WO2019049943A1

WO2019049943A1 - Thermoplastic resin film, thermoelectric conversion film, laminated glass, and thermoelectric conversion laminated glass

Info

Publication number: WO2019049943A1
Application number: PCT/JP2018/033076
Authority: WO
Inventors: 中島　大輔
Original assignee: 積水化学工業株式会社
Priority date: 2017-09-06
Filing date: 2018-09-06
Publication date: 2019-03-14
Also published as: JPWO2019049942A1; JP6683844B2; JPWO2019049943A1; JP7221697B2; WO2019049942A1

Abstract

Provided is a thermoplastic resin film that has excellent flexibility and that is capable of realizing a thermoelectric conversion function. The thermoplastic resin film pertaining to the present invention is used in a state of being connected to an electrode, the thermoplastic resin film including a thermoplastic resin and a thermoelectric conversion material for realizing a thermoelectric conversion function in the thermoplastic resin film connected to the electrode, and the bending rigidity of the thermoplastic resin film being 0.49 N∙cm2/cm or less.

Description

Thermoplastic resin film, thermoelectric conversion film, laminated glass and thermoelectric conversion laminated glass

The present invention relates to a thermoplastic resin film containing a thermoplastic resin. Moreover, this invention relates to the laminated glass provided with the said thermoplastic resin film. In addition, the present invention relates to a thermoelectric conversion film and a thermoelectric conversion laminated glass having a thermoelectric conversion function.

The glass plate containing laminated body by which the thermoplastic resin film was bonded together to the glass plate is known. Among the glass plate-containing laminates, laminated glass is widely used.

Laminated glass is excellent in safety because the amount of scattered glass fragments is small even if it is broken due to external impact. For this reason, the laminated glass is widely used in automobiles, railway vehicles, aircraft, ships, buildings, and the like. The laminated glass is manufactured by sandwiching a thermoplastic resin film between a pair of glass plates. Moreover, a thermoplastic resin film may be bonded together and used for members other than a glass plate besides laminated glass.

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

Patent Document 1 below proposes a laminated glass which can thaw a frozen material 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 provided, and the glass plates are laminated via the intermediate film. The synthetic thermal resistance of the plurality of glass plates and the intermediate film is 0.014 to 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 the frozen material.

The present inventor examined giving a function different from the function described in Patent Document 1 to a laminated glass or the like, and came to complete the present invention.

An object of the present invention is to provide a thermoplastic resin film which has excellent flexibility and can exhibit a thermoelectric conversion function. Another object of the present invention is to provide a laminated glass using the above-mentioned thermoplastic resin film. Another object of the present invention is to provide a thermoelectric conversion film and a thermoelectric conversion laminated glass having excellent flexibility and having a thermoelectric conversion function.

According to a broad aspect of the present invention, it is a thermoplastic resin film used by being connected to an electrode, wherein a thermoplastic resin and a thermoelectric conversion function are exhibited in a state where the thermoplastic resin film is connected to the electrode There is provided a thermoplastic resin film containing a conversion material and having a bending stiffness of 0.49 N · cm ² / cm or less.

According to a broad aspect of the present invention, a thermoplastic resin film and an electrode are provided, the thermoplastic resin film includes a thermoplastic resin and a thermoelectric conversion material, and the thermoplastic resin film is connected to the electrode A thermoelectric conversion film is provided, wherein the thermoplastic resin film has a flexural rigidity of 0.49 N · cm ² / cm or less.

It is preferable that the property of the said thermoelectric conversion material is particulate form or fibrous form. The thermoelectric conversion material is preferably an organic compound. It is preferable that the said thermoplastic resin is polyvinyl acetal resin. The thermoplastic resin film preferably contains a plasticizer. It is preferable that content of the said plasticizer with respect to 100 weight part of said thermoplastic resins is 20 weight part or more and 100 weight part or less. It is preferable that content of the said thermoelectric conversion material is 0.01 weight% or more and 0.5 weight% or less in 100 weight% of the said thermoplastic resin films.

The thermoplastic resin film is preferably an intermediate film for laminated glass. The thermoelectric conversion film is preferably an intermediate film for laminated glass having a thermoelectric conversion function.

According to a broad aspect of the present invention, a first laminated glass member, a second laminated glass member, and the above-mentioned thermoplastic resin film are provided, and the thermoplastic resin film is the first laminated glass member. A laminated glass is provided, which is disposed between the second laminated glass member, and the thermoplastic resin film is used by being connected to an electrode.

According to a broad aspect of the present invention, a first laminated glass member, a second laminated glass member, the above-described thermoplastic resin film, and an electrode are provided, and the thermoplastic resin film is the first laminated member. A thermoelectric conversion laminated glass is provided, which is disposed between a glass member and the second laminated glass member, and the thermoplastic resin film is connected to the electrode.

According to a broad aspect of the present invention, a first laminated glass member, a second laminated glass member, and the above-described thermoelectric conversion film are provided, and the thermoplastic resin film in the thermoelectric conversion film is the first one. A thermoelectric conversion laminated glass is provided, which is disposed between the laminated glass member and the second laminated glass member.

The thermoplastic resin film according to the present invention includes a thermoplastic resin and a thermoelectric conversion material that exhibits a thermoelectric conversion function in a state where the thermoplastic resin film is connected to the electrode, and the bending hardness is 0.49 N · cm ² / Since it is cm or less, it has excellent flexibility, and by connecting the thermoplastic resin film according to the present invention to an electrode, the thermoelectric conversion function can be exhibited.

The thermoelectric conversion film according to the present invention comprises a thermoplastic resin film and an electrode, wherein the thermoplastic resin film includes a thermoplastic resin and a thermoelectric conversion material, and the thermoplastic resin film is connected to the electrode. Since the thermoplastic resin film has a flexural rigidity of 0.49 N · cm ² / cm or less, it has excellent flexibility and a thermoelectric conversion function.

FIG. 1 is a cross-sectional view schematically showing a thermoelectric conversion film according to a first embodiment of the present invention. FIG. 2 is a cross-sectional view schematically showing a thermoelectric conversion film according to a second embodiment of the present invention. FIG. 3: is sectional drawing which shows an example of the thermoelectric conversion laminated glass using the thermoelectric conversion film shown in FIG. FIG. 4: is sectional drawing which shows an example of the thermoelectric conversion laminated glass using the thermoelectric conversion film shown in FIG.

Hereinafter, the present invention will be described in detail.

The thermoplastic resin film according to the present invention is a thermoplastic resin film used by being connected to an electrode. The thermoplastic resin film according to the present invention is a thermoplastic resin film which can be used by being connected to an electrode. The thermoplastic resin film according to the present invention contains a thermoplastic resin and a thermoelectric conversion material. In the thermoplastic resin film according to the present invention, the thermoelectric conversion material exhibits a thermoelectric conversion function in a state where the thermoplastic resin film is connected to the electrode. The thermoelectric conversion material converts thermal energy into electrical energy. In the present invention, when the Seebeck coefficient of the thermoplastic resin film is measured, it is considered that the thermoelectric conversion function is exhibited when the value of the Seebeck coefficient is 10 ⁻⁷ V / K or more. For example, by connecting electrodes to two distant positions in the thermoplastic resin film and connecting the electrodes with a conducting wire, electricity can be extracted from the electrical extraction portion. The bending hardness of the thermoplastic resin film according to the present invention is 0.49 N · cm ² / cm or less.

