JP7252531B2 - Method for producing resin film, method for producing thermoelectric conversion film, method for producing laminated glass, and method for producing thermoelectric conversion laminated glass - Google Patents

Description

The present invention relates to a method for producing a resin film containing resin. The present invention also relates to a thermoelectric conversion film, a laminated glass, and a method for producing a thermoelectric conversion laminated glass using the resin film.

A glass plate-containing laminate in which a thermoplastic resin film is bonded to a glass plate is known. Laminated glass is widely used among glass plate-containing laminates.

Laminated glass is excellent in safety because the amount of glass fragments scattered is small even if it is broken by an external impact. Therefore, the laminated glass is widely used in automobiles, railroad vehicles, aircraft, ships, buildings, and the like. The laminated glass is manufactured by sandwiching a thermoplastic resin film between a pair of glass plates. In addition to laminated glass, a thermoplastic resin film may be used by bonding it to a member other than a glass plate.

In recent years, attempts have been made to impart new functions to laminated glass.

Patent Document 1 below proposes a laminated glass capable of thawing frozen matter on the surface of the laminated glass. The laminated glass described in Patent Document 1 has a structure in which a plurality of glass plates and an intermediate film are laminated, and the glass plates are laminated via the intermediate film. The combined thermal resistance of the plurality of glass plates and the intermediate film is 0.014-0.25 m ² K/W.

JP 2006-137648 A

As described above, in Patent Document 1, the laminated glass is provided with the function of thawing frozen matter.

The inventor of the present invention considered giving a laminated glass or the like a function different from the function described in Patent Document 1. Specifically, the present inventors have considered imparting a thermoelectric conversion function to a resin film, laminated glass, and the like. However, when a resin film is obtained by simply molding a resin composition containing compounding components into a film, the thermoelectric conversion function of the resin film and laminated glass using the resin film cannot be sufficiently enhanced. A problem was found.

Further, the laminated glass is required to have high transparency.

An object of the present invention is to provide a method for producing a resin film that can exhibit high transparency and high thermoelectric conversion function in the resulting resin film. Another object of the present invention is to provide a method for producing a thermoelectric conversion film, a method for producing laminated glass, and a thermoelectric conversion laminated glass using the resin film.

According to a broad aspect of the present invention, there is provided a method for producing a resin film that is used while being connected to an electrode, comprising: a resin; and a thermoelectric conversion material that exhibits a thermoelectric conversion function while the resin film is connected to the electrode. a step of obtaining a resin film-like material by molding the resin composition into a film, and a step of introducing a dopant into the resin film-like material to obtain a resin film containing the dopant. A method for producing a resin film is provided.

In a specific aspect of the method for producing a resin film according to the present invention, in the step of obtaining the resin film containing the dopant, by impregnating the resin film material with a dopant-containing liquid containing the dopant and a solvent, The dopant is introduced into the resin film material.

In a specific aspect of the method for producing a resin film according to the present invention, the thermoelectric conversion material contains a polythiophene compound.

In a specific aspect of the method for producing a resin film according to the present invention, the polythiophene compound is a polythiophene compound having a structure represented by the following formula (1).

In formula (1), R1 and R2 each represent a hydrogen atom or an organic group.

According to a broad aspect of the present invention, there is provided a method for producing a thermoelectric conversion film, comprising a step of obtaining a resin film by the method for producing a resin film described above, and a step of connecting electrodes to the resin film.

According to a broad aspect of the present invention, the step of obtaining a resin film and the step of disposing the resin film between the first laminated glass member and the second laminated glass member by the method for producing a resin film described above. A method for manufacturing laminated glass is provided.

According to a broad aspect of the present invention, the step of obtaining a resin film and the step of disposing the resin film between the first laminated glass member and the second laminated glass member by the method for producing a resin film described above. and connecting electrodes to the resin film.

A method for producing a resin film according to the present invention is a method for producing a resin film that is used while being connected to an electrode. A method for producing a resin film according to the present invention includes a step of obtaining a resin composition containing a resin and a thermoelectric conversion material that exhibits a thermoelectric conversion function in a state where the resin film is connected to the electrode; into a film to obtain a resin film; and introducing a dopant into the resin film to obtain a dopant-containing resin film. Since the method for producing a resin film according to the present invention has the above configuration, the resulting resin film can exhibit high transparency and high thermoelectric conversion function.

FIG. 1 is a cross-sectional view schematically showing a thermoelectric conversion film manufactured by a method for manufacturing a thermoelectric conversion film according to the first embodiment of the present invention. FIG. 2 is a cross-sectional view schematically showing a thermoelectric conversion film manufactured by a method for manufacturing a thermoelectric conversion film according to the second embodiment of the present invention. FIG. 3 is a cross-sectional view showing an example of thermoelectric conversion laminated glass using the thermoelectric conversion film shown in FIG. FIG. 4 is a cross-sectional view showing an example of thermoelectric conversion laminated glass using the thermoelectric conversion film shown in FIG.

The details of the present invention are described below.

A method for producing a resin film according to the present invention is a method for producing a resin film that is used while being connected to an electrode. The resin film is a resin film that can be used by being connected to an electrode. A method for producing a resin film according to the present invention includes a step of obtaining a resin composition containing a resin and a thermoelectric conversion material that exhibits a thermoelectric conversion function in a state where the resin film is connected to the electrode; into a film to obtain a resin film; and introducing a dopant into the resin film to obtain a dopant-containing resin film.

In the present invention, when the Seebeck coefficient of the resin film is measured and the value of the Seebeck coefficient is 10 ⁻⁷ V/K or more, it is considered that the thermoelectric conversion function is exhibited. For example, electricity can be extracted from the electricity extraction portion by connecting electrodes to two positions separated from each other on the resin film and connecting the electrodes with a conducting wire.

Since the method for producing a resin film according to the present invention has the above configuration, the resulting resin film can exhibit high transparency and high thermoelectric conversion function. The resin film obtained by the method for producing a resin film according to the present invention can be used by being connected to an electrode. By connecting the resin film obtained by the resin film manufacturing method according to the present invention to electrodes, a thermoelectric conversion function can be exhibited.

Moreover, since the method for producing a resin film according to the present invention has the above configuration, it is possible to obtain a resin film having a high electrical conductivity.

As a method of obtaining a resin film having a thermoelectric conversion function, a method of forming a resin composition containing a resin, a thermoelectric conversion material, and a dopant into a film shape can be considered. When obtaining the resin composition and when forming it into a film, the raw material is generally heated at a high temperature for a relatively long time. The present inventors have found that when a resin film is obtained by molding a resin composition containing a resin, a thermoelectric conversion material, and a dopant into a film, the thermoelectric conversion function (especially conductivity) of the resulting resin film is sufficient. It was found that the The present inventors obtained a resin film-like material obtained by forming a resin composition containing a resin and a thermoelectric conversion material into a film, and introduced a dopant into the resin film-like material. It has been found that the conversion function (especially conductivity) can be enhanced. The reason why the thermoelectric conversion function of the resin film can be enhanced by the method for producing the resin film according to the present invention is that the dopant exists in a specific dispersed state in the resin film, and the It is conceivable that the effect of improving the thermoelectric conversion function due to the dopant may not be sufficiently exhibited with the dopant that has been heated for a long period of time, but this is not certain.

Hereinafter, the resin film and the thermoelectric conversion film will be described first, and then the method for manufacturing the resin film and the method for manufacturing the thermoelectric conversion film will be described.

(resin film)
A resin film produced by the method for producing a resin film according to the present invention contains a resin, a thermoelectric conversion material, and a dopant. The resin film is a resin film that is used by being connected to an electrode.

The resin film may have a structure of one layer, a structure of two or more layers, a structure of three or more layers, or a structure of four or more layers. You may have The resin film may have a structure of two or more layers, and may include a first surface layer and a second surface layer. The resin film may have a structure of three or more layers, and may include an intermediate layer between the first surface layer and the second surface layer. The resin film may include two or more intermediate layers. The resin film may comprise a first intermediate layer and a second intermediate layer.

The resin film may have a layer containing the thermoelectric conversion material and a layer not containing the thermoelectric conversion material. The resin film may have a layer containing the dopant and a layer not containing the dopant. The resin film may have a layer containing the thermoelectric conversion material and the dopant and a layer not containing the thermoelectric conversion material and the dopant.

The visible light transmittance of the resin film is preferably 40% or higher, more preferably 50% or higher, even more preferably 60% or higher, even more preferably 70% or higher, even more preferably 80% or higher, and particularly preferably 85%. % or more, particularly preferably 88% or more, most preferably 90% or more. When the visible light transmittance of the resin film is equal to or higher than the lower limit, the transparency can be further improved, and the visibility through the resin film can be effectively improved.

When the resin film is an interlayer film for laminated glass, the interlayer film for laminated glass may have a shade region. The visible light transmittance of the intermediate film for laminated glass (resin film) in the region other than the shade region in the intermediate film for laminated glass is referred to as visible light transmittance A. The visible light transmittance A is preferably 40% or higher, more preferably 50% or higher, even more preferably 60% or higher, still more preferably 70% or higher, even more preferably 80% or higher, and particularly preferably 85% or higher. , more preferably 88% or more, most preferably 90% or more. It is preferable that the resin film has a region in which the visible light transmittance is equal to or higher than the lower limit. It is preferable that the visible light transmittance of the central portion of the resin film is equal to or higher than the lower limit.

In 100% of the plane area of the resin film, the area of the region where the visible light transmittance of the resin film is 40% or more (or the above lower limit or more) is preferably 50% or more, more preferably 80% or more.

The visible light transmittance is measured using a laminated glass obtained by placing a resin film between two sheets of clear glass having a visible light transmittance of 90.4% and complying with JIS R3202:2011. be able to. A spectrophotometer ("U-4100" manufactured by Hitachi High-Tech Co., Ltd.) can be used to measure the visible light transmittance of the obtained laminated glass at a wavelength of 380 nm to 780 nm in accordance with JIS R3106:1998.

