Substrate-equipped polarization film, vibration power generation element, organic light-emitting element, and method for manufacturing substrate-equipped polarization film

Abstract

A substrate-equipped polarization film according to the present disclosure comprises: a substrate; and a polarization film formed on at least one of two main surfaces of the substrate. The polarization film contains a compound represented by formula (I). In formula (I), Z is a divalent organic group that imparts a bent structure to the compound and represents a hydrocarbon group having 2 to 80 carbons, a sulfonyl group, an amine group, an ether group, or a thioether group. Some or all of the hydrogen atoms of the hydrocarbon group may be substituted with halogen atoms. A1 and A2 each independently represent a single bond or a divalent linking group. X1 and X2 each independently represent a monovalent aromatic hydrocarbon group having 6 to 80 carbons or a hydrocarbon group having 2 to 80 carbons. In X1 and X2, some or all of the hydrogen atoms of the aromatic hydrocarbon group and the hydrocarbon group are substituted with fluorine atoms. The total number of fluorine atoms included in each of X1 and X2 is greater than the number of halogen atoms included in Z.

Description

Polarizing film with substrate, vibration power generation element, organic light-emitting element, and method for manufacturing polarizing film with substrate

[0001] The present invention relates to a substrate-attached polarizing film, a vibration power generating element, an organic light-emitting element, and a method for manufacturing a substrate-attached polarizing film.

[0002] Electrostatic vibration power generation elements (hereinafter simply referred to as "vibration power generation elements") are known as power generation elements that convert vibrations into electricity. Vibration power generation elements are configured to change the relative position between an electret and an electrode using vibration, thereby sequentially inducing electrostatic induction in the electrodes. Vibration power generation elements can efficiently extract electricity from low-frequency vibrations with small accelerations (e.g., environmental vibrations).

[0003] Research and development of electret films (hereinafter also referred to as "polarized films") obtained by injecting electric charges into polymer films has been the focus of research and development for the electrets used in vibration-powered energy harvesters. The methods used to inject electric charges into polymer films include charging processes (such as corona discharge, electron beam irradiation, thermal poling, and contact charging).

[0004] However, conventional methods for producing polarized films require the application of a high voltage to the polymer film from the outside. This requires large-scale equipment and a complicated manufacturing process. Conventional methods for producing polarized films have low productivity and high costs.

[0005] In recent years, vibration power generation elements that utilize organic thin films that have a surface potential that spontaneously develops during the film formation process have been reported (for example, Patent Documents 1 and 2).

[0006] Patent Document 1 discloses a vibration power generator (hereinafter also referred to as a "vibration power generation element"). The vibration power generation element disclosed in Patent Document 1 generates induced charges in a configuration having a counter electrode facing an electret electrode, and generates electricity by vibrating the electret electrode or the counter electrode to move the induced charges. The electret electrode has at least a first electrode and first polar molecules. A thin film consisting of the first polar molecules substantially containing Al(7-Prq)3, OXD-7, Alq3, TPBi, or BCP is laminated on the first electrode.

[0007] Patent Document 2 discloses a membrane (hereinafter also referred to as a "polarized membrane"). The membrane disclosed in Patent Document 1 contains a compound represented by the following general formula (x):

[0008]

[0009] In general formula (a), R represents a fluorinated alkyl group, 0 to 2 of X, Y, and Z each independently represent a fluorinated alkyl group, and the remaining each independently represent a substituent other than a fluorinated alkyl group.

[0010] Patent Document 1: Japanese Patent No. 7297280 Patent Document 2: Japanese Patent Laid-Open No. 2022-143338

[0011] However, the power generation output of the vibration power generation element disclosed in Patent Document 1 and the power generation output of the vibration power generation element using the polarized film disclosed in Patent Document 2 may be insufficient. It is known that the power generation output of a vibration power generation element is proportional to the square of the surface potential of the polarized film. Therefore, in order to increase the power generation output of a vibration power generation element, a substrate-attached polarized film with a larger absolute value of the surface potential per unit film thickness than conventional films is desired.

[0012] The present disclosure has been made in view of the above. An object of one embodiment of the present disclosure is to provide a substrate-attached polarizing film, a vibration power generating element, an organic light-emitting element, and a method for manufacturing a substrate-attached polarizing film, which have a larger absolute value of surface potential per unit film thickness.

[0013] Means for solving the above problems include the following embodiments: <1> A substrate-attached polarized film comprising a substrate and a polarized film formed on at least one of two main surfaces of the substrate, wherein the polarized film contains a compound represented by the following formula (I):

[0014]

[0015] (In formula (I), Z is a divalent organic group that imparts a bent structure to the compound, and represents a hydrocarbon group having 2 to 80 carbon atoms, a sulfonyl group, an amine group, an ether group, or a thioether group. Some or all of the carbon atoms constituting the hydrocarbon group may be substituted with heteroatoms. Some or all of the hydrogen atoms of the hydrocarbon group may be substituted with halogen atoms. A １ and A ２ each independently represents a single bond or a divalent linking group. １ and X ２ each independently represents a monovalent aromatic hydrocarbon group having 6 to 80 carbon atoms or a hydrocarbon group having 2 to 80 carbon atoms. １ and X ２ In the formula (I), some or all of the hydrogen atoms of the aromatic hydrocarbon group and the hydrocarbon group are substituted with fluorine atoms. １ and X ２ The total number of fluorine atoms contained in each of the groups is greater than the number of halogen atoms contained in the group Z.) <2> The divalent organic group is one selected from the group consisting of groups represented by the following formulas (z-1) to (z-7), １ and X ２ is one selected from the group consisting of groups represented by the following formulas (x-1) to (x-10):

[0016]

[0017] (In formulas (z-1) to (z-7) and formulas (x-1) to (x-10), * indicates a bonding position.) <3> X １ and X ２ is a group represented by the formula (x-1), (x-2) or (x-3), and the divalent organic group is a group represented by the formula (z-1), (z-2) or (z-3). <4> The substrate-attached polarized film according to <2>, wherein the divalent organic group is one selected from the group consisting of groups represented by the formula (z-1) and the formulas (z-3) to (z-7). <5> A １ and A ２each independently represent the divalent linking group, the divalent linking group is an aromatic hydrocarbon group having 6 to 80 carbon atoms, and some or all of the carbon atoms constituting the divalent linking group may be substituted with heteroatoms. <6> The substrate-attached polarized film according to <5>, wherein the divalent linking groups are each independently represented by the following formula (a-1), formula (a-2), or formula (a-3):

[0018]

[0019] (In formulas (a-1), (a-2), and (a-3), * indicates a bonding position.) <7> The substrate-attached polarizing film according to any one of <1> to <6>, wherein the compound has a permanent dipole moment of 4.0 Debye to 25.0 Debye in absolute value. <8> The substrate-attached polarizing film according to any one of <1> to <7>, wherein the absolute value of the surface potential per unit film thickness is 180 mV / nm to 1200 mV / nm. <9> A vibration power generating element comprising the substrate-attached polarizing film according to any one of <1> to <8>. <10> An organic light-emitting element comprising a polarizing film separated from the substrate-attached polarizing film according to any one of <1> to <8>. <11> A method for producing the substrate-attached polarized film according to any one of <1> to <9>, comprising: preparing a raw material containing the compound; and forming the polarized film on at least one of two main surfaces of the substrate by vacuum deposition or wet process using the raw material.

[0020] According to an embodiment of the present disclosure, there are provided a substrate-attached polarizing film, a vibration power generating element, an organic light-emitting element, and a method for manufacturing a substrate-attached polarizing film, which have a larger absolute value of surface potential per unit film thickness.