Since the thermoplastic resin film according to the present invention is provided with the above-described configuration, it has excellent flexibility, and by connecting the thermoplastic resin film according to the present invention to an electrode, a thermoelectric conversion function can be obtained. It can be expressed.

The thermoelectric conversion film according to the present invention comprises a thermoplastic resin film and an electrode. In the thermoelectric conversion film according to the present invention, the thermoplastic resin film contains a thermoplastic resin and a thermoelectric conversion material. The thermoelectric conversion material converts thermal energy into electrical energy. In the thermoelectric conversion film according to the present invention, the thermoplastic resin film is connected to the electrode. For example, by connecting electrodes to two distant positions in the thermoplastic resin film and connecting the electrodes with a conducting wire, electricity can be extracted from the electrical extraction portion. In the thermoelectric conversion film according to the present invention, the bending hardness of the thermoplastic resin film is 0.49 N · cm ² / cm or less.

Since the thermoelectric conversion film according to the present invention is provided with the above configuration, it has excellent flexibility and has a thermoelectric conversion function. The followability to the curved surface of a thermoplastic resin film can be improved as bending hardness is below the above-mentioned upper limit.

From the viewpoint of further enhancing the flexibility, the bending hardness of the thermoplastic resin film is preferably 0.3 N · cm ² / cm or less, more preferably 0.2 N · cm ² / cm or less, still more preferably 0. It is 13 N · cm ² / cm or less.

Specifically, the bending hardness is measured as follows.

(Bending hardness)
After the test pieces are conditioned at 23 ° C. and 50% RH, the test pieces are bent and deformed at a deformation rate of 0.5 cm / sec using a pure bending tester (“KES-FB2-A” manufactured by Kato Tech Co., Ltd.) . The curvature and torque at that time are measured, the bending moment change amount per unit curvature change (per unit specimen width) is determined, and the determined value is regarded as a pure bending hardness (in the present specification, simply “ It is called "flexible hardness").

From the viewpoint of further enhancing the flexibility, the bending recovery of the thermoplastic resin film is preferably 0.58 N · cm / cm or less. The followability to the curved surface of a thermoplastic resin film can be improved as bending recovery nature is below the above-mentioned maximum.

Specifically, the bending recovery is measured as follows.

(Bend recovery)
After the test pieces are conditioned at 23 ° C. and 50% RH, the 2HB value of the test pieces is measured using a pure bending tester (“KES-FB2-A” manufactured by Kato Tech Co., Ltd.), and the measured values are Make it bend recoverable.

The thermoplastic resin film may have a structure of one layer, may have a structure of two or more layers, may have a structure of three or more layers, a structure of four or more layers May be included. The thermoplastic resin film may have a structure of two or more layers, and may include a first surface layer and a second surface layer. The thermoplastic 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 thermoplastic resin film may have two or more layers of the intermediate layer. The thermoplastic resin film may comprise a first intermediate layer and a second intermediate layer.

The visible light transmittance of the thermoplastic resin film is preferably 40% or more, more preferably 50% or more, still more preferably 60% or more, still more preferably 70% or more, still more preferably 80% or more, particularly preferably Is at least 85%, particularly preferably at least 88%, most preferably at least 90%. Transparency can be further improved as the visible light transmittance of the said thermoplastic resin film is more than the said lower limit, and the visibility through a thermoplastic resin film can be improved effectively.

In the case where the thermoplastic resin film is an interlayer for laminated glass, the interlayer for laminated glass may have a shade region. The visible light transmittance of the interlayer for a laminated glass (thermoplastic resin film) in a region excluding the shade region in the interlayer for a laminated glass is defined as a visible light transmittance A. The visible light transmittance A is preferably 40% or more, more preferably 50% or more, still more preferably 60% or more, still more preferably 70% or more, still more preferably 80% or more, particularly preferably 85% or more Particularly preferably 88% or more, most preferably 90% or more. The thermoplastic resin film according to the present invention preferably has a region in which the visible light transmittance is equal to or more than the above lower limit. It is preferable that the visible light transmittance of the central portion of the thermoplastic resin film is not less than the lower limit.

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

The said visible light transmittance | permeability can be measured using the laminated glass obtained by arrange | positioning a thermoplastic resin film between two sheets of green glass based on JISR3208. The visible light transmittance of the obtained laminated glass at a wavelength of 380 nm to 780 nm can be measured according to JIS R 3211: 1998 using a spectrophotometer (“U-4100” manufactured by Hitachi High-Technologies Corporation).

Hereinafter, specific embodiments of the present invention will be described with reference to the drawings.

FIG. 1 is a cross-sectional view schematically showing a thermoelectric conversion film according to a first embodiment of the present invention. In addition, the magnitude | size and dimension of the thermoelectric conversion film in FIG. 1 and the figure mentioned later are suitably changed from the actual magnitude | size and shape for convenience of illustration.

The thermoelectric conversion film 1 shown in FIG. 1 includes a thermoplastic resin film 10 and an electrode 21. The thermoplastic resin film 10 contains a thermoplastic resin and a thermoelectric conversion material. One end of the thermoplastic 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 conducting wire 22. An electrical outlet 23 is disposed in the lead 22.

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

In the present embodiment, the first layer 11 contains a thermoelectric conversion material. One end of the first layer 11 is connected to the electrode 21, and the other end is connected to the electrode 21.

It is preferable that the outer surface on the opposite side to the 1st layer 11 side of the 2nd layer 12 is a surface where a laminated glass member is laminated. It is preferable that the outer surface on the opposite side to the 1st layer 11 side of the 3rd layer 13 is a surface where a laminated glass member is laminated.

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

The thermoelectric conversion film 1A shown in FIG. 2 includes a thermoplastic resin film 10A and an electrode 21. The thermoplastic resin film 10A contains a thermoplastic resin and a thermoelectric conversion material. One end of the thermoplastic resin film 10A is connected to the electrode 21, and the other end is connected to the electrode 21. The two electrodes 21 are connected by a conducting wire 22. An electrical outlet 23 is disposed in the lead 22.

The thermoplastic resin film 10A includes a first layer. The thermoplastic resin film 10A has a structure of one layer of only the first layer, and is a single layer film. The thermoplastic resin film 10A is a first layer.

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

Hereinafter, details of the first layer (including a monolayer film), the second layer and the third layer constituting the thermoplastic resin film according to the present invention, and the first layer, the second layer The details of each component contained in the third layer and the second layer will be described.