(Thermoelectric conversion film)
A thermoelectric conversion film manufactured by the method for manufacturing a thermoelectric conversion film according to the present invention includes the resin film and an electrode, the resin film includes a resin, a thermoelectric conversion material, and a dopant, and the resin film are connected to the electrodes.

FIG. 1 is a cross-sectional view schematically showing a thermoelectric conversion film manufactured by a method for manufacturing a thermoelectric conversion film according to the first embodiment of the present invention. Note that the size and dimensions of the thermoelectric conversion film in FIG. 1 and the figures described later are appropriately changed from the actual size and shape for convenience of illustration.

A thermoelectric conversion film 1 shown in FIG. 1 includes a resin film 10 and electrodes 21 . Resin film 10 includes a resin, a thermoelectric conversion material, and a dopant. One end of the resin film 10 is connected to the electrode 21 and the other end is connected to the electrode 21 . The two electrodes 21 are connected by a conductor 22 . An electrical outlet 23 is arranged in the conductor 22 .

The resin film 10 includes a first layer 11 (intermediate layer), a second layer 12 (surface layer), and a third layer 13 (surface layer). A second layer 12 is arranged and laminated on the first surface side of the first layer 11 . A third layer 13 is arranged and laminated on the second surface side opposite to the first surface of the first layer 11 . The first layer 11 is arranged and sandwiched between the second layer 12 and the third layer 13 . The resin film 10 is a multilayer film.

In this embodiment, the first layer 11 contains a thermoelectric conversion material and a dopant. One end of the first layer 11 is connected to the electrode 21 and the other end is connected to the electrode 21 . In addition, the first layer, the second layer and the third layer may contain a thermoelectric conversion material and a dopant.

The outer surface of the second layer 12 opposite to the first layer 11 side is preferably the surface on which the laminated glass member is laminated. The outer surface of the third layer 13 opposite to the first layer 11 side is preferably the surface on which the laminated glass member is laminated.

FIG. 2 is a cross-sectional view schematically showing a thermoelectric conversion film manufactured by a method for manufacturing a thermoelectric conversion film according to the second embodiment of the present invention.

A thermoelectric conversion film 1A shown in FIG. 2 includes a resin film 10A and electrodes 21 . The resin film 10A contains a resin, a thermoelectric conversion material, and a dopant. One end of the resin film 10A is connected to the electrode 21, and the other end is connected to the electrode 21. As shown in FIG. The two electrodes 21 are connected by a conductor 22 . An electrical outlet 23 is arranged in the conductor 22 .

The resin film 10A has a first layer. The resin film 10A is a single-layer film having a one-layer structure of only the first layer. The resin film 10A is the first layer.

As shown in FIGS. 1 and 2, the resin film may be a multilayer film or a single layer film.

(Manufacturing method of resin film)
A method for producing a resin film according to the present invention comprises the following steps (1) to (3). (1) A step of obtaining a resin composition containing a resin and a thermoelectric conversion material that exhibits a thermoelectric conversion function in a state where the resin film is connected to the electrodes. (2) A step of forming the resin composition into a film to obtain a resin film. (3) A step of introducing a dopant into the resin film material to obtain a resin film containing the dopant.

(1) In the step of obtaining a resin composition, it is preferable to obtain the resin composition by kneading the resin and the thermoelectric conversion material. In addition to the resin and the thermoelectric conversion material, the resin composition may contain a plasticizer, a light stabilizer, a metal salt, an ultraviolet shielding agent, an antioxidant, and the like, which will be described later. In this case, in the step of obtaining the resin composition, the resin composition can be obtained by kneading the resin, the thermoelectric conversion material, and other components blended as necessary. .

The kneading method is not particularly limited. Examples of the kneading method include methods using an extruder, plastograph, kneader, Banbury mixer, calender roll, and the like.

From the viewpoint of uniform kneading, the kneading temperature is preferably 100° C. or higher, more preferably 125° C. or higher, preferably 250° C. or lower, and more preferably 220° C. or lower. If the resin composition does not contain a dopant during kneading, the dopant will not be exposed to heat.

(2) In the step of obtaining a resin film material, the method of forming the resin composition into a film is not particularly limited. Examples of the method for obtaining a single-layer resin film material include a method of extruding the obtained resin composition using an extruder, and a method of press-molding the obtained resin composition. Methods for obtaining a multilayer resin film include a method of forming each layer using each resin composition for forming each layer and then laminating each layer obtained, and a method of laminating each layer using an extruder. Examples include a method of laminating each layer by co-extrusion of each resin composition for forming. A method of extrusion molding using an extruder is preferable, and a method of extrusion molding using a twin-screw extruder is more preferable because it is suitable for continuous production. A resin film may be obtained by laminating a layer containing a thermoelectric conversion material and into which a dopant is introduced and a layer containing neither a thermoelectric conversion material nor a dopant.

The method for forming the resin composition into a film is preferably thermoforming. If the dopant is not introduced at the resin composition stage, the dopant will not be exposed to heat during thermoforming.

The temperature during the molding is preferably 130° C. or higher, more preferably 150° C. or higher, preferably 200° C. or lower, and more preferably 180° C. or lower.

(3) In the step of obtaining a resin film containing a dopant, it is preferable to introduce the dopant into the resin film-like material by impregnating the resin film-like material with a dopant-containing liquid containing the dopant and a solvent. . In this case, the thermoelectric conversion function and electrical conductivity of the resin film can be further enhanced.

The solvent is preferably an organic solvent. Examples of the organic solvent include acetonitrile, chloroform and acetone.

From the viewpoint of further enhancing the thermoelectric conversion function and electrical conductivity of the resin film, the solvent is preferably acetonitrile.

The concentration of the dopant in the dopant-containing liquid is preferably 1 mmol/L or higher, more preferably 5 mmol/L or higher, preferably 200 mmol/L or lower, and more preferably 100 mmol/L or lower. When the dopant concentration is equal to or higher than the lower limit and equal to or lower than the upper limit, the thermoelectric conversion function and electrical conductivity of the resin film can be further enhanced.

Examples of the method for impregnating the resin film-like material with the dopant-containing liquid include a method of immersing the resin film-like material in the dopant-containing liquid, and a method of coating the resin film-like material with the dopant-containing liquid. mentioned.

The method of impregnating the resin film-like material with the dopant-containing liquid is preferably a method of immersing the resin film-like material in the dopant-containing liquid. In this case, a resin film can be obtained in a short time.

In the step of obtaining the resin film containing the dopant, the content of the dopant is preferably 5 parts by weight or more, more preferably 10 parts by weight or more, relative to 100 parts by weight of the thermoelectric conversion material in the resin film obtained. It is preferable that the dopant is introduced into the resin film material so that In the step of obtaining the resin film containing the dopant, the content of the dopant is preferably 40 parts by weight or less, more preferably 30 parts by weight or less with respect to 100 parts by weight of the thermoelectric conversion material in the resin film obtained. It is preferable that the dopant is introduced into the resin film material so that

In the step of obtaining the resin film containing the dopant, when the resin film material is impregnated with the dopant-containing liquid containing the dopant and the solvent, the method for producing a resin film according to the present invention includes (4 ) It is preferable to include a step of removing the solvent.

Examples of the method for removing the solvent include a method of drying a resin film impregnated with a dopant-containing liquid.

A resin film (multilayer film) having a layer containing the thermoelectric conversion material and the dopant and a layer not containing the thermoelectric conversion material and the dopant can be produced, for example, as follows.

A first resin film containing the resin, the thermoelectric conversion material, and the dopant is obtained by the resin film manufacturing method described above. Also, a composition containing a resin and not containing the thermoelectric conversion material and the dopant is molded to obtain a second resin film. A resin film is obtained by laminating a second resin film on the first surface side of the first resin film, or on the first surface side and the second surface side. In the obtained resin film (multilayer film), the layer formed by the first resin film is a layer containing the thermoelectric conversion material and the dopant, and the layer formed by the second resin film is the thermoelectric conversion It is a layer that does not contain materials and the dopants mentioned above.

(Method for producing thermoelectric conversion film)
A method for producing a thermoelectric conversion film according to the present invention preferably includes a step of obtaining a resin film by the method for producing a resin film described above, and a step of connecting electrodes to the resin film.

Hereinafter, details of the first layer (including a single layer film), the second layer and the third layer, which constitute the resin film, and the resin composition, the first layer, the third layer Details of each component contained in the second layer and the third layer will be described.

(resin)
The resin composition contains a resin. The resin film contains a resin. Examples of the resin include thermoplastic resins and thermosetting resins. Only one kind of the resin may be used, or two or more kinds thereof may be used in combination.

The resin is preferably a thermoplastic resin. Therefore, the resin composition preferably contains a thermoplastic resin. The resin film preferably contains a thermoplastic resin. A resin film containing the thermoplastic resin as the resin is a thermoplastic resin film. The resin film is preferably a thermoplastic resin film.

