Polarization film with substrate, vibration power generation element, organic light-emitting element, and method for manufacturing a polarization film with substrate

Abstract

A polarization film with a substrate is provided that has a high surface charge density and a high degree of molecular orientation, even without containing fluorine atoms. [Solution] The polarization film with a substrate 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 the following formula (I). In formula (I), Z represents either a polar functional group or an organic group. 1 and A 2 X represents a single bond or a divalent linking group. 1 and X 2 This represents the other of a polar functional group and an organic group. JPEG2026076969000023.jpg2069

Description

[Technical Field]

[0001] The present invention relates to a polarization film with a substrate, a vibration power generation element, an organic light-emitting element, and a method for manufacturing a polarization film with a substrate. [Background technology]

[0002] As a power generation element that converts vibration into electricity, electrostatic vibration power generation elements (hereinafter also simply referred to as "vibration power generation elements") are known. A vibration power generation element is a power generation element configured to induce sequential electrostatic induction in the electrodes by changing the relative position of the electret (electric stone) and the electrodes through vibration. Vibration power generation elements can efficiently extract power from low-frequency vibrations with low acceleration (for example, environmental vibrations).

[0003] Research and development has focused on electret films (hereinafter also called "polarization films") obtained by implanting electric charge into polymer films as electrets for vibration power generation elements. Charge treatment processes (e.g., corona discharge, electron beam irradiation, thermal poling, or contact charging) have been employed as methods for implanting electric charge into polymer films.

[0004] However, conventional methods for fabricating polarization films require applying a high voltage to the polymer film from an external source. This necessitates large-scale equipment and a complicated manufacturing process. Conventional methods for fabricating polarization films have low productivity and high costs.

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

[0006] Patent Document 1 discloses a membrane (hereinafter also referred to as a "polarization membrane"). The membrane disclosed in Patent Document 1 contains a compound represented by the following general formula (x).

[0007] [ka]

[0008] In general formula (x), R represents an alkyl fluoride. Of X, Y, and Z, 0 to 2 each independently represent an alkyl fluoride, and the remaining ones each independently represent a substituent other than an alkyl fluoride. [Prior art documents] [Patent Documents]

[0009] [Patent Document 1] Japanese Patent Publication No. 2022-143338 [Overview of the project] [Problems that the invention aims to solve]

[0010] However, the manufacture and use of compounds containing fluorine atoms may be restricted from an environmental perspective. In addition, a high degree of molecular orientation of the polarization film is expected to reduce the relative variation in surface potential due to process conditions, as the magnitude of the surface potential does not depend heavily on the deposition process. The "degree of molecular orientation of the polarization film" quantitatively represents the direction in which the molecules constituting the polarization film are facing or their positional relationships. Various factors (e.g., molecular shape, charge distribution, and bonding properties) can influence molecular orientation. Therefore, there is a need for substrate-mounted polarization films that have a high surface charge density and a high degree of molecular orientation, even without containing fluorine atoms.

[0011] This disclosure has been made in view of the above. One embodiment of this disclosure aims to solve the problem of providing a substrate-mounted polarization film, a vibration power generation element, an organic light-emitting element, and a method for manufacturing a substrate-mounted polarization film, which have a high surface charge density and a high degree of molecular orientation, even without containing fluorine atoms. [Means for solving the problem]

[0012] The following embodiments are included as means for solving the above problems. <1> A substrate and a polarization film formed on at least one of the two main surfaces of the substrate. A polarization film with a substrate, wherein the polarization film contains a compound represented by the following formula (I).

[0013]

Chemical formula

[0014] (In formula (I), Z, A 1 A 2 X 1 and X 2 are a first combination or a second combination and do not contain fluorine atoms. In the first combination, Z represents a divalent polar functional group that imparts a bent structure to the compound. A 1 and A 2 each independently represent a single bond or a divalent linking group. X 1 and X 2 each independently represent a monovalent organic group. The monovalent organic group represents an alkyl group having 5 to 24 carbon atoms, a cycloalkyl group having 5 to 20 carbon atoms, or an alkylcycloalkyl group having 5 to 30 carbon atoms. Some or all of the carbon atoms constituting the alkyl group, the cycloalkyl group, and the alkylcycloalkyl group may be substituted with heteroatoms. In the second combination, Z represents a divalent organic group that imparts a bent structure to the compound, and the divalent organic group represents a cycloalkylene group having 7 to 20 carbon atoms, an alkylcycloalkylene group having 7 to 30 carbon atoms, or a divalent aromatic hydrocarbon group having 7 to 80 carbon atoms. A 1 and A 2 each independently represent a single bond or a divalent linking group. X 1 and X 2 each independently represent a monovalent polar functional group. Some or all of the carbon atoms constituting the cycloalkylene group, the alkylcycloalkylene group, and the aromatic hydrocarbon group may be substituted with heteroatoms. <2> The divalent linking group is a C1 methylene group, a group represented by formula (a-1), a group represented by formula (a-2), a group represented by formula (a-3), a group represented by formula (a-4), or a group represented by formula (a-5), <1> A polarization film with a substrate as described above.