(Thermoplastic resin)
It is preferable that the said thermoplastic film contains a thermoplastic resin (Hereinafter, it may describe as a thermoplastic resin (0).). It is preferable that the said thermoplastic film contains polyvinyl acetal resin (Hereafter, it may describe as polyvinyl acetal resin (0)) as thermoplastic resin (0). The first layer preferably contains a thermoplastic resin (hereinafter sometimes referred to as a thermoplastic resin (1)). The first layer preferably contains, as the thermoplastic resin (1), a polyvinyl acetal resin (hereinafter sometimes referred to as a polyvinyl acetal resin (1)). The second layer preferably contains a thermoplastic resin (hereinafter sometimes referred to as a thermoplastic resin (2)). The second layer preferably contains, as the thermoplastic resin (2), a polyvinyl acetal resin (hereinafter sometimes referred to as a polyvinyl acetal resin (2)). The third layer preferably contains a thermoplastic resin (hereinafter sometimes referred to as a thermoplastic resin (3)). The third layer preferably contains, as the thermoplastic resin (3), a polyvinyl acetal resin (hereinafter sometimes referred to as a polyvinyl acetal resin (3)). The thermoplastic resin (1), the thermoplastic resin (2) and the thermoplastic resin (3) may be identical or different. The thermoplastic resin (1) is preferably different from the thermoplastic resin (2) and the thermoplastic resin (3) because the sound insulation property 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 property is further enhanced. 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 be 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 be

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

The thermoplastic resin film preferably contains, as the thermoplastic resin, a polyvinyl acetal resin or an ionomer resin, and more preferably a polyvinyl acetal resin. By the combined use of the polyvinyl acetal resin and the plasticizer, the adhesion of the thermoplastic resin film according to the present invention to a glass plate, a laminated glass member or another film is further enhanced. It is preferable that the surface layer and the intermediate layer contain a polyvinyl acetal resin or an ionomer resin. One type of each of the polyvinyl acetal resin and the ionomer resin may be used, or two or more types may be used in combination.

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 in 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, and most preferably 2700 or more. Preferably it is 5000 or less, More preferably, it is 4000 or less, More preferably, it is 3500 or less. When the average degree of polymerization is at least the lower limit, the penetration resistance is further enhanced. Molding of a thermoplastic resin film becomes it easy that the above-mentioned average polymerization degree is below the above-mentioned maximum.

The average degree of polymerization of the polyvinyl alcohol is determined by a method in accordance with JIS K 6726 "Polyvinyl alcohol test method".

The carbon number of the acetal group contained in the polyvinyl acetal resin is not particularly limited. The aldehyde used in producing the polyvinyl acetal resin is not particularly limited. The carbon number of the acetal group in the polyvinyl acetal resin is preferably 3 to 5, and more preferably 3 or 4. The glass transition temperature of a thermoplastic resin film becomes it low enough that carbon number of the acetal group in the said polyvinyl acetal resin is three or more.

The aldehyde is not particularly limited. In general, aldehydes having 1 to 10 carbon atoms are preferably used. Examples of the above aldehydes having 1 to 10 carbon atoms include formaldehyde, acetaldehyde, propionaldehyde, n-butyraldehyde, isobutyraldehyde, n-valeraldehyde, 2-ethylbutyraldehyde, n-hexyl aldehyde and n-octyl aldehyde, Examples include n-nonyl aldehyde, n-decyl aldehyde and benzaldehyde. Propionaldehyde, n-butyraldehyde, isobutyraldehyde, n-hexyl aldehyde or n-valeraldehyde is preferred, propionaldehyde, n-butyraldehyde or isobutyraldehyde is more preferred, and n-butyraldehyde is even more preferred. Only one type of aldehyde may be used, or two or more types may be used in combination.

The hydroxyl group content (hydroxyl content) of the polyvinyl acetal resin (0) is preferably 15 mol% or more, more preferably 18 mol% or more, preferably 40 mol% or less, more preferably 35 mol% or less is there. The adhesive force of a thermoplastic resin film becomes it still higher that the content rate of the said hydroxyl group is more than the said minimum. Moreover, the softness | flexibility of a thermoplastic resin film becomes it still higher that the content rate of the said hydroxyl group is below the said upper limit, and the handling of a thermoplastic resin film becomes easy.

The hydroxyl content (hydroxyl content) 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. More preferably, it is 27 mol% or less, still more preferably 25 mol% or less, and particularly preferably 24 mol% or less. The mechanical strength of a thermoplastic resin film becomes it still higher that the content rate of the said hydroxyl group is more than the said minimum. In particular, when the content of hydroxyl group of the polyvinyl acetal resin (1) is 20 mol% or more, the reaction efficiency is high and the productivity is excellent, and when it is 28 mol% or less, the sound insulation of the laminated glass is further enhanced. . Moreover, the softness | flexibility of a thermoplastic resin film becomes it still higher that the content rate of the said hydroxyl group is below the said upper limit, and the handling of a thermoplastic resin film becomes easy.

The content of each of hydroxyl groups 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, still more preferably It is 31.5 mol% or more, still more preferably 32 mol% or more, and particularly preferably 33 mol% or more. The content of each hydroxyl group 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, particularly preferably Is 36 mol% or less. The adhesive force of a thermoplastic resin film becomes it still higher that the content rate of the said hydroxyl group is more than the said minimum. Moreover, the softness | flexibility of a thermoplastic resin film becomes it high that the content rate of the said hydroxyl group is below the said upper limit, and the handling of a thermoplastic resin film becomes easy.

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

The hydroxyl group content of the polyvinyl acetal resin is a value indicating 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 as a percentage. The amount of ethylene groups to which the above hydroxyl groups are bonded can be measured, for example, in accordance with JIS K 6728 "Polyvinyl butyral test method".

The degree of acetylation (the amount of acetyl groups) 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, and still more preferably 20 mol% or less. The compatibility of polyvinyl acetal resin and a plasticizer becomes it high that the said degree of acetylation is more than the said minimum. The moisture resistance of a thermoplastic resin film and a laminated glass becomes it high that the said degree of acetylation is below the said upper limit.

The degree of acetylation (amount of acetyl group) 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, and still more preferably 9 It is preferably at most 30 mol%, more preferably at most 25 mol%, still more preferably at most 24 mol%, particularly preferably at most 20 mol%. The compatibility of polyvinyl acetal resin and a plasticizer becomes it high that the said degree of acetylation is more than the said minimum. The moisture resistance of a thermoplastic resin film and a laminated glass becomes it high that the said degree of acetylation is below the said upper limit. 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 each 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. The compatibility of polyvinyl acetal resin and a plasticizer becomes it high that the said degree of acetylation is more than the said minimum. The moisture resistance of a thermoplastic resin film and a laminated glass becomes it high that the said degree of acetylation is below the said upper limit.

The degree of acetylation is a value indicating 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 as a percentage. The amount of ethylene groups to which the acetyl group is bonded can be measured, for example, in accordance with JIS K 6728 "Polyvinyl butyral test method".

The degree of acetalization (the degree of butyralization in the case of polyvinyl butyral resin) of the polyvinyl acetal resin (0) is preferably 60 mol% or more, more preferably 63 mol% or more, preferably 85 mol% or less, more Preferably it is 75 mol% or less, More preferably, it is 70 mol% or less. The compatibility with polyvinyl acetal resin and a plasticizer becomes it high that the said degree of acetalization is more than the said minimum. The reaction time required in order to manufacture polyvinyl acetal resin as the said degree of acetalization is below the said upper limit becomes short.

The degree of acetalization (the degree of butyralization in the case of polyvinyl butyral resin) of the polyvinyl acetal resin (1) is preferably 47 mol% or more, more preferably 60 mol% or more, preferably 85 mol% or less Preferably it is 80 mol% or less, More preferably, it is 75 mol% or less. The compatibility with polyvinyl acetal resin and a plasticizer becomes it high that the said degree of acetalization is more than the said minimum. The reaction time required in order to manufacture polyvinyl acetal resin as the said degree of acetalization is below the said upper limit becomes short.

The acetalization degree (butyralization degree 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 it is 75 mol% or less, More preferably, it is 71 mol% or less. The compatibility with polyvinyl acetal resin and a plasticizer becomes it high that the said degree of acetalization is more than the said minimum. The reaction time required in order to manufacture polyvinyl acetal resin as the said degree of acetalization is below the said upper limit becomes short.