The thermoplastic resin film contains a thermoplastic resin (hereinafter sometimes referred to as thermoplastic resin (0)). The thermoplastic film preferably contains a polyvinyl acetal resin (hereinafter sometimes referred to as polyvinyl acetal resin (0)) as the thermoplastic resin (0). The first layer preferably contains a thermoplastic resin (hereinafter sometimes referred to as thermoplastic resin (1)). The first layer preferably contains a polyvinyl acetal resin (hereinafter sometimes referred to as polyvinyl acetal resin (1)) as the thermoplastic resin (1). The second layer preferably contains a thermoplastic resin (hereinafter sometimes referred to as thermoplastic resin (2)). The second layer preferably contains a polyvinyl acetal resin (hereinafter sometimes referred to as polyvinyl acetal resin (2)) as the thermoplastic resin (2). The third layer preferably contains a thermoplastic resin (hereinafter sometimes referred to as thermoplastic resin (3)). The third layer preferably contains a polyvinyl acetal resin (hereinafter sometimes referred to as polyvinyl acetal resin (3)) as the thermoplastic resin (3). The thermoplastic resin (1), the thermoplastic resin (2), and the thermoplastic resin (3) may be the same or different. It is preferable that the thermoplastic resin (1) is different from the thermoplastic resin (2) and the thermoplastic resin (3), since the sound insulation is further enhanced. The polyvinyl acetal resin (1), the polyvinyl acetal resin (2), and the polyvinyl acetal resin (3) may be the same or different. It is preferable that the polyvinyl acetal resin (1) is different from the polyvinyl acetal resin (2) and the polyvinyl acetal resin (3) because the sound insulation is further enhanced. Each of the thermoplastic resin (0), the thermoplastic resin (1), the thermoplastic resin (2), and the thermoplastic resin (3) may be used alone or in combination of two or more. may Each of the polyvinyl acetal resin (0), the polyvinyl acetal resin (1), the polyvinyl acetal resin (2), and the polyvinyl acetal resin (3) may be used alone or in combination of two or more. may

Examples of the thermoplastic resin include polyvinyl acetal resin, ionomer resin, ethylene-vinyl acetate copolymer resin, ethylene-acrylic acid copolymer resin, polyurethane resin, polyvinyl chloride resin, polyvinyl alcohol resin and cycloolefin resin. be done. Only one kind of the thermoplastic resin may be used, or two or more kinds thereof may be used in combination.

The thermoplastic resin film preferably contains polyvinyl acetal resin, polyvinyl chloride resin or ionomer resin as the thermoplastic resin, more preferably contains polyvinyl acetal resin or polyvinyl chloride resin, and contains polyvinyl acetal resin. is more preferred. The combined use of the polyvinyl acetal resin and the plasticizer further increases the adhesive strength of the thermoplastic resin film to glass plates, laminated glass members, other films, or the like. It is preferable that the surface layer and the intermediate layer contain a polyvinyl acetal resin, a polyvinyl chloride resin, or an ionomer resin. Each of the polyvinyl acetal resin, the polyvinyl chloride resin, and the ionomer resin may be used alone or in combination of two or more.

The polyvinyl acetal resin can be produced, for example, by acetalizing polyvinyl alcohol (PVA) with an aldehyde. The polyvinyl acetal resin is preferably an acetalized product of polyvinyl alcohol. The polyvinyl alcohol is obtained, for example, by saponifying polyvinyl acetate. The degree of saponification of the polyvinyl alcohol is generally within the range of 70 mol % to 99.9 mol %.

The average degree of polymerization of the polyvinyl alcohol (PVA) is preferably 200 or more, more preferably 500 or more, still more preferably 1500 or more, still more preferably 1600 or more, particularly preferably 2600 or more, most preferably 2700 or more, It is preferably 5,000 or less, more preferably 4,000 or less, and still more preferably 3,500 or less. When the average degree of polymerization is equal to or higher than the lower limit, the penetration resistance becomes even higher. When the average degree of polymerization is equal to or less than the upper limit, molding of the thermoplastic resin film is facilitated.

The average degree of polymerization of polyvinyl alcohol is determined by a method based on JIS K6726 "Polyvinyl alcohol test method".

The number of carbon atoms in the acetal group contained in the polyvinyl acetal resin is not particularly limited. Aldehyde used when producing the polyvinyl acetal resin is not particularly limited. The acetal group in the polyvinyl acetal resin preferably has 3 to 5 carbon atoms, more preferably 3 or 4 carbon atoms. When the number of carbon atoms in the acetal group in the polyvinyl acetal resin is 3 or more, the glass transition temperature of the thermoplastic resin film becomes sufficiently low.

The aldehyde is not particularly limited. Generally, aldehydes having 1 to 10 carbon atoms are preferably used. Examples of the aldehyde having 1 to 10 carbon atoms include formaldehyde, acetaldehyde, propionaldehyde, n-butyraldehyde, isobutyraldehyde, n-valeraldehyde, 2-ethylbutyraldehyde, n-hexylaldehyde, n-octylaldehyde, Examples include n-nonylaldehyde, n-decylaldehyde and benzaldehyde. Propionaldehyde, n-butyraldehyde, isobutyraldehyde, n-hexylaldehyde or n-valeraldehyde are preferred, propionaldehyde, n-butyraldehyde or isobutyraldehyde are more preferred, and n-butyraldehyde is even more preferred. Only one kind of the aldehyde may be used, or two or more kinds thereof may be used in combination.

The hydroxyl group content (hydroxyl group amount) of the polyvinyl acetal resin (0) is preferably 15 mol% or more, more preferably 18 mol% or more, and preferably 40 mol% or less, more preferably 35 mol% or less. be. When the hydroxyl content is equal to or higher than the lower limit, the adhesive strength of the thermoplastic resin film is further increased. Moreover, when the content of the hydroxyl group is equal to or less than the upper limit, the thermoplastic resin film becomes more flexible, and the thermoplastic resin film becomes easier to handle.

The hydroxyl content (hydroxyl group amount) of the polyvinyl acetal resin (1) is preferably 17 mol% or more, more preferably 20 mol% or more, still more preferably 22 mol% or more, and preferably 28 mol% or less. It is more preferably 27 mol % or less, still more preferably 25 mol % or less, and particularly preferably 24 mol % or less. When the hydroxyl content is equal to or higher than the lower limit, the mechanical strength of the thermoplastic resin film is further increased. In particular, when the hydroxyl group content of the polyvinyl acetal resin (1) is 20 mol% or more, the reaction efficiency is high and the productivity is excellent. . Moreover, when the content of the hydroxyl group is equal to or less than the upper limit, the thermoplastic resin film becomes more flexible, and the thermoplastic resin film becomes easier to handle.

Each hydroxyl group content of the polyvinyl acetal resin (2) and the polyvinyl acetal resin (3) is preferably 25 mol% or more, more preferably 28 mol% or more, still more preferably 30 mol% or more, and still more preferably 31.5 mol % or more, more preferably 32 mol % or more, and particularly preferably 33 mol % or more. Each hydroxyl group content of the polyvinyl acetal resin (2) and the polyvinyl acetal resin (3) is preferably 38 mol% or less, more preferably 37 mol% or less, still more preferably 36.5 mol% or less, and particularly preferably is 36 mol % or less. When the hydroxyl content is equal to or higher than the lower limit, the adhesive strength of the thermoplastic resin film is further increased. Further, when the content of the hydroxyl group is equal to or less than the upper limit, the thermoplastic resin film becomes more flexible, and the thermoplastic resin film becomes easier to handle.

From the viewpoint of further enhancing sound insulation, the content of hydroxyl groups in the polyvinyl acetal resin (1) is preferably lower than the content of hydroxyl groups in the polyvinyl acetal resin (2). From the viewpoint of further improving sound insulation, the content of hydroxyl groups in the polyvinyl acetal resin (1) is preferably lower than the content of hydroxyl groups in the polyvinyl acetal resin (3). From the viewpoint of further improving sound insulation, the absolute value of the difference between the hydroxyl group content of the polyvinyl acetal resin (1) and the hydroxyl group content of the polyvinyl acetal resin (2) is preferably 1 mol % or more. , more preferably 5 mol % or more, still more preferably 9 mol % or more, particularly preferably 10 mol % or more, and most preferably 12 mol % or more. From the viewpoint of further improving the sound insulation, the absolute value of the difference between the hydroxyl group content of the polyvinyl acetal resin (1) and the hydroxyl group content of the polyvinyl acetal resin (3) is preferably 1 mol % or more. , more preferably 5 mol % or more, still more preferably 9 mol % or more, particularly preferably 10 mol % or more, and most preferably 12 mol % or more. The absolute value of the difference between the hydroxyl group content of the polyvinyl acetal resin (1) and the hydroxyl group content of the polyvinyl acetal resin (2), the hydroxyl group content of the polyvinyl acetal resin (1), and the The absolute value of the difference from the hydroxyl group content of the polyvinyl acetal resin (3) is preferably 20 mol % or less.

The content of hydroxyl groups in the polyvinyl acetal resin is the molar fraction obtained by dividing the amount of ethylene groups to which hydroxyl groups are bonded by the total amount of ethylene groups in the main chain, expressed as a percentage. The amount of ethylene groups to which the hydroxyl groups are bonded can be measured according to, for example, JIS K6728 "Polyvinyl butyral test method".

The degree of acetylation (acetyl group content) of the polyvinyl acetal resin (0) is preferably 0.1 mol% or more, more preferably 0.3 mol% or more, and still more preferably 0.5 mol% or more. is 30 mol % or less, more preferably 25 mol % or less, still more preferably 20 mol % or less. Compatibility of polyvinyl acetal resin and a plasticizer becomes it high that the said degree of acetylation is more than the said minimum. When the degree of acetylation is equal to or less than the upper limit, the thermoplastic resin film and laminated glass have high moisture resistance.

The degree of acetylation (acetyl group content) of the polyvinyl acetal resin (1) is preferably 0.01 mol% or more, more preferably 0.1 mol% or more, still more preferably 7 mol% or more, still more preferably 9 It is mol % or more, preferably 30 mol % or less, more preferably 25 mol % or less, still more preferably 24 mol % or less, and particularly preferably 20 mol % or less. Compatibility of polyvinyl acetal resin and a plasticizer becomes it high that the said degree of acetylation is more than the said minimum. When the degree of acetylation is equal to or less than the upper limit, the thermoplastic resin film and laminated glass have high moisture resistance. In particular, when the degree of acetylation of the polyvinyl acetal resin (1) is 0.1 mol % or more and 25 mol % or less, the penetration resistance is excellent.