[0021] FIG. 1 is a diagram showing the direction of the permanent dipole moment of compound (I-1). FIG. 2 is a cross-sectional view of a vibration power generating element according to a first embodiment of the present disclosure. FIG. 3 is a cross-sectional view of a vibration power generating element according to a second embodiment of the present disclosure. FIG. 4 is a cross-sectional view of a vibration power generating element according to a third embodiment of the present disclosure. FIG. 5 is a cross-sectional view of the compound obtained in Synthesis Example (I-1). １6 is a graph showing the H-NMR of the compound obtained in Synthesis Example (I-2). １ 7 is a graph showing the H-NMR of the compound obtained in Synthesis Example (I-3). １ 8 is a graph showing the H-NMR of the compound obtained in Synthesis Example (I-4). １ 1 is a graph showing H-NMR. FIG. 9 is a graph showing the surface potential versus film thickness for Examples 1 to 8. FIG. 10 is a graph showing the surface potential versus film thickness for Comparative Examples 1 to 4. FIG. 11 is a graph showing the surface potential versus film thickness for Examples 9 and 10. FIG. 12 is a graph showing the surface potential versus film thickness for Examples 11 to 14. FIG. 13 is a top view of an evaluation vibration power generating element. FIG. 14 is a cross-sectional view taken along line VIII-VIII in FIG. 13. FIG. 15 is a graph showing the magnitude of the surface current of the substrate-attached polarized film of Example 15 versus time.

[0022] The contents of the present disclosure will be described in detail below. The following description of the components may be based on representative embodiments of the present disclosure, but the present disclosure is not limited to such embodiments. In the present disclosure, a combination of two or more preferred embodiments is a more preferred embodiment. In the present disclosure, a numerical range expressed using "to" means a range that includes the numerical values ​​written before and after "to" as the lower and upper limits. In the present disclosure, the term "step" includes not only an independent step, but also a step that cannot be clearly distinguished from other steps, as long as the purpose of the step is achieved. In the numerical ranges described in stages in the present disclosure, the upper or lower limit value described in one numerical range may be replaced with the upper or lower limit value of another numerical range described in stages. In the numerical ranges described in the present disclosure, the upper or lower limit value of the numerical range may be replaced with the value shown in the examples.

[0023] (1) Substrate-attached Polarizing Film The substrate-attached polarizing film of the present disclosure comprises a substrate and a polarizing film formed on at least one of the two main surfaces of the substrate. The polarizing film contains a compound represented by the following formula (I) (hereinafter also referred to as "compound (I)").

[0024]

[0025] In formula (I), Z is a divalent organic group that imparts a curved structure to the compound, and is a hydrocarbon group having 2 to 80 carbon atoms, a sulfonyl group (—SO ２ A represents an amine group (-NH-), an ether group (-O-), or a thioether group (-S-). Some or all of the carbon atoms constituting the hydrocarbon group may be substituted with heteroatoms. Some or all of the hydrogen atoms in the hydrocarbon group may be substituted with halogen atoms. A １ and A ２ each independently represents a single bond or a divalent linking group. １ and X ２ X each independently represents a monovalent aromatic hydrocarbon group having 6 to 80 carbon atoms or a hydrocarbon group having 2 to 80 carbon atoms. １ and X ２ In the formula (I), some or all of the hydrogen atoms of the aromatic hydrocarbon group and the hydrocarbon group are substituted with fluorine atoms. １ and X ２ The total number of fluorine atoms contained in each of the groups is greater than the number of halogen atoms contained in Z.

[0026] In the present disclosure, the term "polarized film" refers to a film that semi-permanently maintains polarization in the film thickness direction. In other words, the term "polarized film" refers to a film that has a surface potential. The term "surface potential" refers to the potential difference between the surface of the polarized film (i.e., the surface of the polarized film opposite the substrate) and the substrate (0 V). The surface potential is also called giant surface potential (GSP). The term "divalent organic group that imparts a curved structure to the compound" refers to a bond angle that is not 180°. The term "bond angle" refers to the difference between the A of Z in formula (I) and the GSP of Z in formula (I). １ an atom bonded to X (a sulfur atom when Z is a sulfonyl atom); １ A of １ and the carbon atom bonded to A in Z. ２ and the atom bonded to X ２ A of ２and a second line connecting the carbon atom to which it is bonded. A "divalent linking group" refers to -O-, -S-, -CO-, -N-, a divalent hydrocarbon group having 2 to 80 carbon atoms, or a combination thereof. Some or all of the carbon atoms constituting the divalent hydrocarbon group having 2 to 80 carbon atoms may be substituted with heteroatoms. An "aliphatic hydrocarbon group" refers to a hydrocarbon group that does not have an aromatic ring. An "aromatic hydrocarbon group" refers to a hydrocarbon group that has at least one aromatic ring. An "aromatic ring" refers to a cyclic conjugated compound having 4n+2 π electrons. The aromatic ring may be monocyclic (e.g., benzene, etc.) or polycyclic (e.g., naphthalene, anthracene, phenanthrene, etc.).

[0027] The substrate-attached polarizing film of the present disclosure has the above-mentioned configuration, and therefore the absolute value of the surface potential per unit film thickness is greater than that of conventional polarizing films. As a result, when forming a substrate-attached polarizing film having a constant surface potential, if the substrate-attached polarizing film of the present disclosure is used, the thickness of the polarizing film can be made thinner than when a conventional polarizing film is used. As a result, the substrate-attached polarizing film of the present disclosure can reduce the manufacturing cost of, for example, a vibration power generation element. This effect is presumably due to, but not limited to, the following reasons. The present inventors have fabricated a substrate-attached polarizing film by vacuum deposition using trifluoromethyl (CF ３ When a molecule having a CF group is deposited on a substrate, the CF group in the molecule ３ It has been experimentally found that the CF groups are oriented toward the surface of the film, and a polarized film that spontaneously generates polarization is easily formed. ３ The specific orientation of the groups is thought to be due to the small surface tension. For example, the reason why fluorine-treated frying pans and other surfaces exhibit water and oil repellency is due to the CF ３ This is thought to be because the CF groups (especially fluorine atoms) have the property of being less compatible with other substances (i.e., the property of having low surface tension). Similarly, at the interface between the vacuum and the film during the vacuum deposition process, ３ It is believed that the groups (especially fluorine atoms) tend to orient themselves toward the empty vacuum side (i.e., the surface side of the film). Due to this action, the trifluoromethyl (CF ３In the present disclosure, in formula (I), Z is a divalent organic group that imparts a curved structure to compound (I), and X １ and X ２ The total number of fluorine atoms contained in each of the above is greater than the number of halogen atoms contained in the above Z. In particular, when the polarized film is formed by vacuum deposition, the above-mentioned properties of fluorine atoms cause the polarized film to be polarized at the interface between the vacuum and the film. １ and X ２ Furthermore, the charge distribution in the molecule of compound (I) is such that X of compound (I) is more likely to be oriented on the surface side of the polarized film. １ and X ２ As a result, the degree of polarization of the entire polarized film is greater than in the past. As a result, it is presumed that the absolute value of the surface potential per unit film thickness of the substrate-attached polarized film of the present disclosure is greater than in the past.

[0028] The configuration of the substrate-attached polarizing film is appropriately selected depending on the application of the substrate-attached polarizing film, etc. The polarizing film may be formed directly on the two main surfaces of the substrate, or may be formed indirectly on the two main surfaces of the substrate. When the polarizing film is formed indirectly on the two main surfaces of the substrate, other layers described below may be interposed between the polarizing film and the substrate.

[0029] (1.1) Polarized Film The substrate-attached polarized film includes a polarized film. The polarized film contains compound (I). The polarized film may consist of compound (I) alone. The polarized film may be a film formed by vacuum deposition (i.e., a vacuum-deposited film).

[0030] The thickness of the polarizing film is appropriately selected depending on the application of the substrate-attached polarizing film, etc. The thickness of the polarizing film is preferably 100 nm or more, but may be 500 nm or more, or 1000 nm or more, in order to generate a sufficient surface potential. The film thickness may be 10,000 nm or less, 1000 nm or less, or 500 nm or less. The polarizing film thickness may be 1 nm to 100 nm, 5 nm to 100 nm, 20 nm to 100 nm, or 50 nm to 100 nm. The method for measuring the polarizing film thickness is the same as the method described in the examples.