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

The hydroxyl group content (hydroxyl content), the degree of acetalization (butyralization) and the degree of acetylation are preferably calculated from the results measured by the method according to JIS K 6728 "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 content of the hydroxyl group (hydroxyl content), the degree of acetalization (degree of butyralization) and the degree of acetylation are methods according to JIS K 6728 "Polyvinyl butyral test method" It can be calculated from the result measured by

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

The plasticizer is not particularly limited. Conventionally known plasticizers can be used as the above-mentioned plasticizer. The plasticizer may be used alone or in combination of two or more.

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. The plasticizer is preferably a liquid plasticizer.

As said monobasic organic acid ester, the glycol ester etc. which are obtained by reaction of glycol and a monobasic organic acid are mentioned. 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 ester include ester compounds of a polybasic organic acid and an alcohol 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-ethyl butyrate, triethylene glycol di-2-ethyl hexanoate, 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-ethyl butyrate, 1,3-propylene glycol di-2-ethyl butyrate, 1,4-butylene glycol di-2-ethyl butyrate, diethylene glycol di-2-ethyl Tylate, diethylene glycol di-2-ethylhexanoate, dipropylene glycol di-2-ethyl butyrate, triethylene glycol di-2-ethyl pentanoate, tetraethylene glycol di-2-ethyl butyrate, diethylene glycol dicaprylate Maleic acid dibutyl, bis (2-butoxyethyl) adipate, dibutyl adipate, diisobutyl adipate, 2,2-butoxyethoxy adipate, glycol ester of benzoic acid, 1,3-butylene glycol adipate polyester, adipic acid Dihexyl, dioctyl adipate, hexyl cyclohexyl adipate, a mixture of heptyl adipate and nonyl adipate, diisononyl adipate, diisodecyl adipate, heptyl noni adipate , Tributyl citrate, acetyl tributyl citrate, diethyl carbonate, dibutyl sebacate, bis (2-ethylhexyl) phthalate, oil-modified sebacic alkyds, and mixtures of phosphoric acid esters and adipic acid esters. Organic ester plasticizers other than these may be used. Other adipates may be used other than the adipates described above.

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

The plasticizer is preferably a diester plasticizer represented by the following formula (1).

In the above formula (1), 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 R 1 and R 2 in the above formula (1) is preferably an organic group having 6 to 10 carbon atoms.

The above plasticizers are triethylene glycol di-n-butanoate (3 GB), bis (2-ethylhexyl) phthalate, triethylene glycol di-2-ethylhexanoate (3GO) or triethylene glycol di-2-ethyl butyrate It is preferred to include a rate (3 GH). The plasticizer preferably includes triethylene glycol di-n-butanoate (3 GB), triethylene glycol di-2-ethylhexanoate (3GO) or triethylene glycol di-2-ethyl butyrate (3GH). Preferably, triethylene glycol di-2-ethylhexanoate is more preferably included.

Let content of the said plasticizer (0) with respect to 100 weight part of said thermoplastic resins (0) in the said thermoplastic resin film be 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, more preferably Is 50 parts by weight or less. When the content (0) is at least the lower limit, the penetration resistance is further enhanced. The transparency of the thermoplastic resin film is further enhanced when the content (0) is less than or equal to the upper limit.

In the first layer, the content of the plasticizer (1) with respect to 100 parts by weight of the thermoplastic resin (1) is taken as the 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, more preferably Is at most 85 parts by weight, particularly preferably at most 80 parts by weight. The softness | flexibility of a thermoplastic resin film becomes it high that the said content (1) is more than the said lower limit, and the handling of a thermoplastic resin film becomes easy. When the content (1) is less than or equal to the upper limit, the penetration resistance is further enhanced.

In the second layer, the content of the plasticizer (2) with respect to 100 parts by weight of the thermoplastic resin (2) is taken as the content (2). In the third layer, the content of the plasticizer (3) with respect to 100 parts by weight of the thermoplastic resin (3) is taken as the content (3). The content (2) and the content (3) are each 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, most preferably 25 parts by weight or more. The content (2) and the content (3) are each 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, most preferably It is 30 parts by weight or less. The softness | flexibility of a thermoplastic resin film becomes it high that the said content (2) and the said content (3) are more than the said lower limit, and the handling of a thermoplastic resin film becomes easy. When the content (2) and the content (3) are less than or equal to the upper limit, penetration resistance is further enhanced.

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

From the viewpoint of further enhancing the sound insulation of 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 further preferably Preferably it is 20 parts by weight or more. From the viewpoint of further enhancing the sound insulation of 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 further preferably 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 each preferably at most 80 parts by weight, More preferably, it is 75 parts by weight or less, still more preferably 70 parts by weight or less.

(Thermoelectric material)
The thermoplastic resin film contains a thermoelectric conversion material. The surface layer may contain the thermoelectric conversion material. It is preferable that the said intermediate | middle layer contains the said thermoelectric conversion material.

From the viewpoint of effectively enhancing the thermoelectric conversion efficiency, the property of 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 enhancing the thermoelectric conversion efficiency, the thermoelectric conversion material is preferably an organic compound.

Examples of the thermoelectric conversion material include polythiophene and carbon nanotubes. The thermoelectric conversion material may be a charge transfer complex containing polythiophene such as PEDOT PSS. There is a carbon nanotube as a thermoelectric conversion material. However, when carbon nanotubes are used, it may be difficult to increase the visible light transmittance of the thermoplastic resin film.

From the viewpoint of further enhancing the transparency of the thermoplastic resin film, the thermoelectric conversion material preferably contains polythiophene.

When the said thermoelectric conversion material is contained in the surface of a thermoplastic resin film, the adhesiveness of a thermoplastic resin film may fall.

In the multilayer film, the intermediate layer preferably contains a thermoelectric conversion material. In the multilayer film in which the first layer is disposed 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 disposed between the second layer and the third layer, the content of the thermoelectric conversion material in the first layer is the second layer and the third layer. The content is preferably more than the content of the thermoelectric conversion material in, more preferably 0.005% by weight or more, and still more preferably 0.01% by weight or more. Each of the second layer and the third layer may not contain the 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, may be less than 0.03% by weight, and less than 0.01% by weight. It may be.

The content of the thermoelectric conversion material is preferably 0.01% by weight or more, more preferably 0.03% by weight or more, and more preferably 100% by weight of the thermoplastic resin film and 100% by weight of the layer containing the thermoelectric conversion material. 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 is preferably 0.5% by weight or less, more preferably 0.2% by weight or less, more preferably 100% by weight of the thermoplastic resin film and 100% by weight of the layer containing the thermoelectric conversion material. Is 0.1 wt% or less, particularly preferably 0.05 wt% or less. The thermoelectric conversion function becomes high effectively as content of the said thermoelectric conversion material is below the said upper limit.

(Dopant)
The thermoplastic resin film preferably contains a dopant. The use of the dopant improves the thermoelectric conversion efficiency and conductivity of the resulting thermoplastic resin film. Only one type of the dopant may be used, or two or more types may be used in combination.