The degree of acetylation of the polyvinyl acetal resin (2) and the polyvinyl acetal resin (3) is preferably 0.01 mol% or more, more preferably 0.5 mol% or more, and preferably 10 mol% or less. More preferably, it is 2 mol % or less. Compatibility of polyvinyl acetal resin and a plasticizer becomes it high that the said degree of acetylation is more than the said minimum. When the degree of acetylation is equal to or less than the upper limit, the thermoplastic resin film and laminated glass have high moisture resistance.

The degree of acetylation is the molar fraction obtained by dividing the amount of ethylene groups to which acetyl groups are bonded by the total amount of ethylene groups in the main chain, expressed as a percentage. The amount of ethylene groups to which the acetyl groups are bonded can be measured according to, for example, JIS K6728 "Polyvinyl butyral test method".

The degree of acetalization of the polyvinyl acetal resin (0) (degree of butyralization in the case of polyvinyl butyral resin) is preferably 60 mol% or more, more preferably 63 mol% or more, preferably 85 mol% or less, and more It is preferably 75 mol % or less, more preferably 70 mol % or less. Compatibility of polyvinyl acetal resin and a plasticizer becomes it high that the said degree of acetalization is more than the said minimum. When the degree of acetalization is equal to or less than the upper limit, the reaction time required for producing the polyvinyl acetal resin is shortened.

The degree of acetalization of the polyvinyl acetal resin (1) (the degree of butyralization in the case of a polyvinyl butyral resin) is preferably 47 mol% or more, more preferably 60 mol% or more, and preferably 85 mol% or less. It is preferably 80 mol % or less, more preferably 75 mol % or less. Compatibility of polyvinyl acetal resin and a plasticizer becomes it high that the said degree of acetalization is more than the said minimum. When the degree of acetalization is equal to or less than the upper limit, the reaction time required for producing the polyvinyl acetal resin is shortened.

The degree of acetalization (degree of butyralization in the case of polyvinyl butyral resin) of the polyvinyl acetal resin (2) and the polyvinyl acetal resin (3) is preferably 55 mol% or more, more preferably 60 mol% or more. , preferably 75 mol % or less, more preferably 71 mol % or less. Compatibility of polyvinyl acetal resin and a plasticizer becomes it high that the said degree of acetalization is more than the said minimum. When the degree of acetalization is equal to or less than the upper limit, the reaction time required for producing the polyvinyl acetal resin is shortened.

The degree of acetalization is determined as follows. First, a value is obtained by subtracting the amount of ethylene groups to which hydroxyl groups are bonded and the amount of ethylene groups to which acetyl groups are bonded from the total amount of ethylene groups in the main chain. The obtained value is divided by the total amount of ethylene groups in the main chain to obtain the mole fraction. The degree of acetalization is the value of this mole fraction expressed as a percentage.

The hydroxyl content (hydroxyl group amount), the degree of acetalization (degree of butyralization) and the degree of acetylation are preferably calculated from the results of measurements according to JIS K6728 "Polyvinyl butyral test method". However, measurement according to ASTM D1396-92 may be used. When the polyvinyl acetal resin is a polyvinyl butyral resin, the hydroxyl content (hydroxyl group amount), the degree of acetalization (degree of butyralization), and the degree of acetylation are determined according to JIS K6728 "Polyvinyl butyral test method". can be calculated from the results measured by

(Plasticizer)
From the viewpoint of further increasing the adhesive strength of the resin film, the resin composition preferably contains a plasticizer. From the viewpoint of further increasing the adhesive strength of the resin film, the resin film preferably contains a plasticizer (hereinafter sometimes referred to as plasticizer (0)). The first layer preferably contains a plasticizer (hereinafter sometimes referred to as plasticizer (1)). The second layer preferably contains a plasticizer (hereinafter sometimes referred to as plasticizer (2)). The third layer preferably contains a plasticizer (hereinafter sometimes referred to as plasticizer (3)). When the resin contained in the resin film is a polyvinyl acetal resin, it is particularly preferable that the resin film (each layer) contain a plasticizer. The layer containing polyvinyl acetal resin preferably contains a plasticizer.

The plasticizer is not particularly limited. Conventionally known plasticizers can be used as the plasticizer. Only one type of the plasticizer may be used, or two or more types may be used in combination.

Examples of the plasticizer include organic ester plasticizers such as monobasic organic acid esters and polybasic organic acid esters, and organic phosphoric acid plasticizers such as organic phosphoric acid plasticizers and organic phosphorous acid plasticizers. . Organic ester plasticizers are preferred. Preferably, the plasticizer is a liquid plasticizer.

Examples of the monobasic organic acid esters include glycol esters obtained by reacting a glycol with a monobasic organic acid. Examples of the glycol include triethylene glycol, tetraethylene glycol and tripropylene glycol. Examples of the monobasic organic acids include butyric acid, isobutyric acid, caproic acid, 2-ethylbutyric acid, heptylic acid, n-octylic acid, 2-ethylhexylic acid, n-nonylic acid and decylic acid.

Examples of the polybasic organic acid esters include ester compounds of polybasic organic acids and alcohols having a linear or branched structure having 4 to 8 carbon atoms. Examples of the polybasic organic acids include adipic acid, sebacic acid and azelaic acid.

Examples of the organic ester plasticizer include triethylene glycol di-2-ethylpropanoate, triethylene glycol di-2-ethylbutyrate, triethylene glycol di-2-ethylhexanoate, triethylene glycol dicaprylate, Triethylene glycol di-n-butanoate, triethylene glycol di-n-octanoate, triethylene glycol di-n-heptanoate, tetraethylene glycol di-n-heptanoate, dibutyl sebacate, dioctyl azelate, dibutyl carbitol adipate, ethylene Glycol di-2-ethylbutyrate, 1,3-propylene glycol di-2-ethylbutyrate, 1,4-butylene glycol di-2-ethylbutyrate, diethylene glycol di-2-ethylbutyrate, diethylene glycol di-2 - ethylhexanoate, dipropylene glycol di-2-ethylbutyrate, triethylene glycol di-2-ethylpentanoate, tetraethylene glycol di-2-ethylbutyrate, diethylene glycol dicaprylate, dibutyl maleate, adipine bis(2-butoxyethyl) acid, dibutyl adipate, diisobutyl adipate, 2,2-butoxyethoxyethyl adipate, glycol benzoate, 1,3-butylene glycol polyester adipate, dihexyl adipate, dioctyl adipate, Hexylcyclohexyl adipate, mixture of heptyl adipate and nonyl adipate, diisononyl adipate, diisodecyl adipate, heptyl nonyl adipate, tributyl citrate, acetyl tributyl citrate, diethyl carbonate, dibutyl sebacate, bis(2- ethylhexyl), bis(2-ethylhexyl) phthalate, oil-modified alkyd sebacate, and a mixture of phosphate and adipate. Organic ester plasticizers other than these may be used. Other adipic acid esters than those mentioned above may be used.

Examples of the organic phosphoric acid plasticizer include tributoxyethyl phosphate, isodecylphenyl phosphate and triisopropyl phosphate.

The plasticizer is preferably a diester plasticizer represented by the following formula (2).

In the above formula (2), R1 and R2 each represent an organic group having 5 to 10 carbon atoms, R3 represents an ethylene group, an isopropylene group or an n-propylene group, and p represents an integer of 3 to 10. . Each of R1 and R2 in the above formula (2) is preferably an organic group having 6 to 10 carbon atoms.

The plasticizer is triethylene glycol di-n-butanoate (3GB), bis(2-ethylhexyl) sebacate, bis(2-ethylhexyl) phthalate, triethylene glycol di-2-ethylhexanoate (3GO) or It preferably contains triethylene glycol di-2-ethylbutyrate (3GH). The plasticizer more preferably includes triethylene glycol di-n-butanoate (3GB), triethylene glycol di-2-ethylhexanoate (3GO) or triethylene glycol di-2-ethylbutyrate (3GH). More preferably, it contains triethylene glycol di-2-ethylhexanoate.

The content of the plasticizer (0) with respect to 100 parts by weight of the thermoplastic resin (0) in the thermoplastic resin film is defined as content (0). The content (0) is preferably 20 parts by weight or more, more preferably 25 parts by weight or more, still more preferably 30 parts by weight or more, preferably 100 parts by weight or less, more preferably 60 parts by weight or less, and still more preferably is 50 parts by weight or less. When the content (0) is equal to or higher than the lower limit, the penetration resistance becomes even higher. If the content (0) is equal to or less than the upper limit, the thermoplastic resin film will have even higher transparency.

In the first layer, the content of the plasticizer (1) with respect to 100 parts by weight of the thermoplastic resin (1) is defined as content (1). The content (1) is preferably 50 parts by weight or more, more preferably 55 parts by weight or more, still more preferably 60 parts by weight or more, preferably 100 parts by weight or less, more preferably 90 parts by weight or less, and even more preferably is 85 parts by weight or less, particularly preferably 80 parts by weight or less. When the content (1) is equal to or higher than the lower limit, the thermoplastic resin film becomes more flexible, and the thermoplastic resin film becomes easier to handle. When the content (1) is equal to or less than the upper limit, the penetration resistance becomes even higher.

In the second layer, the content of the plasticizer (2) with respect to 100 parts by weight of the thermoplastic resin (2) is referred to as content (2). In the third layer, the content (3) is defined as the content of the plasticizer (3) with respect to 100 parts by weight of the thermoplastic resin (3). Each of the content (2) and the content (3) is preferably 10 parts by weight or more, more preferably 15 parts by weight or more, still more preferably 20 parts by weight or more, particularly preferably 24 parts by weight or more, and most preferably 25 parts by weight or more. Each of the content (2) and the content (3) is preferably 45 parts by weight or less, more preferably 40 parts by weight or less, still more preferably 35 parts by weight or less, particularly preferably 32 parts by weight or less, and most preferably 30 parts by weight or less. When the content (2) and the content (3) are equal to or higher than the lower limit, the thermoplastic resin film has a high flexibility and can be easily handled. When the content (2) and the content (3) are equal to or less than the upper limit, the penetration resistance is further enhanced.