[0031] The polarized film exhibits a positive or negative surface potential on its surface due to the structure and polarization of the compound represented by (I). It is preferable that the surface potential of the polarized film varies depending on the thickness of the polarized film.

[0032] The absolute value of the surface potential of the polarized film is not particularly limited, and may be 100 V to 1000 V, 1000 V to 10,000 V, or 10,000 V to 100,000 V. An example of a method for adjusting the absolute value of the surface potential of the polarized film to fall within the above-mentioned range is a method in which compound (I) is vacuum-deposited to form a polarized film. The method for measuring the surface potential of the polarized film is the same as the method described in the Examples.

[0033] The absolute value of the surface potential per unit thickness of the polarizing film is preferably 180 mV / nm to 1200 mV / nm. The absolute value of the surface potential per unit thickness of the polarizing film of 180 mV / nm to 1200 mV / nm indicates that the absolute value of the surface potential per unit thickness of the polarizing film is higher than conventional ones. As a result, the substrate-attached polarizing film of the present disclosure can further increase the output of the vibration power generating element. From the viewpoints of the performance and manufacturing cost of the vibration power generating element, the absolute value of the surface potential per unit thickness of the polarizing film is preferably 180 mV / nm to 1200 mV / nm, more preferably 300 mV / nm to 1200 mV / nm, and even more preferably 500 mV / nm to 1200 mV / nm. The absolute value of the surface potential per unit thickness of the polarizing film may be 140 mV / mm to 1200 mV / nm, or may be 200 mV / mm to 1200 mV / nm. The absolute value of the surface potential per unit thickness of the polarized film can be adjusted to fall within the above-mentioned range by forming the polarized film by vacuum deposition of compound (I). The method for measuring the surface potential per unit thickness of the polarized film is the same as that described in the Examples.

[0034] (1.1.1) Compound (I) Compound (I) is represented by the following formula (I): The polarizable film may contain one type of compound (I), or two or more types of compound (I).

[0035]

[0036] In formula (I), Z is a divalent organic group that imparts a curved structure to the compound, and represents a hydrocarbon group having 2 to 80 carbon atoms, a sulfonyl group, an amine group, an ether group, or a thioether group. Some or all of the carbon atoms constituting the hydrocarbon group may be substituted with heteroatoms. Some or all of the hydrogen atoms in the hydrocarbon group may be substituted with halogen atoms.

[0037] The "hydrocarbon group having 2 to 80 carbon atoms" represented by Z may be linear, branched, or cyclic. The "hydrocarbon group having 2 to 80 carbon atoms" represented by Z may be a saturated hydrocarbon group or an unsaturated hydrocarbon group. The number of carbon atoms in the "hydrocarbon group having 2 to 80 carbon atoms" represented by Z may be 2 to 10, 11 to 40, or 41 to 80. Examples of heteroatoms with which "some or all of the carbon atoms constituting the hydrocarbon group" represented by Z may be substituted include oxygen atoms, nitrogen atoms, sulfur atoms, phosphorus atoms, and boron atoms. Examples of halogen atoms with which "some or all of the hydrogen atoms of the hydrocarbon group" represented by Z may be substituted include fluorine, chlorine, bromine, and iodine. The number of halogen atoms with which "some or all of the hydrogen atoms of the hydrocarbon group" represented by Z may be substituted is determined by the formula X. １ and X ２ The number of carbon atoms contained in each of the groups may be less than the number of fluorine atoms contained in each of the groups, and may be 1 or more, or may be 0. Examples of the "hydrocarbon group having 2 to 80 carbon atoms" represented by Z include groups represented by the following formulas (z-1) to (z-7), and hydrocarbon groups containing fullerene.

[0038]

[0039] In formula (I), A １ and A ２ each independently represents a single bond or a divalent linking group.

[0040] A １ and A ２ The "divalent linking group" represented by the formula (I) represents -O-, -S-, -CO-, -N-, a divalent hydrocarbon group having 1 to 80 carbon atoms, or a combination thereof. １ and A ２ The "divalent hydrocarbon group having 1 to 80 carbon atoms" represented by the formula (I) may be linear, branched, or cyclic. １ and A ２ The "divalent hydrocarbon group having 1 to 80 carbon atoms" represented by the formula (I) may be a saturated hydrocarbon group or an unsaturated hydrocarbon group. １ and A ２The number of carbon atoms in the "divalent hydrocarbon group having 1 to 80 carbon atoms" represented by the formula (I) may be 1 to 10, 11 to 40, or 41 to 80. １ and A ２ Examples of heteroatoms with which "a part or all of the carbon atoms constituting the hydrocarbon group" may be substituted include oxygen atoms, nitrogen atoms, sulfur atoms, phosphorus atoms, and boron atoms. １ and A ２ Some or all of the carbon atoms constituting the "divalent hydrocarbon group having 1 to 80 carbon atoms" represented by the formula (I) may be substituted with a heteroatom (e.g., nitrogen, oxygen, sulfur, or a halogen (e.g., fluorine, chlorine, bromine, or iodine)). １ and A ２ Examples of the "divalent hydrocarbon group having 1 to 80 carbon atoms" represented by the formula (a-1) include groups represented by the following formulas (a-1) to (a-3).

[0041]

[0042] In formula (I), X １ and X ２ X each independently represents a monovalent aromatic hydrocarbon group having 6 to 80 carbon atoms or a hydrocarbon group having 2 to 80 carbon atoms. １ and X ２ In the formula (I), some or all of the hydrogen atoms of the aromatic hydrocarbon group and the hydrocarbon group are substituted with fluorine atoms. １ and X ２ The total number of fluorine atoms contained in each of the groups is greater than the number of halogen atoms contained in Z.

[0043] X １ and X ２ The "monovalent aromatic hydrocarbon group having 6 to 80 carbon atoms" represented by the formula (1) may be linear, branched, or cyclic. １ and X ２ The "monovalent aromatic hydrocarbon group having 6 to 80 carbon atoms" represented by the formula (I) may be a saturated hydrocarbon group or an unsaturated hydrocarbon group. １ and X ２The number of carbon atoms in the "monovalent aromatic hydrocarbon group having 6 to 80 carbon atoms" represented by the formula (I) may be 6 to 20, 21 to 50, or 51 to 80. X １ and X ２ The "hydrocarbon group having 2 to 80 carbon atoms" represented by the formula (1) may be linear, branched, or cyclic. １ and X ２ The "hydrocarbon group having 2 to 80 carbon atoms" represented by the formula (I) may be a saturated hydrocarbon group or an unsaturated hydrocarbon group. １ and X ２ The number of carbon atoms in the "hydrocarbon group having 2 to 80 carbon atoms" represented by the formula X may be 2 to 10, 11 to 40, or 41 to 80. １ and X ２ Examples of heteroatoms that may substitute "carbon atoms constituting the aromatic hydrocarbon group or a part or all of the carbon atoms constituting the hydrocarbon group" include oxygen atoms, nitrogen atoms, sulfur atoms, phosphorus atoms, and boron atoms. １ and X ２ The total number of fluorine atoms contained in each of X may be greater than the number of halogen atoms contained in Z, and may be 1 to 10, or 11 to 30. １ and X ２ The difference between the total number of fluorine atoms contained in each of X and the number of halogen atoms contained in Z is preferably as large as possible, and may be 1 to 10 or 11 to 30. １ and X ２ Examples of the "monovalent aromatic hydrocarbon group having 6 to 80 carbon atoms or hydrocarbon group having 2 to 80 carbon atoms" represented by the formula (x-1) to (x-10) below can be mentioned.

[0044]

[0045] The molecular weight of compound (I) is not particularly limited, but from the viewpoint of further increasing the absolute value of the surface potential of the polarizable film, it is preferably 400 to 2000, more preferably 600 to 1500, even more preferably 700 to 1300, and particularly preferably 800 to 1200.