Examples of the dopant include halogens, Lewis acids, protic 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 PF ₅ , AsF ₅ , SbF ₅ , BF ₃ , BCl ₃ , BBr ₃ or SO ₃ . The protonic acid is preferably HF, HCl, HNO ₃ , H ₂ SO ₄ , HClO ₄ , FSO ₃ H, CISO ₃ H or CF ₃ SO ₃ H. The transition metal compounds are FeCl ₃ , FeOCl, AgCl, AuCl ₃ , TiCl ₄ , ZrCl ₄ , ZrCl ₄ , HfCl ₄ , NbF ₅ , NbCl ₅ , TaCl ₅ , MoF ₅ , MoCl ₅ , WF ₆ , WCl ₆ , UF ₆ or LnCl ₃ (Ln = lanthanoid such as La, Ce, Pr, Nd or Sm) is preferable. 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 by 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 thermoplastic resin film. The content of the dopant is preferably 10 parts by weight or more based on 100 parts by weight of the thermoelectric conversion material in the thermoplastic resin film from the viewpoint of further enhancing the effect by doping or effectively enhancing the effect. Preferably it is 40 parts by weight or less, more preferably 30 parts by weight or less.

(Light stabilizer)
It is preferable that the thermoplastic resin film, the surface layer, and the intermediate layer contain a light stabilizer. By the use of the light stabilizer, even if the thermoplastic resin film is used for a long time or exposed to sunlight, the color change is further suppressed and the visible light transmittance is less likely to be further reduced. The light stabilizers may be used alone or in combination of two or more.

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

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

Examples of hindered amine light stabilizers in which an alkyl group is bonded to the nitrogen atom of the piperidine structure include “Tinuvin 765” and “Tinuvin 622 SF” manufactured by BASF, and “Adekastab LA-52” manufactured by ADEKA.

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

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

From the viewpoint of further suppressing the color change, the molecular weight of the light stabilizer is preferably 2000 or less, more preferably 1000 or less, and still more preferably 700 or less.

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

(Metal salt)
The thermoplastic resin film and the surface layer preferably contain a magnesium salt, an alkali metal salt or an alkaline earth metal salt (hereinafter, these may be collectively referred to as a metal salt M). The intermediate layer may contain the metal salt M. The use of the metal salt M makes it easier to control the adhesion of the thermoplastic resin film according to the present invention to a glass plate, a laminated glass member, another film or the like. The metal salt M may be used alone or in combination of two or more.

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 thermoplastic 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 preferable, and a carboxylic acid magnesium salt having 2 to 16 carbon atoms or a potassium salt of carboxylic acid having 2 to 16 carbon atoms is more preferable.

The above-mentioned magnesium salt of carboxylic acid having 2 to 16 carbon atoms and potassium salt of carboxylic acid having 2 to 16 carbon atoms include magnesium acetate, potassium acetate, magnesium propionate, potassium propionate, magnesium 2-ethyl butyric acid, 2-ethyl butanoic acid Examples thereof include potassium, magnesium 2-ethylhexanoate and potassium 2-ethylhexanoate.

The total content of Mg and K in the thermoplastic resin film and the total content of Mg and K in a layer containing Mg or K (such as a surface layer) is preferably 5 ppm or more, more preferably 10 ppm or more. More preferably, it is 20 ppm or more, preferably 300 ppm or less, more preferably 250 ppm or less, and still more preferably 200 ppm or less. The adhesive force of the thermoplastic resin film with respect to a glass plate, a laminated glass member, another film, etc. as the sum total of content of Mg and K is more than the said lower limit and below the said upper limit can be controlled still more favorably.

(UV screening agent)
The thermoplastic resin film, the surface layer and the intermediate layer preferably contain an ultraviolet shielding agent. Even when the thermoplastic resin film is used for a long time or under high temperature, the use of the above-mentioned ultraviolet shielding agent further suppresses the color change, and the visible light transmittance is less likely to be reduced. The ultraviolet screening agent may be used alone or in combination of two or more.

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

Examples of the UV shielding agent include metal UV shielding agents (UV shielding agents containing metal), metal oxide UV shielding agents (UV shielding agents including metal oxide), benzotriazole UV shielding agents ( UV screening agent having a benzotriazole structure), benzophenone UV shielding agent (UV screening agent having a benzophenone structure), triazine UV shielding agent (UV screening agent having a triazine structure), malonic acid ester UV shielding agent (malonic acid) UV shielding agents having an ester structure), oxalic acid anilide UV shielding agents (UV shielding agents having an anilide oxalate structure), and benzoate based UV shielding agents (a UV shielding agent having a benzoate structure).

Examples of the metal-based ultraviolet shielding agent include platinum particles, particles obtained by coating the surface of platinum particles with silica, palladium particles, particles obtained by coating the surface of palladium particles with silica, and the like. Preferably, the UV screening agent is not a thermal barrier particle.

The UV screening agent is preferably a benzotriazole UV screening agent, a benzophenone UV screening agent, a triazine UV screening agent or a benzoate UV screening agent, more preferably a benzotriazole UV screening agent or a benzophenone UV shielding agent More preferably, it is a benzotriazole-based ultraviolet screening agent.

Examples of the metal oxide ultraviolet shielding agent include zinc oxide, titanium oxide and cerium oxide. Furthermore, the surface may be coat | covered regarding the said metal oxide type ultraviolet-ray shielding agent. As a coating material of the surface of the said metal oxide type ultraviolet-ray shielding agent, an insulating metal oxide, a hydrolysable organosilicon compound, a silicone compound, etc. are mentioned.

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

Examples of the benzotriazole-based ultraviolet screening agent include 2- (2′-hydroxy-5′-methylphenyl) benzotriazole (“TinuvinP” manufactured by BASF), 2- (2′-hydroxy-3 ′, 5 ′). -Di-t-butylphenyl) benzotriazole ("Tinuvin 320" manufactured by BASF), 2- (2'-hydroxy-3'-t-butyl-5-methylphenyl) -5-chlorobenzotriazole (manufactured by BASF) Tinuvin 326 ′ ′) and 2- (2′-hydroxy-3 ′, 5′-di-amylphenyl) benzotriazole (“Tinuvin 328” manufactured by BASF Corporation). It is preferable that it is a benzotriazole-type ultraviolet-ray shielding agent containing a halogen atom, and it is more preferable that it is a benzotriazole-type ultraviolet-ray shielding agent containing a chlorine atom, since it is excellent in the performance which absorbs an ultraviolet-ray.

As said benzophenone series ultraviolet screening agent, octabenzone ("Chimassorb 81" by BASF Corporation) etc. are mentioned, for example.

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

As the above-mentioned malonic acid ester-based ultraviolet screening agent, dimethyl 2- (p-methoxybenzylidene) malonate, tetraethyl-2,2- (1,4-phenylene dimethylidene) bismalonate, 2- (p-methoxybenzylidene) -bis (1,2,2,6,6-pentamethyl 4-piperidinyl) malonate and the like can be mentioned.

Examples of commercially available products of the malonic acid ester-based ultraviolet screening agent include Hostavin B-CAP, Hostavin PR-25, and Hostavin PR-31 (all manufactured by Clariant Co.).

N- (2-ethylphenyl) -N '-(2-ethoxy-5-t-butylphenyl) oxalic acid diamide, N- (2-ethylphenyl) -N' as the above oxalic acid anilide type ultraviolet screening agent Oxalic acid diamides having an aryl group or the like substituted on a nitrogen atom, such as-(2-ethoxy-phenyl) oxalic acid diamide, 2-ethyl-2'-ethoxy-oxyanilide ("Sanduvor VSU" manufactured by Clariant) It can be mentioned.

