| Parent | PCT/JP2015/071428 | Jul 2015 | US |
| Child | 15419084 | US |