[0046] (1.1.1.1) Preferred embodiment of compound (I): The divalent organic group is one selected from the group consisting of groups represented by the following formulas (z-1) to (z-7), and X １ and X ２ is preferably one selected from the group consisting of groups represented by the following formulas (x-1) to (x-10). １ and X ２ The absolute value of the magnitude of the permanent dipole moment of compound (I) is larger than that of a compound not having the above group. As a result, the absolute value of the surface potential per unit film thickness of the polarized film with the substrate is larger than that of the compound (I).

[0047]

[0048] In formulas (z-1) to (z-7) and formulas (x-1) to (x-10), * indicates a bonding position.

[0049] Hereinafter, the divalent organic group is one selected from the group consisting of groups represented by formulas (z-1) to (z-7), and X １ and X ２ is one selected from the group consisting of groups represented by formulas (x-1) to (x-10), is also referred to as "compound (IA)".

[0050] In compound (IA), X １ and X ２ is preferably a group represented by the formula (x-1), (x-2) or (x-3), and the divalent organic group is preferably a group represented by the formula (z-1), (z-2) or (z-3). １ and X ２ The absolute value of the magnitude of the permanent dipole moment of compound (I) tends to be larger than that of compounds not having the above group. As a result, the absolute value of the surface potential per unit film thickness of the polarized film with the substrate tends to be larger than that of the polarized film with the substrate.

[0051] In compound (IA), the divalent organic group is preferably one selected from the group consisting of groups represented by formula (z-1) and formulas (z-3) to (z-7). In other words, the divalent organic group preferably does not contain a halogen atom. This results in a larger absolute value of the magnitude of the permanent dipole moment of compound (I) than a compound having the same configuration as compound (I) except that the divalent organic group contains a halogen atom. As a result, the absolute value of the surface potential per unit film thickness of the substrate-attached polarized film is larger than.

[0052] A １ and A ２ each independently represents the divalent linking group, and the divalent linking group is preferably an aromatic hydrocarbon group having 6 to 80 carbon atoms. Some or all of the carbon atoms constituting the divalent linking group may be substituted with heteroatoms. That is, A １ and A ２ Preferably, A contains an aromatic ring. １ and A ２ The steric hindrance of compound (I) is greater than when the polarized film is composed only of single bonds (alkyl groups). In other words, the rigidity of compound (I) is superior. Therefore, when a polarized film is formed by vacuum deposition, compound (I) is more likely to align regularly on the substrate. The glass transition temperature indicates the temperature at which the physical properties (e.g., viscosity or fluidity) of the object being measured change drastically when the temperature is continuously changed. Therefore, the glass transition temperature of the polarized film is higher. Depending on its application, the polarized film with substrate may be exposed to a high-temperature atmosphere after fabrication. If the temperature of the high-temperature atmosphere exceeds the glass transition temperature of the polarized film with substrate, the molecular arrangement of compound (I) in the polarized film may be disrupted, and the absolute value of the surface potential of the polarized film may decrease. A higher glass transition temperature of the polarized film increases the lower limit of the temperature at which the surface potential of the polarized film decreases. In other words, the surface potential of the polarized film can be maintained even at relatively high environmental temperatures. As a result, the polarized film with substrate can be applied to a wide range of processing processes. Therefore, the applications of the polarized film with substrate are broadened.

[0053] Below, A １ and A ２each independently represent the divalent linking group, and compound (I) in which the divalent linking group is an aromatic hydrocarbon group having 6 to 80 carbon atoms is also referred to as "compound (IB)".

[0054] In the compound (IB), the divalent linking groups are preferably each independently represented by the following formula (a-1), formula (a-2), or formula (a-3). １ and A ２ The glass transition temperature of the polarized film tends to be higher than when the group represented by formula (a-1), formula (a-2), or formula (a-3) is not present. As a result, the polarized film with a substrate can be applied to a wider range of processing processes. Therefore, the applications of the polarized film with a substrate are broader.

[0055]

[0056] In formulas (a-1), (a-2) and (a-3), * indicates a bonding position.

[0057] (1.1.1.2) Specific Examples of Compound (I) Compound (I) may include at least one of compound (I-1) represented by formula (I-1) below, compound (I-2) represented by formula (I-2) below, compound (I-3) represented by formula (I-3) below, compound (I-4) represented by formula (I-4) below, and compound (I-5) represented by formula (I-5) below, or may be at least one of compound (I-1), compound (I-2), compound (I-3), compound (I-4), and compound (I-5).

[0058]

[0059] (1.1.1.3) Physical Properties of Compound (I) Compound (I) preferably has a permanent dipole moment of 4.0 to 25.0 Debye in absolute value. Compound (I) having a permanent dipole moment of 4.0 to 25.0 Debye in absolute value indicates that the absolute value of the permanent dipole moment of the compound is high. As a result, the absolute value of the surface potential per unit film thickness of the substrate-attached polarized film is larger than when the compound has a permanent dipole moment of less than 4.0 Debye in absolute value. From the viewpoint of forming a polarized film with a large surface potential, the absolute value of the permanent dipole moment of compound (I) may be 4.0 to 7.0 Debye, 7.0 to 14.0 Debye, or 14.0 to 25.0 Debye. The absolute value of the permanent dipole moment was calculated in the same manner as described in the Examples. When compound (I) has conformational isomers, the magnitude of the permanent dipole moment differs between the isomers, and therefore the permanent dipole moment of the structure with the highest probability of existence was taken as the permanent dipole moment of compound (I).

[0060] The direction of the permanent dipole moment of compound (I) is usually from the site where the negative charge is biased to the site where the positive charge is biased in the charge distribution within the molecule of compound (I). For example, the direction of the permanent dipole moment of compound (I-1) is shown in Figure 1. The direction of the arrow in Figure 1 indicates the direction of the permanent dipole moment of compound (I-1). Therefore, the polarity of the surface potential of a polarized film using compound (I-1) tends to be negative. The directions of the permanent dipole moments of compound (I-2), compound (I-4), and compound (I-5) tend to be the same as the direction of the permanent dipole moment of compound (I-1). Due to the strong electron-withdrawing properties of the sulfonyl group, the direction of the permanent dipole moment of compound (I-3) tends to be opposite to the direction of the permanent dipole moment of compound (I-1).

[0061] (1.1.2) Other Components The polarizing film may further contain other components different from compound (I), or may not contain other components, depending on the intended use of the substrate-attached polarizing film, etc.

[0062] Examples of other components include a host material. The "host material" satisfies the following requirements: it is a matrix material that maintains compound (I) in a constant orientation in the polarizable film, it is solid at room temperature, and it is an organic material composed of molecules with a permanent dipole moment of 1 Debye or less. Specific examples of the host material include CBP (4,4-N,N'-Dicarbazole-1,1'-biphenyl), SF3-TRZ (2-(9,9'-spirobi[fluoren]-3-yl)-4,6-diphenyl-1,3,5-triazine), and TCTA (4,4',4"-Tris(carbazol-9-yl)triphenylamine).

[0063] When the polarizing film contains a host material, the content of compound (I) is not particularly limited and is preferably 10% by mass to 99% by mass, more preferably 50% by mass to 99% by mass, and even more preferably 70% by mass to 95% by mass, relative to the total amount of the polarizing film.

[0064] (1.2) Substrate The substrate-attached polarizing film includes a substrate. The substrate holds the polarizing film. The material of the substrate is appropriately selected depending on the intended use of the substrate-attached polarizing film, and examples thereof include glass, silicon, resin, and metal. The size of the substrate is appropriately selected depending on the intended use of the substrate-attached polarizing film.

[0065] (1.3) Other Layers The substrate-attached polarizing film may or may not include other layers. The other layers may be interposed between the polarizing film and the substrate, or may be formed directly on the regions of the two main surfaces of the substrate where the polarizing film is not formed. The other layers are appropriately selected depending on the application of the substrate-attached polarizing film, and examples thereof include conductive layers (e.g., electrode layers).

[0066] (1.4) Applications Examples of applications of the substrate-attached polarized film include power sources (vibration power sources) for wireless communications (e.g., Bluetooth, etc.), organic electroluminescence (organic EL) displays, and the like.