Examples of the benzoate series ultraviolet screening agent include 2,4-di-tert-butylphenyl-3,5-di-tert-butyl-4-hydroxybenzoate ("Tinuvin 120" manufactured by BASF Corp.).

The content of the UV shielding agent is preferably 0.1% by weight or more, more preferably 0.2% by weight or more, and 100% by weight of the thermoplastic resin film and 100% by weight of the layer containing the UV shielding agent. Preferably, it is 0.3% by weight or more, particularly preferably 0.5% by weight or more. The content of the UV shielding agent is preferably 2.5% by weight or less, more preferably 2% by weight or less, and further preferably 100% by weight of the thermoplastic resin film and 100% by weight of the layer containing the UV shielding agent. It is 1% by weight or less, particularly preferably 0.8% by weight or less. When the content of the ultraviolet shielding agent is not less than the lower limit and not more than the upper limit, the discoloration is further suppressed, and the decrease in visible light transmittance is further suppressed.

(Antioxidant)
The thermoplastic resin film, the surface layer and the intermediate layer preferably contain an antioxidant. By the use of the above-mentioned antioxidant, even if the thermoplastic resin film is used for a long time or under high temperature, the color change is further suppressed and the visible light transmittance is less likely to be reduced. As the above-mentioned antioxidant, only 1 type may be used and 2 or more types may be used together.

As said antioxidant, a phenol type antioxidant, a sulfur type antioxidant, phosphorus type antioxidant etc. are mentioned. The said phenolic antioxidant is an antioxidant which has a phenol frame. The sulfur-based antioxidant is a sulfur atom-containing antioxidant. The phosphorus-based antioxidant is a phosphorus atom-containing antioxidant.

It is preferable that the said antioxidant is a phenolic antioxidant or phosphorus type antioxidant.

Examples of the above-mentioned phenolic antioxidants 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-hydride) Roxy-5-tert-butylphenol) butane, 1,3,5-trimethyl-2,4,6-tris (3,5-di-tert-butyl-4-hydroxybenzyl) benzene, bis (3,3'-) t-Butylphenol) butyric acid glycol ester and bis (3-t-butyl-4-hydroxy-5-methylbenzenepropanoic acid) ethylene bis (oxyethylene). One or more of these antioxidants are preferably used.

The above-mentioned phosphorus-based antioxidants include tridecyl phosphite, tris (tridecyl) phosphite, triphenyl phosphite, torinylphenyl phosphite, bis (tridecyl) pentaerythritol diphosphite, bis (decyl) pentaerythritol diphos Phytos, tris (2,4-di-t-butylphenyl) phosphite, bis (2,4-di-t-butyl-6-methylphenyl) ethyl ester phosphorous acid, and 2,2′-methylene bis (4 And 6-di-t-butyl-1-phenyloxy) (2-ethylhexyloxy) phosphorus. One or more of these antioxidants are preferably used.

As a commercial item of the above-mentioned antioxidant, for example, "IRGANOX 245" made by BASF, "IRGAFOS 168" made by BASF, "IRGAFOS 38" made by BASF, "Sumilyzer BHT" made by Sumitomo Chemical Co., Ltd., Sakai Chemical Industry Co., Ltd. Examples thereof include "H-BHT", "IRGANOX 1010" manufactured by BASF, and "Adekastab AO-40" manufactured by ADEKA.

From the viewpoint of further suppressing the color change and further suppressing the decrease in the visible light transmittance, the content of the antioxidant is 100% by weight of the thermoplastic resin film and 100% by weight of the layer containing an antioxidant. It is preferable that it is 0.1 weight% or more. Moreover, since the addition effect of antioxidant is saturated, it is preferable that content of the said antioxidant is 2 weight% or less in 100 weight% of said thermoplastic resin films.

(Other ingredients)
The thermoplastic resin film, the surface layer, and the intermediate layer are, if necessary, an adhesive force modifier other than a coupling agent, a dispersant, a surfactant, a flame retardant, an antistatic agent, a pigment, a dye, and a metal salt. Additives such as moisture proofing agents, optical brighteners and infrared absorbers may be included. One of these additives may be used alone, or two or more thereof may be used in combination.

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

The thickness of the thermoplastic resin film is not particularly limited. The thickness of the thermoplastic resin film is preferably 0.1 mm or more, more preferably 0.25 mm or more, preferably 3 mm or less, more preferably from the viewpoint of practical use and from the viewpoint of sufficiently enhancing the heat shielding properties. It is 1.5 mm or less. The penetration resistance of a glass plate containing laminated body becomes it still higher that the thickness of the said thermoplastic resin film is more than the said minimum. When the thickness of the thermoplastic resin film is equal to or less than the upper limit, the transparency of the thermoplastic resin film is further improved.

The manufacturing method of the said thermoplastic resin film is not specifically limited. A conventionally known method can be used as a method for producing the thermoplastic resin film. For example, the manufacturing method etc. which knead | mix a compounding component and shape | mold a thermoplastic resin film are mentioned. Extrusion is preferred because it is suitable for continuous production.

The method of kneading is not particularly limited. Examples of this method include a method using an extruder, a plastograph, a kneader, a Banbury mixer, a calender roll, or the like. As it is suitable for continuous production, a method using an extruder is preferred, and a method using a twin screw extruder is more preferred.

(Uses of thermoplastic resin film and thermoelectric conversion film)
The thermoplastic resin film is preferably an intermediate film for laminated glass. It is preferable that the said thermoelectric conversion film is an intermediate film for laminated glasses which has a thermoelectric conversion function.

The said thermoplastic resin film and the said thermoelectric conversion film are bonded together to a glass plate, and in order to obtain a glass plate containing laminated body, it is used suitably. By connecting an electrode to the above-mentioned thermoplastic resin film, a thermoelectric conversion-glass plate containing laminate can be obtained.

The said thermoplastic resin film is arrange | positioned between a 1st laminated glass member and a 2nd laminated glass member, and in order to obtain laminated glass, it is used suitably. A thermoelectric conversion laminated glass can be obtained by connecting an electrode to the thermoplastic resin film in the laminated glass. The thermoelectric conversion laminated glass is a laminated glass having a thermoelectric conversion function.

It is preferable that the said laminated glass is equipped with a 1st laminated glass member, a 2nd laminated glass member, and the thermoplastic resin film mentioned above. It is preferable that the said thermoplastic resin film is arrange | positioned between a said 1st laminated glass member and a said 2nd laminated glass member. It is preferable that the said thermoplastic resin film is connected and used for an electrode.

It is preferable that the said thermoelectric conversion laminated glass is equipped with a 1st laminated glass member, a 2nd laminated glass member, the thermoplastic resin film mentioned above, and an electrode. The thermoplastic resin film is disposed between the first laminated glass member and the second laminated glass member. The thermoplastic resin film is connected to the electrode.

Moreover, it is preferable that the said thermoelectric conversion laminated glass is equipped with a 1st laminated glass member, a 2nd laminated glass member, and the thermoelectric conversion film mentioned above. Preferably, the thermoplastic resin film in the thermoelectric conversion film is disposed between the first laminated glass member and the second laminated glass member.

FIG. 3: is sectional drawing which shows an example of the thermoelectric conversion laminated glass using the thermoelectric conversion film shown in FIG.