In order to improve the sound insulation of the laminated glass, the content (1) is preferably greater than the content (2), and the content (1) is preferably greater than the content (3).

From the viewpoint of further enhancing the sound insulation of the laminated glass, the absolute value of the difference between the content (2) and the content (1) is preferably 10 parts by weight or more, more preferably 15 parts by weight or more, and Preferably, it is 20 parts by weight or more. From the viewpoint of further enhancing the sound insulation of the laminated glass, the absolute value of the difference between the content (3) and the content (1) is preferably 10 parts by weight or more, more preferably 15 parts by weight or more, and Preferably, it is 20 parts by weight or more. The absolute value of the difference between the content (2) and the content (1) and the absolute value of the difference between the content (3) and the content (1) are preferably 80 parts by weight or less, More preferably 75 parts by weight or less, still more preferably 70 parts by weight or less.

(thermoelectric conversion material)
The resin material includes a thermoelectric conversion material. The resin film contains a thermoelectric conversion material. It is preferable that the surface layer contains the thermoelectric conversion material. It is preferable that the intermediate layer contains the thermoelectric conversion material. Only one type of the thermoelectric conversion material may be used, or two or more types may be used in combination.

From the viewpoint of effectively increasing the thermoelectric conversion efficiency, the thermoelectric conversion material is preferably particulate or fibrous, and more preferably fibrous.

The thermoelectric conversion material may be an inorganic compound or an organic compound. From the viewpoint of effectively increasing the thermoelectric conversion efficiency, the thermoelectric conversion material is preferably an organic compound. Also, the thermoelectric conversion material is preferably organic nanofibers.

Examples of the thermoelectric conversion material include polythiophene compounds and charge-transfer complexes containing polythiophene compounds such as PEDOT PSS. From the viewpoint of further enhancing the transparency of the resin film, the thermoelectric conversion material preferably contains a polythiophene compound.

The above polythiophene compound is preferably a polythiophene compound having a structure represented by the following formula (1). In this case, the polythiophene compound having the structure represented by formula (1) may be contained in the resin composition and resin film in the form of a charge transfer complex. Moreover, the polythiophene compound having the structure represented by the formula (1) may be contained in the resin composition and the resin film in a nanofiber state.

In formula (1) above, R1 and R2 each represent a hydrogen atom or an organic group.

From the viewpoint of further increasing the thermoelectric conversion efficiency, the polythiophene compound having the structure represented by the above formula (1) preferably has a structure in which a plurality of the structures represented by the above formula (1) are continuous. From the viewpoint of further increasing the thermoelectric conversion efficiency, the polythiophene compound having the structure represented by the above formula (1) is preferably a polythiophene compound having the structure represented by the following formula (1A).

In formula (1A) above, R1 and R2 each represent a hydrogen atom or an organic group, and n represents an integer of 5 or more and 500 or less.

From the viewpoint of effectively increasing the thermoelectric conversion efficiency, either one of R1 and R2 in the above formula (1) and the above formula (1A) is preferably a hydrogen atom, a methyl group, or an ethyl group, and R1 and the other of R2 is preferably an organic group having 1 to 12 carbon atoms. The organic group having 1 to 12 carbon atoms is preferably a hydrocarbon group having 1 to 12 carbon atoms, more preferably an alkyl group having 1 to 12 carbon atoms. The hydrocarbon group having 1 to 12 carbon atoms and the alkyl group having 1 to 12 carbon atoms may have a linear structure or a branched structure. The organic group having 1 to 12 carbon atoms may have atoms other than carbon atoms and hydrogen atoms, and may have a substituent. The alkyl group having 1 to 12 carbon atoms is more preferably an alkyl group having 3 to 8 carbon atoms, and more preferably an alkyl group having 6 carbon atoms (such as a hexyl group).

In the above formula (1A), n is preferably an integer of 50 or more, and preferably an integer of 400 or less, from the viewpoint of effectively increasing the thermoelectric conversion efficiency.

When the thermoelectric conversion material is contained on the surface of the resin film, the adhesiveness of the resin film may deteriorate.

In the multilayer film, the intermediate layer preferably contains a thermoelectric conversion material. In the multilayer film in which the first layer is arranged between the second layer and the third layer, the first layer preferably contains a thermoelectric conversion material.

In the multilayer film in which the first layer is arranged between the second layer and the third layer, the content of the thermoelectric conversion material in the first layer is the same as that of the second layer and the third layer. It is preferably higher than the content of the thermoelectric conversion material inside, more preferably 0.005% by weight or more, and even more preferably 0.01% by weight or more. Each of the second layer and the third layer may not contain a thermoelectric conversion material. The content of the thermoelectric conversion material in the second layer and the third layer may be 0.05% by weight or less in 100% by weight of the second layer and 100% by weight of the third layer. It may be less than 0.03 wt%, and may be less than 0.01 wt%.

The content of the thermoelectric conversion material in 100% by weight of the resin film and 100% by weight of the layer containing the thermoelectric conversion material is preferably 0.01% by weight or more, more preferably 0.03% by weight or more, and still more preferably It is 0.05% by weight or more. When the content of the thermoelectric conversion material is at least the lower limit, the thermoelectric conversion function is further enhanced. The content of the thermoelectric conversion material in 100% by weight of the resin film and 100% by weight of the layer containing the thermoelectric conversion material is preferably 0.5% by weight or less, more preferably 0.2% by weight or less, and still more preferably 0.1% by weight or less, particularly preferably 0.06% by weight or less. When the content of the thermoelectric conversion material is equal to or less than the upper limit, the thermoelectric conversion function is effectively enhanced.

(dopant)
The resin film contains a dopant. The use of dopants improves the thermoelectric conversion efficiency and electrical conductivity of the resin film. Only one kind of the dopant may be used, or two or more kinds thereof may be used in combination.

Examples of the dopants include halogens, Lewis acids, protonic acids, fiber metal compounds, anions and acidic compounds. The halogen is preferably Cl ₂ , Br ₂ , I ₂ , ICl, ICl ₃ , IBr or IF. The Lewis acid is preferably _PF5 , _AsF5 , _SbF5 , _BF3 , _BCl3 , _BBr3 or _SO3 . _The protonic acid is preferably HF, HCl, _HNO3 , _H2SO4 , _{HClO4 , FSO3H} , _CISO3H or _CF3SO3H . The transition metal compound is _FeCl3 , FeOCl, AgCl, AuCl3, _TiCl4 , ZrCl4, _HfCl4 , _NbF5 , _NbCl5 , _{TaCl5 , MoF5} , _{MoCl5 , WF6} , _WCl6 , _UF6 or LnCl ₃ (Ln=Lanthanoid such as La, Ce, Pr, Nd, Sm). The anion is preferably Cl ⁻ , Br ⁻ , I ⁻ , ClO ₄ ⁻ , PF ₆ ⁻ , AsF ₆ ⁻ , SbF ₆ ⁻ or BF ₄ ⁻ .

From the viewpoint of further enhancing the effect of doping, the content of the dopant is preferably 5 parts by weight or more with respect to 100 parts by weight of the thermoelectric conversion material in the resin film. From the viewpoint of further enhancing the effect of doping, the content of the dopant is preferably 10 parts by weight or more, preferably 40 parts by weight or less, with respect to 100 parts by weight of the thermoelectric conversion material in the resin film. More preferably, it is 30 parts by weight or less.

(light stabilizer)
The resin film, the surface layer and the intermediate layer preferably contain a light stabilizer. By using a light stabilizer, even if the resin film is used for a long period of time or exposed to sunlight, discoloration is further suppressed, and the decrease in visible light transmittance becomes even more difficult. Only one kind of the light stabilizer may be used, or two or more kinds thereof may be used in combination.

From the viewpoint of further suppressing discoloration, the light stabilizer is preferably a hindered amine light stabilizer.

Examples of the hindered amine light stabilizer include hindered amine light stabilizers in which an alkyl group, an alkoxy group, or a hydrogen atom is bonded to the nitrogen atom of the piperidine structure. From the viewpoint of further suppressing discoloration, hindered amine light stabilizers in which an alkyl group or an alkoxy group is bonded to the nitrogen atom of the piperidine structure are preferred. The hindered amine light stabilizer is preferably a hindered amine light stabilizer in which an alkyl group is bonded to the nitrogen atom of the piperidine structure, and is a hindered amine light stabilizer in which an alkoxy group is bonded to the nitrogen atom of the piperidine structure. is also preferred.

Examples of the hindered amine light stabilizer having an alkyl group bonded to the nitrogen atom of the piperidine structure include "Tinuvin 765" and "Tinuvin 622SF" manufactured by BASF, and "ADEKA STAB LA-52" manufactured by ADEKA.

Examples of the hindered amine light stabilizer having an alkoxy group bonded to the nitrogen atom of the piperidine structure include "TinuvinXT-850FF" and "TinuvinXT-855FF" manufactured by BASF, and "ADEKA STAB LA-81" manufactured by ADEKA. .

Examples of the hindered amine light stabilizer in which a hydrogen atom is bonded to the nitrogen atom of the piperidine structure include "Tinuvin 770DF" manufactured by BASF and "Hostavin N24" manufactured by Clariant.

From the viewpoint of further suppressing discoloration, the molecular weight of the light stabilizer is preferably 2,000 or less, more preferably 1,000 or less, and even more preferably 700 or less.

From the viewpoint of further suppressing excessive color unevenness and discoloration, the content of the light stabilizer in 100% by weight of the resin film and 100% by weight of the layer containing the light stabilizer is preferably 0.0025% by weight or more. , more preferably 0.025% by weight or more, preferably 0.5% by weight or less, and more preferably 0.3% by weight or less.