[0067] (2) Vibration Power Generation Element The vibration power generation element of the present disclosure includes the substrate-attached polarizing film of the present disclosure.

[0068] Since the vibration power generating element of the present disclosure has the above-described configuration, the output of the vibration power generating element is higher than conventional ones.

[0069] A vibration power generating element converts vibration energy into electrical power. A vibration power generating element typically includes a substrate-attached polarized film according to the present disclosure and an electrode (hereinafter also referred to as a "counter electrode") that faces the polarized film across an air gap. The configuration of the vibration power generating element may be the same as that of a known vibration power generating element, except that it includes a substrate-attached polarized film according to the present disclosure. The polarity of the substrate-attached polarized film according to the present disclosure may be negative or positive.

[0070] The vibration power generation element is preferably used as a vibration power generator or a vibration sensor. In a vibration power generator, by vibrating at least one of the substrate-attached polarized film and the counter electrode of the present disclosure, electric charges are induced in the counter electrode, and the induced electric charges are output as a current. In a vibration sensor, when the detection target vibrates, at least one of the substrate-attached polarized film and the counter electrode of the present disclosure vibrates in conjunction with the vibration, and the vibration of the detection target is detected using the current due to the electric charges induced in the counter electrode by the vibration as a detection signal.

[0071] (2.1) First to Third Embodiments The vibration power generating elements of the first to third embodiments will be described with reference to Figures 2 to 4. In the figures, the same or corresponding parts are designated by the same reference characters, and description thereof will not be repeated.

[0072] (2.1.1) First Embodiment As shown in FIG. 2, a vibration power generating element 1A according to a first embodiment includes a substrate-attached polarizing film 10, an electrode substrate 20A, and a load resistor 30.

[0073] The substrate-attached polarizing film 10 includes a polarizing film 11, a substrate 12, and an electrode 13. The polarizing film 11 is formed on a main surface S12 of the substrate 12. The electrode 13 is interposed between the polarizing film 11 and the substrate 12. The substrate-attached polarizing film 10 is similar to the examples of substrate-attached polarizing films of the present disclosure.

[0074] The electrode substrate 20A has a counter electrode 21 and a substrate 22. The counter electrode 21 is formed on a main surface S22 of the substrate 22. The counter electrode 21 faces the polarizing film 11 of the substrate-attached polarizing film 10. The electrode substrate 20A is supported so that the polarizing film 11 and the counter electrode 21 are spaced apart. The electrode substrate 20A is configured to vibrate in the thickness direction of the electrode substrate 20A due to external stress. For example, the substrate 22 may be a substrate with relatively low rigidity (e.g., a substrate made of polyethylene terephthalate). The counter electrode 21 and the substrate 22 may be any known materials.

[0075] The load resistor 30 is electrically connected to the electrode 13 and the counter electrode 21. The load resistor 30 may be a known resistor.

[0076] In the vibration power generating element 1A, when the electrode substrate 20A vibrates in its thickness direction V, the counter electrode 21 is displaced relative to the polarizing film 11. As a result, the charge induced in the counter electrode 21 is output as a current.

[0077] In the first embodiment, the electrode substrate 20A is configured to vibrate due to an external stress. However, the present disclosure is not limited to this, and the substrate-attached polarizing film 10 may be configured to vibrate due to an external stress, or each of the substrate-attached polarizing film 10 and the electrode substrate 20A may be configured to vibrate due to an external stress.

[0078] (2.1.2) Second Embodiment The vibration power generating element 1B of the second embodiment is similar to the vibration power generating element 1A of the first embodiment, except that it includes a spacer 40. The vibration power generating element 1B includes a substrate-attached polarizing film 10, an electrode substrate 20A, a load resistor 30, and the spacer 40.

[0079] The spacer 40 separates the substrate-attached polarizing film 10 from the electrode substrate 20A. The spacer 40 supports the electrode substrate 20A so that the electrode substrate 20A vibrates in the thickness direction V of the electrode substrate 20A due to external stress. The spacer 40 is made of an electrically insulating material (e.g., resin, etc.).

[0080] In the second embodiment, the electrode substrate 20A is configured to vibrate due to an external stress. However, the present disclosure is not limited to this, and the substrate-attached polarizing film 10 may be configured to vibrate due to an external stress, or each of the substrate-attached polarizing film 10 and the electrode substrate 20A may be configured to vibrate due to an external stress.

[0081] (2.1.3) Third Embodiment A vibration power generating element 1C of the third embodiment is similar to the vibration power generating element 1A of the first embodiment, except that the electrode substrate further includes a polarizing film. The vibration power generating element 1C includes a substrate-attached polarizing film 10, an electrode substrate 20B, and a load resistor 30.

[0082] The electrode substrate 20B has a counter electrode 21, a substrate 22, and a polarizing film 23. The polarizing film 23, the counter electrode 21, and the substrate 22 are stacked in this order. The counter electrode 21 faces the polarizing film 11 of the substrate-attached polarizing film 10 via the polarizing film 23. The electrode substrate 20B is supported so that the polarizing film 11 and the polarizing film 23 are spaced apart. The electrode substrate 20B is configured to vibrate in the thickness direction V of the electrode substrate 20B due to external stress. The polarizing film 23 has a surface potential polarity opposite to that of the polarizing film 11 of the substrate-attached polarizing film 10. The electrode substrate 20B is similar to the example of the substrate-attached polarizing film of the present disclosure.

[0083] In the vibration power generating element 1C, when the electrode substrate 20B vibrates in its thickness direction V, the counter electrode 21 is displaced relative to the polarizing film 11, and the polarizing film 23 is displaced relative to the electrode 13. As a result, the charge induced in the counter electrode 21 is output as a first current, and the charge induced in the electrode 13 is output as a second current. Therefore, the vibration power generating element 1C can generate more power than the vibration power generating element 1A.

[0084] In the third embodiment, the electrode substrate 20B is configured to vibrate due to an external stress. However, the present disclosure is not limited to this, and the substrate-attached polarizing film 10 may be configured to vibrate due to an external stress, or each of the substrate-attached polarizing film 10 and the electrode substrate 20B may be configured to vibrate due to an external stress.

[0085] (3) Organic Light-Emitting Element The organic light-emitting element of the present disclosure includes a polarizing film (hereinafter also referred to as the "separating film of the present disclosure") separated from the substrate-attached polarizing film of the present disclosure.

[0086] The organic light-emitting element of the present disclosure has the above-described configuration, and by inserting a polarizing film into the stacked interface, it is possible to reduce the charge injection barrier due to energy level mismatch at the interface between the electrode and the charge transport layer, the interface between the charge transport layer and the exciton blocking layer, or the interface between the charge transport layer and the light-emitting layer, and to reduce the driving voltage of the organic light-emitting element.

[0087] The organic light-emitting element emits light when an electric field is applied. The configuration of the organic light-emitting element may be the same as that of a known organic light-emitting element, except that it includes the polarizing film of the present disclosure.

[0088] The organic light-emitting device is preferably used as an organic photoluminescence device (ie, an organic PL device) or an organic electroluminescence device (ie, an organic EL device).

[0089] The organic electroluminescent device has an anode, a cathode, and an organic layer formed between the anode and the cathode, the organic layer including a light-emitting layer and the polarizing film of the present disclosure.

[0090] The organic layer may consist of an emitting layer and the polarizing film of the present disclosure, or may further include another organic layer different from the emitting layer and the polarizing film of the present disclosure. Examples of other organic layers include a hole transport layer, a hole injection layer, an electron blocking layer, a hole blocking layer, an electron injection layer, an electron transport layer, or an exciton blocking layer. The hole transport layer may be a hole injection transport layer having a hole injection function. The electron transport layer may be an electron injection transport layer having an electron injection function. Materials for these organic layers can be selected from known materials.