The thermoelectric conversion laminated glass 31 shown in FIG. 3 includes a laminated glass 40, an electrode 21, a conducting wire 22, and an electrical extraction portion 23. The thermoelectric conversion laminated glass 31 includes the thermoelectric conversion film 1.

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

The thermoplastic resin film 10 is disposed between the first laminated glass member 41 and the second laminated glass member 42 and is sandwiched. The first laminated glass member 41 is laminated on the first surface (one surface) of the thermoplastic 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 thermoplastic resin film 10.

FIG. 4: is sectional drawing which shows an example of the thermoelectric conversion laminated glass using the thermoelectric conversion film shown in FIG.

The thermoelectric conversion laminated glass 31A shown in FIG. 4 includes a laminated glass 40A, an electrode 21, a lead 22, and an electrical extraction part 23. The thermoelectric conversion laminated glass 31A includes the thermoelectric conversion film 1A.

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

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

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

Inorganic glass and organic glass are mentioned as said glass plate. Examples of the inorganic glass include float plate glass, heat ray absorbing plate glass, heat ray reflecting plate glass, polished plate glass, template glass, and lined plate glass. The organic glass is a synthetic resin glass instead of inorganic glass. As said organic glass, a polycarbonate board, a poly (meta) acrylic resin board, etc. are mentioned. As said poly (meth) acryl resin board, a polymethyl (meth) acrylate board etc. are mentioned.

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. Moreover, the thickness of the said glass plate becomes like this. Preferably it is 1 mm or more, Preferably it is 5 mm or less, More preferably, it is 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.

The manufacturing method of the said glass plate containing laminated body is not specifically limited. A glass plate containing laminated body can be obtained by bonding the said thermoplastic resin film together to the said 1st glass plate. Furthermore, for example, a thermoplastic resin film is sandwiched between the first laminated glass member and the second laminated glass member, and the thermoplastic resin film is inserted into a pressure roll or put into a rubber bag and suctioned under reduced pressure. The air remaining between the first laminated glass member and the thermoplastic resin film and between the second laminated glass member and the thermoplastic resin film is degassed. Thereafter, pre-bonding is performed at about 70 ° C. to 110 ° C. to obtain a laminate. The laminate is then placed in an autoclave or pressed and pressed at a pressure of about 120 ° C. to 150 ° C. and a pressure of 1 MPa to 1.5 MPa. Thus, laminated glass which is a glass plate containing laminated body can be obtained.

The thermoplastic resin film and the laminated glass can be used for automobiles, railway vehicles, aircraft, ships, buildings and the like. The said thermoplastic resin film and the said laminated glass can be used besides these uses. The thermoplastic resin film and the laminated glass are preferably a thermoplastic resin film and a laminated glass for vehicles or for construction, and more preferably a thermoplastic resin film and a laminated glass for vehicles. The thermoplastic resin film and the laminated glass can be used as a front glass, a side glass, a rear glass or a roof glass of an automobile. The thermoplastic resin film and the laminated glass are suitably used in automobiles. The said thermoplastic resin film is used in order to obtain the laminated glass of a motor vehicle.

The present invention will be described in more detail by way of the following Examples and Comparative Examples. The present invention is not limited to these examples.

The following materials were used.

In the polyvinyl acetal resin used, n-butyraldehyde having 4 carbon atoms is used for acetalization. With respect to the polyvinyl acetal resin, the degree of acetalization (butyralization), the degree of acetylation and the hydroxyl group content were measured by a method according to JIS K 6728 "Polyvinyl butyral test method". In addition, when measured by ASTM D1396-92, the same numerical value as the method according to JIS K6728 "polyvinyl butyral test method" was shown.

(Thermoplastic resin)
Polyvinyl acetal resin (in the table, “PVB”, average polymerization degree 1700, hydroxyl content 30.5 mol%, degree of acetylation 1 mol%, degree of acetalization 68.5 mol%)

(Plasticizer)
Triethylene glycol di-2-ethylhexanoate (3GO)
Triethylene glycol di-n-butanoate (3 GB)

(Thermoelectric material)
Poly (3,4-ethylenedioxythiophene): Poly (4-styrene sulfonate) (PEDOT PSS)
Polythiophene carbon nanotube (CNT)

(Dopant)
Anhydrous ferric chloride (III)

(Metal salt)
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)
(UV screening agent)
BASF "Tinuvin 326"
(Antioxidant)
BHT (2,6-di-t-butyl-p-cresol)

Example 1
Preparation of composition for forming interlayer:
The following blending components were blended and sufficiently kneaded with a mixing roll to obtain a composition for forming an intermediate film.

Polyvinyl acetal resin (average polymerization degree 1700, hydroxyl content 30.5 mol%, acetylation degree 1 mol%, acetalization degree 68.5 mol%) 100 parts by weight triethylene glycol di-2-ethylhexanoate ( 3GO) 40 parts by weight Thermoelectric conversion material (PEDOT PSS) in an amount of 0.05% by weight in the obtained interlayer film
Mixture of magnesium acetate and magnesium 2-ethyl butyric acid in an amount of 60 ppm of Mg in the resulting interlayer film BASF "Tinuvin 326" in an amount of 0.2 wt% in the resulting interlayer film
BHT (2,6-di-t-butyl-p-cresol) in an amount of 0.2% by weight in the resulting interlayer film
Anhydrous iron chloride (III) in an amount of 12.5 parts by weight with respect to 100 parts by weight of the thermoelectric conversion material in the resulting interlayer film

Preparation of interlayer:
The composition for forming the intermediate film was extruded using an extruder to obtain an intermediate film (thermoplastic resin film) having a thickness of 760 μm.

Preparation of laminated glass (for visible light transmittance measurement):
The obtained interlayer was cut into a size of 5 cm long × 5 cm wide. Next, two sheets of green glass (5 cm long × 5 cm wide × 2 mm thick) in accordance with JIS R3208 were prepared. The obtained interlayer film was sandwiched between the two sheets of green glass, held at 90 ° C. for 30 minutes with a vacuum laminator, and vacuum pressed to obtain a laminate. In the laminated body, the intermediate film portion protruding from the glass plate was cut off to obtain a laminated glass.

Preparation of thermoelectric conversion laminated glass:
An electrode was connected to the intermediate film (thermoplastic resin film) exposed at both ends of the laminated glass. The electrode was connected to an electrical extraction part (provided with a power meter) via a conducting wire to obtain a thermoelectric conversion laminated glass.

(Examples 2 to 12)
An interlayer film, a laminated glass, and a thermoelectric material were prepared in the same manner as in Example 1 except that the type and blending amount of the thermoelectric conversion material, and the type and blending amount of the plasticizer were set as shown in Tables 1 and 2 below. A conversion laminated glass was obtained.

(Comparative example 1)
The polyester film was stuck on the glass substrate. Next, an aqueous solution of poly (3,4-ethylenedioxythiophene): poly (4-styrene sulfonate) (PEDOT PSS) is applied on a polyester film by spin coating, and the applied PEDOT PSS aqueous solution is heated and dried. The PEDOT PSS membrane was formed on a polyester film. Next, the laminate of the polyester film and the PEDOT PSS film was peeled off from the glass substrate. This laminate was used as an intermediate film to obtain laminated glass and thermoelectric conversion laminated glass.