(metal salt)
The resin film and the surface layer preferably contain a magnesium salt, an alkali metal salt, or an alkaline earth metal salt (hereinafter collectively referred to as metal salt M). The intermediate layer may contain the metal salt M described above. Use of the metal salt M makes it easier to control the adhesion of the resin film to a glass plate, laminated glass member, other film, or the like. Only one kind of the metal salt M may be used, or two or more kinds thereof may be used in combination.

The metal salt M preferably contains Li, Na, K, Rb, Cs, Mg, Ca, Sr or Ba as a metal. The metal salt contained in the resin film is preferably K or Mg. In this case, both K and Mg may be included.

The metal salt M is an alkali metal salt of an organic acid having 2 to 16 carbon atoms, an alkaline earth metal salt of an organic acid having 2 to 16 carbon atoms, or a magnesium salt of an organic acid having 2 to 16 carbon atoms. is more preferred, and a magnesium salt of a carboxylic acid having 2 to 16 carbon atoms or a potassium salt of a carboxylic acid having 2 to 16 carbon atoms is more preferred.

Examples of the magnesium salt of a carboxylic acid having 2 to 16 carbon atoms and the potassium salt of a carboxylic acid having 2 to 16 carbon atoms include magnesium acetate, potassium acetate, magnesium propionate, potassium propionate, magnesium 2-ethylbutyrate, and 2-ethylbutanoic acid. potassium, magnesium 2-ethylhexanoate and potassium 2-ethylhexanoate;

The total content of Mg and K in the resin film and the total content of Mg and K in the layer containing Mg or K (surface layer, etc.) are preferably 5 ppm or more, more preferably 10 ppm or more, and still more preferably is 20 ppm or more, preferably 300 ppm or less, more preferably 250 ppm or less, and still more preferably 200 ppm or less. When the total content of Mg and K is at least the above lower limit and below the above upper limit, the adhesion of the resin film to a glass plate, laminated glass member, other film, or the like can be better controlled.

(Ultraviolet shielding agent)
The resin film, the surface layer and the intermediate layer preferably contain an ultraviolet shielding agent. By using the ultraviolet shielding agent, discoloration is further suppressed even when the resin film is used for a long period of time or at high temperatures, and the decrease in visible light transmittance becomes even more difficult. Only one type of the ultraviolet shielding agent may be used, or two or more types may be used in combination.

The ultraviolet shielding agent includes an ultraviolet absorber. The ultraviolet shielding agent is preferably an ultraviolet absorber.

Examples of the ultraviolet shielding agent include, for example, a metal ultraviolet shielding agent (an ultraviolet shielding agent containing a metal), a metal oxide ultraviolet shielding agent (an ultraviolet shielding agent containing a metal oxide), a benzotriazole ultraviolet shielding agent ( benzophenone-based UV-screening agent (benzophenone structure-based UV-screening agent), triazine-based UV-screening agent (triazine-based UV-screening agent), malonic acid ester-based UV-screening agent (malonic acid ester structure), oxalic acid anilide type UV blocking agent (ultraviolet blocking agent having oxalic acid anilide structure), benzoate type UV blocking agent (ultraviolet blocking agent having benzoate structure), and the like.

Examples of the metallic ultraviolet shielding agent include platinum particles, particles obtained by coating the surface of platinum particles with silica, palladium particles, and particles obtained by coating the surface of palladium particles with silica. It is preferred that the UV shielding agent is not heat shielding particles.

The above ultraviolet shielding agent is preferably a benzotriazole ultraviolet shielding agent, a benzophenone ultraviolet shielding agent, a triazine ultraviolet shielding agent or a benzoate ultraviolet shielding agent, more preferably a benzotriazole ultraviolet shielding agent or a benzophenone ultraviolet shielding agent. and more preferably a benzotriazole-based ultraviolet shielding agent.

Examples of the metal oxide-based ultraviolet shielding agents include zinc oxide, titanium oxide, and cerium oxide. Furthermore, the surface of the metal oxide-based ultraviolet shielding agent may be coated. Examples of coating materials for the surface of the metal oxide-based ultraviolet shielding agent include insulating metal oxides, hydrolyzable organosilicon compounds, and silicone compounds.

Examples of the insulating metal oxide include silica, alumina and zirconia. The insulating metal oxide has a bandgap energy of, for example, 5.0 eV or more.

Examples of the benzotriazole-based ultraviolet shielding agents include 2-(2'-hydroxy-5'-methylphenyl)benzotriazole ("TinuvinP" manufactured by BASF), 2-(2'-hydroxy-3',5' -Di-t-butylphenyl) benzotriazole (BASF "Tinuvin 320"), 2-(2'-hydroxy-3'-t-butyl-5-methylphenyl)-5-chlorobenzotriazole (BASF " Tinuvin326”), and 2-(2′-hydroxy-3′,5′-di-amylphenyl)benzotriazole (“Tinuvin328” manufactured by BASF). The ultraviolet shielding agent is preferably a benzotriazole-based ultraviolet shielding agent containing a halogen atom, more preferably a benzotriazole-based ultraviolet shielding agent containing a chlorine atom, because of its excellent ability to absorb ultraviolet rays.

Examples of the benzophenone-based ultraviolet shielding agent include octabenzone (“Chimassorb 81” manufactured by BASF).

Examples of the triazine-based ultraviolet shielding agent include "LA-F70" manufactured by ADEKA and 2-(4,6-diphenyl-1,3,5-triazin-2-yl)-5-[(hexyl)oxy] - phenol (“Tinuvin 1577FF” manufactured by BASF) and the like.

Examples of the malonic acid ester-based ultraviolet shielding agents include dimethyl 2-(p-methoxybenzylidene) malonate, tetraethyl-2,2-(1,4-phenylenedimethylidene) bismalonate, 2-(p-methoxybenzylidene)-bis and (1,2,2,6,6-pentamethyl-4-piperidinyl)malonate.

Commercially available products of the malonic acid ester-based ultraviolet shielding agents include Hostavin B-CAP, Hostavin PR-25, and Hostavin PR-31 (all manufactured by Clariant).

Examples of the oxalic acid anilide ultraviolet shielding agent include N-(2-ethylphenyl)-N'-(2-ethoxy-5-t-butylphenyl)oxalic acid diamide, N-(2-ethylphenyl)-N' -(2-Ethoxy-phenyl) oxalic acid diamide, 2-ethyl-2'-ethoxy-oxyanilide ("Sanduvor VSU" manufactured by Clariant), and other oxalic acid diamides having an aryl group substituted on the nitrogen atom. mentioned.

Examples of the benzoate-based ultraviolet shielding agent include 2,4-di-tert-butylphenyl-3,5-di-tert-butyl-4-hydroxybenzoate (“Tinuvin 120” manufactured by BASF).

The content of the ultraviolet shielding agent in 100% by weight of the resin film and 100% by weight of the layer containing the ultraviolet shielding agent is preferably 0.1% by weight or more, more preferably 0.2% by weight or more, and still more preferably 0.3% by weight or more, particularly preferably 0.5% by weight or more. The content of the ultraviolet shielding agent in 100% by weight of the resin film and 100% by weight of the layer containing the ultraviolet shielding agent is preferably 2.5% by weight or less, more preferably 2% by weight or less, and still more preferably 1% by weight. % or less, particularly preferably 0.8 wt % or less. When the content of the ultraviolet shielding agent is at least the lower limit and at most the upper limit, discoloration is further suppressed, and a decrease in visible light transmittance is further suppressed.

(Antioxidant)
The resin film, the surface layer and the intermediate layer preferably contain an antioxidant. By using the antioxidant, even if the resin film is used for a long period of time or at high temperatures, discoloration is further suppressed, and visible light transmittance is further less likely to decrease. Only one kind of the antioxidant may be used, or two or more kinds thereof may be used in combination.

Examples of the antioxidant include phenol antioxidants, sulfur antioxidants, phosphorus antioxidants, and the like. The phenol-based antioxidant is an antioxidant having a phenol skeleton. The sulfur-based antioxidant is an antioxidant containing a sulfur atom. The phosphorus antioxidant is an antioxidant containing a phosphorus atom.

The antioxidant is preferably a phenolic antioxidant or a phosphorus antioxidant.

Examples of the phenolic antioxidant include 2,6-di-t-butyl-p-cresol (BHT), butylhydroxyanisole (BHA), 2,6-di-t-butyl-4-ethylphenol, stearyl- β-(3,5-di-t-butyl-4-hydroxyphenyl)propionate, 2,2′-methylenebis-(4-methyl-6-butylphenol), 2,2′-methylenebis-(4-ethyl-6 -t-butylphenol), 4,4′-butylidene-bis-(3-methyl-6-t-butylphenol), 1,1,3-tris-(2-methyl-hydroxy-5-t-butylphenyl)butane , tetrakis[methylene-3-(3′,5′-butyl-4-hydroxyphenyl)propionate]methane, 1,3,3-tris-(2-methyl-4-hydroxy-5-t-butylphenol)butane, 1,3,5-trimethyl-2,4,6-tris(3,5-di-t-butyl-4-hydroxybenzyl)benzene, bis(3,3'-t-butylphenol)butyric acid glycol ester and bis(3-t-butyl-4-hydroxy-5-methylbenzenepropanoic acid)ethylenebis(oxyethylene). One or more of these antioxidants are preferably used.

Examples of the phosphorus antioxidant include tridecyl phosphite, tris(tridecyl) phosphite, triphenyl phosphite, trinonylphenyl phosphite, bis(tridecyl) pentaerythritol diphosphite, bis(decyl) pentaerythritol diphosphite. Phyto, tris(2,4-di-t-butylphenyl)phosphite, bis(2,4-di-t-butyl-6-methylphenyl)ethyl ester phosphorous acid, and 2,2′-methylenebis(4 ,6-di-t-butyl-1-phenyloxy)(2-ethylhexyloxy) phosphorous and the like. One or more of these antioxidants are preferably used.