[0091] The film of the present disclosure may be disposed at any position in the organic light-emitting element. When the polarity of the surface potential of the separation film of the present disclosure is negative, the separation film of the present disclosure is preferably disposed between the anode and the light-emitting layer, and more preferably disposed in contact with the anode or between the hole injection layer and the light-emitting layer so as to be in contact with the hole injection layer. This allows the separation film of the present disclosure to promote hole injection from the anode to the organic layer.

[0092] A laminate (hereinafter simply referred to as "laminate") of a polarizable film of the present disclosure having a negative surface potential and a polarizable film of the present disclosure having a positive surface potential may be provided between the light-emitting layer and the cathode, with the film having the positive surface potential facing the cathode. The laminate is preferably provided so that the film having the positive surface potential is in contact with the cathode or in contact with the electron injection layer between the electron injection layer and the light-emitting layer. This allows the laminate to promote electron injection from the cathode to the organic layer.

[0093] (4) Manufacturing Method of Substrate-Attached Polarized Film The manufacturing method of the substrate-attached polarized film of the present disclosure is a method for manufacturing the substrate-attached polarized film of the present disclosure. This manufacturing method includes preparing a raw material containing the compound (hereinafter also referred to as the "preparation step"), and forming the polarized film on at least one of the two main surfaces of the substrate using the raw material by vacuum deposition or wet processing (hereinafter also referred to as the "formation step"). The preparation step and the formation step are performed in this order.

[0094] The manufacturing method of the present disclosure has the above-described configuration, and therefore the substrate-attached polarized film of the present disclosure can be obtained.

[0095] (4.1) Preparation Step In the preparation step, a raw material containing compound (I) is prepared. The raw material is appropriately selected depending on the composition of the polarized film, the method for forming the polarized film, etc. The raw material may consist of compound (I) alone, or may contain the other components described above, or may contain a known solvent. The method for preparing the raw material is not particularly limited and is appropriately selected depending on the composition of the polarized film, the method for forming the polarized film, etc. Compound (I) may be a compound obtained by synthesis.

[0096] (4.2) Formation Step In the formation step, the polarized film is formed on at least one of the two main surfaces of the substrate using the raw material by vacuum deposition or wet processing. Examples of wet processing include spin coating and dip coating. Among these, vacuum deposition is preferred as the method for forming the polarized film. When the polarized film is formed by vacuum deposition, it is easier to obtain a polarized film in which multiple compounds (I) are arranged so that the permanent dipole moments of the compounds (I) are oriented in the same direction than when formed by wet processing. In other words, it is easier to obtain a polarized film with a larger absolute value of the surface potential per unit film thickness.

[0097] The present disclosure will be described in more detail below based on examples, but the present disclosure is not limited to these examples. The materials, amounts used, ratios, processing procedures, etc. shown in the following examples can be changed as appropriate without departing from the spirit of the present disclosure.

[0098] [1] Measurement Methods Physical properties in the examples were measured by the following methods.

[0099] [1.1] Permanent dipole moment of compound The ground state of the compound molecule was optimized using the electronic structure program "Gaussian 16." A density functional theory (DFT) model at the B3LYP 6-31G(d) calculation level was used. The calculation result of the permanent dipole moment of the molecule of the compound whose ground state was optimized was used as the "permanent dipole moment of the compound."

[0100] [1.2] Thickness of Polarizing Film The thickness of the organic thin film formed by vacuum deposition was measured using an optical non-contact film thickness measuring device (ThetaMetrisis: FR-ES).

[0101] [1.3] Surface Potential of Polarized Film Using an ultra-high vacuum Kelvin probe system (KP Technology: UHVKP020), the surface potential of the film with the substrate was measured in a dark place under vacuum by the Kelvin probe method, with the ITO (indium tin oxide) potential as the origin.

[0102] [1.4] Absolute value of surface potential per unit film thickness The absolute value of the surface potential per unit film thickness was calculated from the measurement results of the thickness of the polarized film and the surface potential of the polarized film. The allowable range of the absolute value of the surface potential per unit film thickness is 140 mV / nm or more.

[0103] [1.5] Glass transition temperature The glass transition temperature of the powder of the compound used as the raw material for the polarized film (hereinafter also referred to as "raw material powder") was measured using a differential scanning calorimeter (DSC7000X manufactured by Hitachi High-Tech Corporation). The glass transition temperature of the raw material powder was taken as the "glass transition temperature of the polarized film." This is because the glass transition temperature of the raw material powder and the glass transition temperature of the polarized film having a nanoscale thickness can be considered to be equivalent.

[0104] [2] Synthesis of Compounds Compounds (I-1), (I-2) and (I-3) were synthesized as follows.

[0105] [2.1] Synthesis Example (I-1) 4,4'-(hexafluoroisopropylidene)diphthalic anhydride, 4-amino-3',5'-bis(trifluoromethyl)biphenyl, 1,3-dimethyl-2-imidazolidinone, and thoroughly dried molecular sieves (3A) were placed in a recovery flask, and the mixture was stirred for 9 hours using a magnetic stirrer while heating to 150°C in an oil bath. After heating was stopped, distilled water was added to the reaction solution, and the resulting precipitate was filtered, collected, and dried. The precipitate was purified by column chromatography using chloroform as a developing solvent to obtain a solid. The resulting solid was １ H-NMR (solvent: CDCl ３ ) The measurement results are shown in Figure 5. From the measurement results, the obtained solid was identified as the following compound (I-1). The permanent dipole moment of compound (I-1) was 5.40 Debye.

[0106]

[0107] [2.2] Synthesis Example (I-2) 9,9-bis(3,4-dicarboxyphenyl)fluorene dianhydride, 4-amino-3',5'-bis(trifluoromethyl)biphenyl, 1,3-dimethyl-2-imidazolidinone, and thoroughly dried molecular sieves (3A) were placed in a recovery flask, and the mixture was stirred for 9 hours using a magnetic stirrer while heating to 150°C in an oil bath. After heating was stopped, distilled water was added to the reaction solution, and the resulting precipitate was filtered, collected, and dried. The precipitate was purified by column chromatography using chloroform as a developing solvent to obtain a solid. The resulting solid was １ H-NMR (solvent: CDCl ３ ) The measurement results are shown in Figure 6. From the measurement results, the obtained solid was identified as the following compound (I-2). The permanent dipole moment of compound (I-2) was 7.98 Debye.

[0108]

[0109] [2.3] Synthesis Example (I-3) Bis(4-aminophenyl)sulfone, tetrafluorophthalic anhydride, benzoic acid, 1,3-dimethyl-2-imidazolidinone, and thoroughly dried molecular sieves (4A) were added to a recovery flask, and the mixture was stirred for 15 hours using a magnetic stirrer while being heated to 150°C in an oil bath. After heating was stopped, distilled water was added to the reaction solution, and the resulting precipitate was filtered, collected, and then dried. The mixture was purified by column chromatography using chloroform and ethyl acetate as the developing solvent to obtain a solid. The resulting solid was １ H-NMR (solvent: CDCl ３ ) The measurement results are shown in Figure 7. From the measurement results, the obtained solid was identified as the following compound (I-3). The permanent dipole moment of compound (I-3) was 5.98 Debye.

[0110]

[0111] [2.4] Synthesis Example (I-4) 9,9-bis(3,4-dicarboxyphenyl)fluorene dianhydride, 1H,1H-heptafluorobutylamine, benzoic acid, 1,3-dimethyl-2-imidazolidinone, and thoroughly dried molecular sieves (4A) were added to a recovery flask and stirred for 5 hours using a magnetic stirrer at room temperature. The mixture was then heated to 90°C in an oil bath and stirred for 20 hours. After heating was stopped, distilled water was added to the reaction solution, and the resulting precipitate was filtered, collected, and dried. Purification was performed by column chromatography using chloroform as a developing solvent to obtain a solid. The resulting solid was analyzed by 1H-NMR (solvent: CDC ｌ３ ) The measurement results are shown in Figure 8. From the measurement results, the obtained solid was identified as the following compound (I-4). The permanent dipole moment of compound (I-4) was 6.95 Debye.