(Comparative example 2)
The polyester film was stuck on the glass substrate. Then, carbon nanotubes (CNTs) were dispersed in an aqueous solution containing polyvinyl alcohol to prepare a CNT dispersion. The obtained CNT dispersion was applied onto a polyester film by spin coating, and the coated CNT dispersion was dried by heating to form a CNT film on the polyester film. Subsequently, the laminated body of a polyester film and a CNT film | membrane was peeled from the glass substrate. This laminate was used as an intermediate film to obtain laminated glass and thermoelectric conversion laminated glass.

(Comparative example 3)
An intermediate film, a laminated glass, and a thermoelectric conversion laminated glass were obtained in the same manner as in Example 1 except that the thermoelectric conversion material was not used.

(Comparative Examples 4 to 5)
An intermediate film, a laminated glass, and a thermoelectric conversion laminated glass were obtained in the same manner as in Example 1 except that the type and blending amount of the thermoelectric conversion material were set as shown in Table 3 below.

(Evaluation)
(1) Bending hardness After conditioning the test piece at 23 ° C. and 50% RH, using a pure bending tester (“KES-FB2-A” manufactured by Kato Tech Co., Ltd.), the deformation rate of the test piece is 0.5 cm / It was bent and deformed in seconds. The curvature and torque at that time were measured, the bending moment change amount per unit curvature change (per unit specimen width) was determined, and the determined value was used as the pure bending hardness (in the present specification, simply " It is called "flexible hardness").

(2) Bending test The intermediate film (thermoplastic composition resin film) after bending once and the intermediate film (thermoplastic composition resin film) after bending 10 times were observed, and the bending property was judged based on the following criteria. .

[Bending test]
:: No fold was observed in the interlayer (thermoplastic composition resin film) after bending 10 times. X: a fold was observed in the interlayer (thermoplastic composition resin film) after bending.

(3) Visible light transmittance (A light Y value, initial A-Y (380 nm to 780 nm))
The visible light transmittance (Visible Transmittance) at a wavelength of 380 nm to 780 nm of the obtained laminated glass E was measured according to JIS R 3211: 1998 using a spectrophotometer ("U-4100" manufactured by Hitachi High-Technologies Corporation) .

(4) Thermoelectric conversion function (thermal conductivity)
The thermal conductivity λ was determined 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 (intermediate 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 from the weight measurement value and the volume measurement value of the test piece.

(conductivity)
A constant current was supplied from a current source to the test piece (intermediate film) in a vacuum atmosphere by the four-terminal method, and the voltage value was read by a digital multimeter to calculate the conductivity.

(Seebeck coefficient)
The test piece was fixed to the wiring board arrange | positioned so that an electrode might each contact at the both ends of a test piece (intermediate film). A heater was provided on one electrode side of the wiring substrate on which the test piece was fixed, and the heater was placed in a vacuum chamber to heat one end of the test piece in a vacuum environment. In addition, a chromel-almel thermocouple was disposed at a position adjacent to the electrode to measure a temperature difference generated at both ends of the sample. Each electrode was connected to a voltmeter, and the thermoelectromotive force generated at both ends of the test piece was measured. In addition, the one end which is not heated is kept at about 20 degreeC, and the other end heated by the heater rose in temperature from 21 degreeC to 31 degreeC. The thermal electromotive force at that time was measured, and the Seebeck coefficient was calculated from the slope.

Details and results are shown in Tables 1 to 3 below. In Tables 1 to 3, the descriptions of the dopant, metal salt, UV shielding agent and antioxidant used in Examples 1 to 12 and Comparative Examples 3 to 5 are omitted.

DESCRIPTION OF SYMBOLS 1, 1A ...

Thermoelectric conversion film

10, 10A ... Thermoplastic resin film 11 ... 1st layer 12 ... 2nd layer 13 ... 3rd layer 21 ... Electrode 22 ... Lead wire 23 ...

Electric extraction part

31, 31A ... Thermoelectric conversion Laminated

glass

40, 40A: laminated glass 41: first laminated glass member 42: second laminated glass member

Claims

A thermoplastic resin film used by being connected to an electrode,
With thermoplastic resin,
And a thermoelectric conversion material that exhibits a thermoelectric conversion function in a state where the thermoplastic resin film is connected to the electrode,
The thermoplastic resin film whose bending hardness is 0.49 N * cm < 2 > / cm or less.
The thermoplastic resin film according to claim 1, wherein the property of the thermoelectric conversion material is particulate or fibrous.
The thermoplastic resin film according to claim 1, wherein the thermoelectric conversion material is an organic compound.
The thermoplastic resin film according to any one of claims 1 to 3, wherein the thermoplastic resin is a polyvinyl acetal resin.
The thermoplastic resin film according to any one of claims 1 to 4, which contains a plasticizer.
The thermoplastic resin film according to claim 5, wherein a content of the plasticizer with respect to 100 parts by weight of the thermoplastic resin is 20 parts by weight or more and 100 parts by weight or less.
The thermoplastic resin according to any one of claims 1 to 6, wherein the content of the thermoelectric conversion material is 0.01 wt% or more and 0.5 wt% or less in 100 wt% of the thermoplastic resin film. the film.
The thermoplastic resin film according to any one of claims 1 to 7, which is an interlayer for laminated glass.
Thermoplastic resin film,
Equipped with electrodes,
The thermoplastic resin film includes a thermoplastic resin and a thermoelectric conversion material,
The thermoplastic resin film is connected to the electrode,
The thermoelectric conversion film whose bending hardness of the said thermoplastic resin film is 0.49 N * cm < 2 > / cm or less.
The thermoelectric conversion film according to claim 9, wherein the property of the thermoelectric conversion material is particulate or fibrous.
The thermoelectric conversion film according to claim 9, wherein the thermoelectric conversion material is an organic compound.
The thermoelectric conversion film according to any one of claims 9 to 11, wherein the thermoplastic resin is a polyvinyl acetal resin.
The thermoelectric conversion film according to any one of claims 9 to 12, wherein the thermoplastic resin film contains a plasticizer.
The thermoelectric conversion film according to claim 13, wherein a content of the plasticizer with respect to 100 parts by weight of the thermoplastic resin is 20 parts by weight or more and 100 parts by weight or less.
The thermoelectric conversion film according to any one of claims 9 to 14, wherein the content of the thermoelectric conversion material is 0.01 wt% or more and 0.5 wt% or less in 100 wt% of the thermoplastic resin film. .
The thermoelectric conversion film according to any one of claims 9 to 15, which is an intermediate film for laminated glass having a thermoelectric conversion function.
A first laminated glass member,
A second laminated glass member,
And the thermoplastic resin film according to claim 8.
The thermoplastic resin film is disposed between the first laminated glass member and the second laminated glass member,
Laminated glass, wherein the thermoplastic resin film is used by being connected to an electrode.
A first laminated glass member,
A second laminated glass member,
The thermoplastic resin film according to claim 8,
Equipped with electrodes,
The thermoplastic resin film is disposed between the first laminated glass member and the second laminated glass member,
Thermoelectric conversion laminated glass, wherein the thermoplastic resin film is connected to the electrode.
A first laminated glass member,
A second laminated glass member,
And the thermoelectric conversion film according to claim 16;
The thermoelectric conversion laminated glass, wherein the thermoplastic resin film in the thermoelectric conversion film is disposed between the first laminated glass member and the second laminated glass member.