Examples of commercially available antioxidants include "IRGANOX 245" manufactured by BASF, "IRGAFOS 168" manufactured by BASF, "IRGAFOS 38" manufactured by BASF, "Sumilizer BHT" manufactured by Sumitomo Chemical Co., Ltd., manufactured by Sakai Chemical Industry Co., Ltd. "H-BHT", "IRGANOX 1010" manufactured by BASF, and "ADEKA STAB AO-40" manufactured by ADEKA.

From the viewpoint of further suppressing discoloration and further suppressing a decrease in visible light transmittance, the content of the antioxidant in 100% by weight of the resin film and in 100% by weight of the layer containing the antioxidant is 0.5%. It is preferably 1% by weight or more. Moreover, since the effect of adding the antioxidant is saturated, the content of the antioxidant is preferably 2% by weight or less in 100% by weight of the resin film.

(other ingredients)
The resin composition, the resin film, the surface layer, and the intermediate layer may optionally contain a coupling agent, a dispersant, a surfactant, a flame retardant, an antistatic agent, a pigment, a dye, or an adhesive agent other than a metal salt. Additives such as force control agents, moisture resistance agents, optical brighteners and infrared absorbers may also be included. Only one of these additives may be used, or two or more thereof may be used in combination.

(Other details of the resin film)
From the viewpoint of effectively enhancing sound insulation, the intermediate layer preferably includes a layer having a glass transition temperature of 10° C. or less.

The thickness of the resin film is not particularly limited. From the viewpoint of practical use and the viewpoint of sufficiently improving heat shielding properties, the thickness of the resin film is preferably 0.1 mm or more, more preferably 0.25 mm or more, and preferably 3 mm or less, more preferably 1.0 mm or more. 5 mm or less. When the thickness of the resin film is at least the lower limit, the penetration resistance of the glass plate-containing laminate is further enhanced. When the thickness of the resin film is equal to or less than the upper limit, the transparency of the resin film is further improved.

(Use of resin film and thermoelectric conversion film)
The resin film is preferably an interlayer film for laminated glass. The thermoelectric conversion film is preferably an interlayer film for laminated glass having a thermoelectric conversion function.

The said resin film and said thermoelectric conversion film are suitably used in order to obtain a glass plate containing laminated body by bonding together to a glass plate. By connecting electrodes to the resin film, a thermoelectric conversion-glass plate-containing laminate can be obtained.

The resin film is disposed between the first laminated glass member and the second laminated glass member, and is preferably used to obtain laminated glass. A thermoelectric conversion laminated glass can be obtained by connecting an electrode to the resin film in the laminated glass. The thermoelectric conversion laminated glass is laminated glass having a thermoelectric conversion function.

The laminated glass preferably includes a first laminated glass member, a second laminated glass member, and the resin film described above. It is preferable that the resin film is arranged between the first laminated glass member and the second laminated glass member. It is preferable that the resin film is used by being connected to an electrode.

The thermoelectric conversion laminated glass preferably includes a first laminated glass member, a second laminated glass member, the resin film described above, and electrodes. The resin film is arranged between the first laminated glass member and the second laminated glass member. The resin film is connected to the electrode.

Moreover, the thermoelectric conversion laminated glass preferably includes a first laminated glass member, a second laminated glass member, and the thermoelectric conversion film described above. It is preferable that the resin film in the thermoelectric conversion film is arranged between the first laminated glass member and the second laminated glass member.

FIG. 3 is a cross-sectional view showing an example of thermoelectric conversion laminated glass using the thermoelectric conversion film shown in FIG.

Thermoelectric conversion laminated glass 31 shown in FIG. Thermoelectric conversion laminated glass 31 includes thermoelectric conversion film 1 .

The laminated glass 40 includes a first laminated glass member 41 , a second laminated glass member 42 and a resin film 10 .

The resin film 10 is arranged and sandwiched between the first laminated glass member 41 and the second laminated glass member 42 . A first laminated glass member 41 is laminated on the first surface (one surface) of the resin film 10 . A second laminated glass member 42 is laminated on a second surface (the other surface) opposite to the first surface of the resin film 10 .

FIG. 4 is a cross-sectional view showing an example of thermoelectric conversion laminated glass using the thermoelectric conversion film shown in FIG.

A thermoelectric conversion laminated glass 31A shown in FIG. Thermoelectric conversion laminated glass 31A includes thermoelectric conversion film 1A.

The laminated glass 40A includes a first laminated glass member 41, a second laminated glass member 42, and a resin film 10A.

The resin film 10A is arranged and sandwiched between the first laminated glass member 41 and the second laminated glass member 42 . A first laminated glass member 41 is laminated on the first surface (one surface) of the resin film 10A. A second laminated glass member 42 is laminated on a second surface (the other surface) opposite to the first surface of the resin film 10A.

Examples of the laminated glass member include a glass plate and a PET (polyethylene terephthalate) film. Laminated glass includes not only laminated glass in which a resin film is sandwiched between two glass plates, but also laminated glass in which a resin film is sandwiched between a glass plate and a PET film or the like. Laminated glass is a laminate comprising glass plates, and preferably at least one glass plate is used. It is preferable that the second laminated glass member is a glass plate or a PET film.

Examples of the glass plate include inorganic glass and organic glass. Examples of the inorganic glass include float plate glass, heat-absorbing plate glass, heat-reflecting plate glass, polished plate glass, figured glass, and lined plate glass. The organic glass is a synthetic resin glass that replaces inorganic glass. Examples of the organic glass include a polycarbonate plate and a poly(meth)acrylic resin plate. Examples of the poly(meth)acrylic resin plate include a polymethyl(meth)acrylate plate.

The thickness of the laminated glass member is preferably 1 mm or more, preferably 5 mm or less, and more preferably 3 mm or less. The thickness of the glass plate is preferably 1 mm or more, preferably 5 mm or less, and more preferably 3 mm or less. When the laminated glass member is a PET film, the thickness of the PET film is preferably 0.03 mm or more and preferably 0.5 mm or less.

(Method for manufacturing laminated glass and thermoelectric conversion laminated glass)
In the method for producing a laminated glass according to the present invention, the resin film is arranged between the step of obtaining the resin film and the first laminated glass member and the second laminated glass member by the above-described method for producing a resin film. It is preferable to have a step of performing.

In the method for producing a thermoelectric conversion laminated glass according to the present invention, the resin film is provided between the step of obtaining a resin film and the first laminated glass member and the second laminated glass member by the above-described method for producing a resin film. and a step of connecting electrodes to the resin film.

In the step of disposing the resin film in the method for manufacturing the laminated glass and the method for manufacturing the thermoelectric conversion laminated glass, the resin is placed between the first laminated glass member and the second laminated glass member as follows. Film can be placed.

A resin film is sandwiched between the first laminated glass member and the second laminated glass member and passed through a pressing roll, or placed in a rubber bag and vacuum-sucked to form the first laminated glass. Air remaining between the member and the resin film and between the second laminated glass member and the resin film is removed. After that, pre-bonding is performed at about 70° C. to 110° C. to obtain a laminate. Next, the laminate is put into an autoclave or pressed to be crimped at about 120° C.-150° C. and a pressure of 1 MPa-1.5 MPa.

The resin film and the laminated glass can be used for automobiles, railway vehicles, aircraft, ships, buildings, and the like. The resin film and the laminated glass can be used for applications other than these applications. The resin film and laminated glass are preferably a resin film and laminated glass for vehicles or buildings, and more preferably a resin film and laminated glass for vehicles. The resin film and the laminated glass can be used for automobile windshields, side glasses, rear glasses, roof glasses, and the like. The resin film and the laminated glass are suitably used for automobiles. The resin film is used to obtain laminated glass for automobiles.

The present invention will be described in more detail below with reference to examples and comparative examples. The invention is not limited only to these examples.

The following materials were used.

In the polyvinyl acetal resin used, n-butyraldehyde having 4 carbon atoms is used for acetalization. Regarding the polyvinyl acetal resin, the degree of acetalization (degree of butyralization), the degree of acetylation, and the content of hydroxyl groups were measured according to JIS K6728 "Polyvinyl butyral test method". When measured according to ASTM D1396-92, values similar to those obtained by the method based on JIS K6728 "Polyvinyl butyral test method" were obtained.

(Thermoplastic resin)
Polyvinyl acetal resin ("PVB" in the table, average degree of polymerization 1700, content of hydroxyl group 30.5 mol%, degree of acetylation 1 mol%, degree of acetalization 68.5 mol%)
Vinyl chloride resin ("PVC" in the table, vinyl chloride-ethylene-glycidyl methacrylate copolymer)

(Plasticizer)
Triethylene glycol-2-ethylhexanoate (3GO)
Bis(2-ethylhexyl) sebacate

(thermoelectric conversion material)
Poly(3-hexylthiophene-2,5-diyl): P3HT nanofibers

P3HT nanofibers were made as follows.

P3HT was added to a mixed solution of anisole and chloroform (mixture ratio (volume ratio) of anisole and chloroform: 3:7) so as to be 0.05% by weight, and then mixed at 60°C to dissolve P3HT. . The resulting solution was then slowly cooled to obtain P3HT nanofibers as precipitates.

(dopant)
Gold chloride ( _AuCl3 )

(metal salt)
A mixture of magnesium acetate and magnesium 2-ethylbutyrate (weight ratio of magnesium acetate:weight ratio of magnesium 2-ethylbutyrate=50% by weight:50% by weight)

(Ultraviolet shielding agent)
"Tinuvin 326" manufactured by BASF

(Antioxidant)
BHT (2,6-di-t-butyl-p-cresol)

(Example 1)
Preparation of dopant-containing liquid:
A dopant and acetonitrile were mixed to obtain a dopant-containing liquid. The dopant concentration in the dopant-containing liquid was 10 mmol/L.