[0112]

[0113] [3] Examples and Comparative Examples [3.1] Example 1 A glass substrate on which a 100 nm thick layer of indium tin oxide (ITO) (hereinafter also referred to as "electrode") was formed was prepared. On this electrode, a thin film was deposited by vacuum deposition at a vacuum level of 1×10 －４ Compound (I-1) was vapor-deposited under conditions of 0.1 Pa or less to form a polarized film. This resulted in a polarized film with a substrate. The thickness of the polarized film was 69 nm. The surface potential of the obtained polarized film with a substrate was measured. The measured values ​​are shown in FIG. 9. The glass transition temperature of the polarized film was 125.1°C. The glass transition temperatures of the polarized films of Examples 2 to 4 were also the same as the glass transition temperature of the polarized film of Example 1.

[0114] [3.2] Example 2 A polarized film with a substrate was obtained in the same manner as in Example 1, except that the thickness of the polarized film was changed to 34 nm. The surface potential of the polarized film with the substrate obtained was measured. The measurement results are shown in FIG.

[0115] [3.3] Example 3 A polarized film with a substrate was obtained in the same manner as in Example 1, except that the thickness of the polarized film was changed to 7 nm. The surface potential of the polarized film with the substrate obtained was measured. The measurement results are shown in FIG.

[0116] [3.4] Example 4 A polarized film with a substrate was obtained in the same manner as in Example 1, except that the thickness of the polarized film was changed to 3 nm. The surface potential of the polarized film with the substrate obtained was measured. The measurement results are shown in Figure 9.

[0117] [3.5] Example 5 A polarized film with a substrate was obtained in the same manner as in Example 1, except that compound (I-1) was changed to compound (I-2) and the thickness of the polarized film was changed to 69 nm. The surface potential of the obtained polarized film with a substrate was measured. The measured value is shown in Figure 9. The glass transition temperature of the polarized film was 166.3°C. The glass transition temperatures of the polarized films of Examples 6 to 8 were also the same as the glass transition temperature of the polarized film of Example 5.

[0118] [3.6] Example 6 A polarized film with a substrate was obtained in the same manner as in Example 1, except that compound (I-1) was changed to compound (I-2) and the thickness of the polarized film was changed to 34 nm. The surface potential of the polarized film with the substrate obtained was measured. The measured values ​​are shown in FIG.

[0119] [3.7] Example 7 A polarized film with a substrate was obtained in the same manner as in Example 1, except that compound (I-1) was changed to compound (I-2) and the thickness of the polarized film was changed to 7 nm. The surface potential of the polarized film with the substrate obtained was measured. The measured values ​​are shown in FIG.

[0120] [3.8] Example 8 A polarized film with a substrate was obtained in the same manner as in Example 1, except that compound (I-1) was changed to compound (I-2) and the thickness of the polarized film was changed to 3 nm. The surface potential of the polarized film with the substrate obtained was measured. The measured values ​​are shown in FIG.

[0121] [3.9] Comparative Example 1 A polarized film with a substrate was obtained in the same manner as in Example 1, except that compound (I-1) was changed to a known compound (X-1) represented by the following formula (X-1) and the thickness of the polarized film was changed to 83 nm. The surface potential of the polarized film with the substrate obtained was measured. The measured values ​​are shown in FIG.

[0122]

[0123] [3.10] Comparative Example 2 A polarized film with a substrate was obtained in the same manner as in Example 1, except that compound (I-1) was changed to the known compound (X-1) represented by the above formula (X-1) and the thickness of the polarized film was changed to 42 nm. The surface potential of the polarized film with the substrate obtained was measured. The measured values ​​are shown in FIG.

[0124] [3.11] Comparative Example 3 A polarized film with a substrate was obtained in the same manner as in Example 1, except that compound (I-1) was changed to a known compound (X-1) represented by the following formula (X-1) and the thickness of the polarized film was changed to 8 nm. The surface potential of the polarized film with the substrate obtained was measured. The measured values ​​are shown in FIG.

[0125] [3.12] Comparative Example 4 A polarized film with a substrate was obtained in the same manner as in Example 1, except that compound (I-1) was changed to a known compound (X-1) represented by the following formula (X-1) and the thickness of the polarized film was changed to 4 nm. The surface potential of the polarized film with the substrate obtained was measured. The measured values ​​are shown in FIG.

[0126] [3.13] Example 9 A polarized film with a substrate was obtained in the same manner as in Example 1, except that compound (I-1) was changed to compound (I-3) and the thickness of the polarized film was changed to 27 nm. The surface potential of the polarized film with the substrate obtained was measured. The measured values ​​are shown in FIG.

[0127] [3.14] Example 10 A polarized film with a substrate was obtained in the same manner as in Example 1, except that compound (I-1) was changed to compound (I-3) and the thickness of the polarized film was changed to 64 nm. The surface potential of the polarized film with the substrate obtained was measured. The measured values ​​are shown in FIG.

[0128] [3.15] Example 11 A polarized film with a substrate was obtained in the same manner as in Example 1, except that compound (I-1) was changed to compound (I-4) and the thickness of the polarized film was changed to 29 nm. The surface potential of the polarized film with the substrate obtained was measured. The measured values ​​are shown in FIG.

[0129] [3.16] Example 12 A polarized film with a substrate was obtained in the same manner as in Example 1, except that compound (I-1) was changed to compound (I-4) and the thickness of the polarized film was changed to 58 nm. The surface potential of the polarized film with the substrate obtained was measured. The measured values ​​are shown in FIG.

[0130] [3.17] Example 13 A polarized film with a substrate was obtained in the same manner as in Example 1, except that compound (I-1) was changed to compound (I-4) and the thickness of the polarized film was changed to 86 nm. The surface potential of the polarized film with the substrate obtained was measured. The measured values ​​are shown in FIG.

[0131] [3.18] Example 14 A polarized film with a substrate was obtained in the same manner as in Example 1, except that compound (I-1) was changed to compound (I-4) and the thickness of the polarized film was changed to 115 nm. The surface potential of the polarized film with the substrate obtained was measured. The measured values ​​are shown in FIG.

[0132] [3.15] Example 15 A polarized film with a substrate was obtained in the same manner as in Example 1, except that compound (I-1) was changed to compound (I-2) and the thickness of the polarized film was changed to 0.35 μm.

[0133] Using the obtained substrate-attached polarizing film, a vibration power generating element 100 for evaluation shown in FIGS. 13 and 14 was fabricated, and its performance as a vibration power generating element was evaluated.

[0134] [3.15.1] Evaluation Vibration Power Generating Element As shown in FIG. 13, the evaluation vibration power generating element 100 includes a substrate-attached polarizing film 110, an electrode substrate 120, a spacer 140, an amplifier 150 (see FIG. 14), and an oscilloscope 160 (see FIG. 14).

[0135] The substrate-attached polarizing film 110 is the substrate-attached polarizing film obtained in Example 15. Specifically, as shown in FIG. 14 , the substrate-attached polarizing film 110 includes a polarizing film 111, which is a vacuum-deposited film of compound (I-2), a glass substrate 112, and an electrode 113, which is a layer made of ITO. The polarizing film 111 is formed on a main surface S112 of the glass substrate 112. The outer edge of the polarizing film 111 is rectangular. The thickness of the polarizing film 111 is 0.35 μm. The ITO electrode 113 is interposed between the polarizing film 111 and the glass substrate 112.

[0136] The electrode substrate 120 has a counter electrode 121, which is a layer made of ITO, and a polyethylene terephthalate (PET) substrate 122. The counter electrode 121 is formed on a main surface S122 of the PET substrate 122. The counter electrode 121 faces the polarizing film 111 of the substrate-attached polarizing film 110.

[0137] The spacer 140 is formed so as to surround the periphery of the polarizing film 111. The spacer 140 separates the substrate-attached polarizing film 110 from the electrode substrate 120. The spacer 140 supports the electrode substrate 120 so that the electrode substrate 120 vibrates in the thickness direction V of the electrode substrate 120 due to external stress. The spacer 140 is made of insulating tape.

[0138] The oscilloscope 160 is electrically connected to the counter electrode 121 via the amplifier 150. The time change of the current generated in the counter electrode 121 is observed by the oscilloscope 160.

[0139] [3.15.2] Performance Evaluation The PET substrate 122 was vibrated, and the change in the generated current over time was measured with an oscilloscope 160. Specifically, the PET substrate 122 was periodically vibrated with a finger, and the distance between the PET substrate 122 and the polarizing film 111 was modulated to generate an oscillating current. It was confirmed that a negative current flowed when the PET substrate 122 was pressed with a finger.

[0140] The measurement results are shown in Fig. 15. In Fig. 15, the symbol "R1" indicates the point in time when the PET substrate 122 is farthest from the polarizing film 111 in one cycle of the vibration of the PET substrate 122. The symbol "R2" indicates the point in time when the PET substrate 122 is closest to the polarizing film 111 in one cycle of the vibration of the PET substrate 122.

[0141] From the measurement results of the time change of the current generated by vibrating the PET substrate 122, it was confirmed that a current with reversed polarity was generated when the distance between the PET substrate 122 and the polarizing film 111 was modulated, and that the current was generated by the vibration. It was confirmed that the current fluctuated with the same period as the period of the vibration of the PET substrate 122, and that the magnitude of the current fluctuated corresponding to the magnitude of the vibration of the PET substrate 122.

[0142] [4] Results The absolute value of the surface potential per unit film thickness was calculated by the least squares method using the measurement results of Examples 1 to 4 (see FIG. 9). As a result, the absolute value of the surface potential per unit film thickness of the polarized film made of compound (I-1) was 147 mV / nm.

[0143] The absolute value of the surface potential per unit film thickness was calculated by the least squares method using the measurement results of Examples 5 to 8 (see FIG. 9 ). As a result, the absolute value of the surface potential per unit film thickness of the polarized film made of compound (I-2) was 231 mV / nm.

[0144] The absolute value of the surface potential per unit film thickness was calculated by the least squares method using the measurement results of Examples 9 and 10 (see FIG. 11 ). As a result, the absolute value of the surface potential per unit film thickness of the polarized film made of compound (I-3) was 144 mV / nm.

[0145] The absolute value of the surface potential per unit film thickness was calculated by the least squares method using the measurement results of Examples 11 to 14 (see FIG. 12). As a result, the absolute value of the surface potential per unit film thickness of the polarized film made of compound (I-4) was 315 mV / nm.

[0146] The absolute value of the surface potential per unit film thickness was calculated by the least squares method using the measurement results (see) of Comparative Examples 1 to 4. As a result, the absolute value of the surface potential per unit film thickness of the polarized film made of compound (X-1) was 108 mV / nm.

[0147] The substrate-attached polarizing films of Comparative Examples 1 to 4 included a glass substrate and a polarizing film. The polarizing films did not contain compound (I-1). Therefore, as shown in FIG. 10, the absolute value of the surface potential per unit film thickness was 108 mV / nm (acceptable range: 140 mV / nm or more). These results indicate that the substrate-attached polarizing films of Comparative Examples 1 to 4 are not substrate-attached polarizing films with a larger absolute value of the surface potential per unit film thickness.

[0148] The substrate-attached polarizing films of Examples 1 to 4 and 15 included a glass substrate and a polarizing film. The polarizing film contained compound (I-1). Therefore, as shown in FIG. 9, the absolute value of the surface potential per unit film thickness was 147 mV / nm (acceptable range: 140 mV / nm or more). The substrate-attached polarizing films of Examples 5 to 8 included a glass substrate and a polarizing film. The polarizing film contained compound (I-2). Therefore, as shown in FIG. 9, the absolute value of the surface potential per unit film thickness was 231 mV / nm (acceptable range: 140 mV / nm or more). The substrate-attached polarizing films of Examples 9 and 10 included a glass substrate and a polarizing film. The polarizing film contained compound (I-3). Therefore, as shown in FIG. 11, the absolute value of the surface potential per unit film thickness was 144 mV / nm (acceptable range: 140 mV / nm or more). The substrate-attached polarized films of Examples 11 to 14 included a glass substrate and a polarized film. The polarized film contained compound (I-4). As a result, as shown in FIG. 12, the absolute value of the surface potential per unit film thickness was 315 mV / nm (acceptable range: 140 mV / nm or more). These results demonstrate that the substrate-attached polarized films of Examples 1 to 15 were substrate-attached polarized films with a larger absolute value of the surface potential per unit film thickness.

[0149] The disclosure of Japanese Patent Application No. 2023-135051, filed on August 22, 2023, is incorporated herein by reference in its entirety. All documents, patent applications, and technical standards described herein are incorporated herein by reference to the same extent as if each individual document, patent application, and technical standard was specifically and individually indicated to be incorporated by reference.

Claims

1. A substrate-attached polarized film comprising a substrate and a polarized film formed on at least one of the two main surfaces of the substrate, the polarized film comprising a compound represented by the following formula (I): (In formula (I), Z is a divalent organic group that imparts a bent structure to the compound, and represents a hydrocarbon group having 2 to 80 carbon atoms, a sulfonyl group, an amine group, an ether group, or a thioether group. A part or all of the carbon atoms constituting the hydrocarbon group may be substituted with a heteroatom. A part or all of the hydrogen atoms of the hydrocarbon group may be substituted with a halogen atom. １ and A ２ Each of X independently represents a single bond or a divalent linking group. １ and X ２ Each of X independently represents a monovalent aromatic hydrocarbon group having 6 to 80 carbon atoms or a hydrocarbon group having 2 to 80 carbon atoms. １ and X ２ In the above-mentioned aromatic hydrocarbon group and the above-mentioned hydrocarbon group, some or all of the hydrogen atoms are substituted with fluorine atoms. １ and X ２ The total number of fluorine atoms contained in each of the groups is greater than the number of halogen atoms contained in the group Z.

2. The divalent organic group is one selected from the group consisting of groups represented by the following formulas (z-1) to (z-7): X １ and X ２ The substrate-attached polarizing film according to claim 1, wherein is one selected from the group consisting of groups represented by the following formulas (x-1) to (x-10): (In formulas (z-1) to (z-7) and formulas (x-1) to (x-10), * indicates a bonding position.) 3. X １ and X ２ is a group represented by the formula (x-1), the formula (x-2) or the formula (x-3), and the divalent organic group is a group represented by the formula (z-1), the formula (z-2) or the formula (z-3).

4. The substrate-attached polarizing film according to claim 2, wherein the divalent organic group is one selected from the group consisting of groups represented by formula (z-1) and formulas (z-3) to (z-7).

5. A １ and A ２ each independently represents the divalent linking group, the divalent linking group is an aromatic hydrocarbon group having 6 to 80 carbon atoms, and some or all of the carbon atoms constituting the divalent linking group may be substituted with a heteroatom.

6. The substrate-attached polarizing film according to claim 5, wherein the divalent linking groups are each independently represented by the following formula (a-1), formula (a-2) or formula (a-3): (In formulas (a-1), (a-2) and (a-3), * indicates a bonding position.) 7. A substrate-attached polarized film according to any one of claims 1 to 4, wherein the compound has a permanent dipole moment of 4.0 Debye to 25.0 Debye in absolute value.

8. The substrate-attached polarized film according to any one of claims 1 to 4, wherein the absolute value of the surface potential per unit film thickness is 180 mV / nm to 1200 mV / nm.

9. A vibration power generating element comprising a substrate-attached polarizing film according to any one of claims 1 to 4.

10. An organic light-emitting device comprising a polarizing film separated from the substrate-attached polarizing film according to any one of claims 1 to 4.

11. A method for producing a substrate-attached polarized film according to any one of claims 1 to 4, comprising: preparing a raw material containing the compound; and using the raw material to form the polarized film on at least one of the two main surfaces of the substrate by vacuum deposition or wet process.

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