Preparation of resin composition:
The following ingredients were blended and thoroughly kneaded with a mixing roll to obtain a resin composition.

Polyvinyl acetal resin (average degree of polymerization 1700, content of hydroxyl group 30.5 mol%, degree of acetylation 1 mol%, degree of acetalization 68.5 mol%) 100 parts by weight Triethylene glycol-2-ethylhexanoate (3GO ) 40 parts by weight Thermoelectric conversion material (P3HT nanofiber) in an amount that is 0.05% by weight in the resulting resin film (intermediate film)
A mixture of magnesium acetate and magnesium 2-ethylbutyrate in an amount that Mg is 60 ppm in the resulting intermediate film BASF Co. "Tinuvin 326" in an amount that is 0.2% by weight in the resulting intermediate film) Interlayer film obtained BHT (2,6-di-t-butyl-p-cresol) in an amount to be 0.2% by weight in

Preparation of resin film:
The resulting resin composition was press-molded to obtain a resin film.

Production of resin film (interlayer film):
A dopant was introduced during the preparation of the resin film (post-introduction). The obtained resin film material was immersed in the obtained dopant-containing liquid for 60 minutes to introduce the dopant into the resin film material. Next, the resin film material impregnated with the dopant-containing liquid was dried. Thus, a resin film (intermediate film) having a thickness of 0.810 mm was obtained.

Production of laminated glass (for visible light transmittance measurement):
The obtained intermediate film was cut into a size of 5 cm long×5 cm wide. Next, two sheets of clear glass (length 5 cm, width 5 cm, thickness 2.5 mm) having a visible light transmittance of 90.4% and complying with JIS R3202:2011 were prepared. The resulting intermediate film was sandwiched between the two sheets of clear glass, held at 90° C. for 30 minutes in a vacuum laminator, and vacuum-pressed to obtain a laminate. In the laminate, the portion of the intermediate film protruding from the glass plate was cut off to obtain a laminated glass.

Fabrication of thermoelectric conversion laminated glass:
Electrodes were connected to the intermediate films (resin films) exposed at both ends of the laminated glass. A thermoelectric conversion laminated glass was obtained by connecting the electrodes to an electricity extraction part (equipped with a wattmeter) via a lead wire.

(Examples 2 to 10)
Example 1 except that the concentration of the dopant in the dopant-containing liquid, the type and amount of the thermoplastic resin, the type and amount of the plasticizer, and the thickness of the resin film were set as shown in Tables 1 and 2 below. An intermediate film, laminated glass, and thermoelectric conversion laminated glass were obtained in the same manner as above.

(Comparative example 1)
Preparation of resin composition:
A dopant was introduced (pre-introduction) during preparation of the resin composition. Among the following ingredients, P3HT nanofibers and gold chloride were mixed and doped. Next, the rest of the ingredients were blended and sufficiently kneaded with a mixing roll to obtain a resin composition.

Polyvinyl acetal resin (average degree of polymerization 1700, content of hydroxyl group 30.5 mol%, degree of acetylation 1 mol%, degree of acetalization 68.5 mol%) 100 parts by weight Triethylene glycol-2-ethylhexanoate (3GO ) 40 parts by weight Thermoelectric conversion material (P3HT nanofiber) in an amount that is 0.05% by weight in the resulting resin film (intermediate film)
Dopant (gold chloride) in an amount of 0.05 parts by weight with respect to 100 parts by weight of the thermoelectric conversion material in the resulting resin film (intermediate film)
A mixture of magnesium acetate and magnesium 2-ethylbutyrate in an amount that Mg is 60 ppm in the resulting intermediate film BASF Co. "Tinuvin 326" in an amount that is 0.2% by weight in the resulting intermediate film) Interlayer film obtained BHT (2,6-di-t-butyl-p-cresol) in an amount to be 0.2% by weight in

Production of resin film (interlayer film):
The obtained resin composition was press-molded to obtain a resin film having a thickness of 0.781 mm.

A laminated glass and a thermoelectric conversion laminated glass were obtained in the same manner as in Example 1 using this resin film (intermediate film).

(Comparative Examples 2-4)
An interlayer film, a laminated glass, and a thermoelectric conversion laminated glass were obtained in the same manner as in Comparative Example 1, except that the type and amount of the plasticizer and the thickness of the resin film were set as shown in Table 3 below. .

(evaluation)
(1) Visible light transmittance (A light Y value, initial AY (380 nm to 780 nm))
Using a spectrophotometer (“U-4100” manufactured by Hitachi High-Tech Co., Ltd.), the visible light transmittance of the obtained laminated glass at wavelengths of 380 nm to 780 nm was measured according to JIS R3106:1998.

(2) Thermoelectric conversion function (2-1) Seebeck coefficient S
A test piece (intermediate film) was fixed to a wiring board arranged so that electrodes were in contact with both ends of the test piece (intermediate film). A heater was provided on one electrode side of the wiring board on which the test piece was fixed, and the test piece was placed in a vacuum chamber to heat one end of the test piece in a vacuum environment. A chromel-alumel thermocouple was placed adjacent to the electrode to measure the temperature difference between both ends of the sample. Each electrode was connected to a voltmeter to measure the thermoelectromotive force generated at both ends of the test piece. One end that was not heated was kept at approximately 20°C, and the temperature of the other end heated by the heater increased from 21°C to 31°C. The thermoelectromotive force at that time was measured, and the Seebeck coefficient S was calculated from the slope.

(2-2) Conductivity σ
A constant current was passed through the test piece (intermediate film) from a current source in a vacuum atmosphere by the four-probe method, the voltage value was read with a digital multimeter, and the electrical conductivity σ was calculated.

(2-3) Thermal Diffusivity The obtained resin film was cut into a size of 1 cm×1 cm to prepare a measurement sample. A measurement sample was evaluated by periodic steady heating using "ai-phase" manufactured by Hitachi High-Tech Science Co., Ltd., and the thermal diffusivity was calculated from the phase difference of the temperature waves.

(2-4) Constant pressure specific heat The constant pressure specific heat was measured according to JIS K7123 using "thermo plus DSC8230" manufactured by Rigaku.

(2-5) Thermal conductivity λ
A thermal conductivity λ was obtained based on the following equation.

λ=α・Cp・ρ

Cp is the specific heat, α is the thermal diffusivity, and ρ is the density of the test piece (interlayer film). The thermal diffusivity α was measured by the laser flash method, the specific heat Cp was measured by the differential scanning calorimetry (DSC) method, and the density ρ of the test piece was measured by weight measurement and volume measurement of the test piece.

(2-6) PF
PF was obtained based on the following formula.

PF = σ x S x S

Note that σ is conductivity and S is Seebeck coefficient.

(2-7) ZT (300K)
From the calculated PF and thermal conductivity λ, ZT (300K) was determined based on the following equation.

ZT=PF/λ×300

(3) Density The density of the obtained intermediate film was measured.

(4) Flexibility (bendability)
Bending test The intermediate film (resin film) after being bent once and the intermediate film (resin film) after being bent 10 times were observed, and the bending property was judged according to the following criteria.

[Bending test]
○: no creases were observed in the intermediate film (resin film) after bending 10 times ×: creases were observed in the intermediate film (resin film) after bending once

Details and results are shown in Tables 1-3 below. In the column of "Introduction of dopant" in Tables 1 to 3, "pre-introduction" is described when the dopant is introduced during preparation of the resin composition, and when the dopant is introduced during preparation of the resin film. It was described as "post-introduction". In addition, in Tables 1 to 3, descriptions of the metal salts, ultraviolet shielding agents and antioxidants used in Examples 1 to 10 and Comparative Examples 1 to 4 are omitted.

The intermediate films obtained in Comparative Examples 1 to 4 had low conductivity values and could not be measured. In addition, since the conductivity of the intermediate films obtained in Comparative Examples 1 to 4 could not be measured, it was determined that the Seebeck coefficient was not measured, and the Seebeck coefficient was not measured. Therefore, in Comparative Examples 1 to 4, PF and ZT (300K) were not evaluated either. Furthermore, the interlayer films obtained in Comparative Examples 1 to 4 were not evaluated for flexibility.

DESCRIPTION OF SYMBOLS 1,1A... Thermoelectric conversion film 10,10A... Resin film 11... 1st layer 12... 2nd layer 13... 3rd layer 21... Electrode 22... Conducting wire 23... Electricity extraction part 31, 31A... Thermoelectric conversion laminated glass 40, 40A... Laminated glass 41... First laminated glass member 42... Second laminated glass member

Claims (5)

A method for producing a resin film used by being connected to an electrode, comprising:
a step of obtaining a resin composition containing a resin and a thermoelectric conversion material that exhibits a thermoelectric conversion function in a state where the resin film is connected to the electrodes;
a step of forming the resin composition into a film to obtain a resin film;
introducing a dopant into the resin film material to obtain a resin film containing the dopant ;
The thermoelectric conversion material contains a polythiophene compound,
In the step of obtaining the resin film containing the dopant, the dopant is introduced into the resin film-like material by impregnating the resin film-like material with a dopant-containing liquid containing the dopant and a solvent. Production method. 2. The method for producing a resin film according to claim 1 , wherein the polythiophene compound is a polythiophene compound having a structure represented by the following formula (1).

In formula (1), R1 and R2 each represent a hydrogen atom or an organic group. A step of obtaining a resin film by the method for producing a resin film according to claim 1 or 2 ;
and connecting electrodes to the resin film. A step of obtaining a resin film by the method for producing a resin film according to claim 1 or 2 ;
A method for manufacturing laminated glass, comprising the step of disposing the resin film between a first laminated glass member and a second laminated glass member. A step of obtaining a resin film by the method for producing a resin film according to claim 1 or 2 ;
placing the resin film between the first laminated glass member and the second laminated glass member;
A method for producing thermoelectric conversion laminated glass, comprising a step of connecting electrodes to the resin film.

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