[0015] [ka]

[0016] (In equations (a-1) to (a-5), * indicates the bonding position.) <3> Z_A 1 , A 2 , X 1 and X 2 However, this is the first combination, The divalent polar functional group is a sulfonyl group, a 1-15 ring arylphosphine oxide group, a benzonitrile group, a phthalimide group, or a pyridine group. <2> A polarization film with a substrate as described above. <4> The monovalent organic group represents a C5-C8 alkyl group, a C5-C8 cycloalkyl group, or a C5-C8 alkylcycloalkyl group. <3> A polarization film with a substrate as described above. <5> Z_A 1 , A 2 , X 1 and X 2 However, this is the second combination, The monovalent polar functional group is a monocyclic arylsulfonyl group, a bicyclic arylphosphine oxide group, a nitrile group, a phthalimide group, or a pyridine group. <2> A polarization film with a substrate as described above. <6> The divalent organic group represents a cycloalkylene group having 7 to 10 carbon atoms, an alkylcycloalkylene group having 7 to 10 carbon atoms, or a divalent aromatic hydrocarbon group having 7 to 22 carbon atoms. <5> A polarization film with a substrate as described above. <7> The compound has a permanent dipole moment of 1.0 Debye to 30.0 Debye in absolute value, <1> A polarization film with a substrate as described above. <8> The absolute value of the surface potential per unit film thickness is 50 mV / nm to 1500 mV / nm, <1> A polarization film with a substrate as described above. <9> The aforementioned <1> ~ <8> A vibration power generation element comprising a polarization film with a substrate as described in any one of the following. <10> The aforementioned <1> ~ <8> An organic light-emitting element comprising a polarization film separated from a substrate-mounted polarization film described in any one of the above. <11> The aforementioned <1> ~ <8> A method for manufacturing a substrate-mounted polarization film as described in any one of the following: To prepare a raw material containing the aforementioned compound, Using the aforementioned raw materials, the polarization film is formed on at least one of the two main surfaces of the substrate by vacuum deposition or a wet process method. A method for manufacturing a polarization film with a substrate, including the method described above. [Effects of the Invention]

[0017] According to one embodiment of the present disclosure, a substrate-mounted polarization film having a high surface charge density and a high degree of molecular orientation, a vibration power generation element, an organic light-emitting element, and a method for manufacturing a substrate-mounted polarization film are provided, even without containing fluorine atoms. [Brief explanation of the drawing]

[0018] [Figure 1] Figure 1 shows the orientation of the permanent dipole moment of compound (I-1). [Figure 2] Figure 2 is a cross-sectional view of a vibration power generation element according to the first embodiment of this disclosure. [Figure 3] Figure 3 is a cross-sectional view of a vibration power generation element according to the second embodiment of this disclosure. [Figure 4] Figure 4 is a cross-sectional view of a vibration power generation element according to the third embodiment of this disclosure. [Figure 5] Figure 5 is a graph showing the 1H-NMR spectrum of the compound obtained in synthesis example (I-1). [Figure 6]Figure 6 is a graph showing the 1H-NMR spectrum of the compounds obtained in synthesis example (I-2). [Figure 7] Figure 7 is a graph showing the 1H-NMR spectrum of the compound obtained in the synthesis example (CE). [Figure 8] Figure 8 is a graph showing the surface potential as a function of film thickness for Examples 1 to 4 and Comparative Examples 1 to 4. [Figure 9] Figure 9 is a graph showing the surface potential against film thickness for Examples 5 to 8. [Figure 10] Figure 10 is a graph showing the current density as a function of time in vibration power generation tests using a deposited thin film of compound (I-1) and a deposited thin film of 6FDI-2oBN. [Figure 11] Figure 11 is a graph showing the brightness characteristics with respect to voltage in experiments using an organic light-emitting device (A) containing a deposited thin film of compound (I-1) and an organic light-emitting device (B) without a deposited thin film of compound (I-1). [Figure 12] Figure 12 is a graph showing the current efficiency as a function of current density in experiments using an organic light-emitting device (A) containing a deposited thin film of compound (I-1) and an organic light-emitting device (B) without a deposited thin film of compound (I-1). [Modes for carrying out the invention]

[0019] The contents of this disclosure are described in detail below. The following descriptions of constituent elements may be based on representative embodiments of this disclosure, but this disclosure is not limited to such embodiments. In this disclosure, a combination of two or more preferred embodiments is a more preferred embodiment. In this disclosure, a numerical range represented by "~" means a range that includes the numbers written before and after "~" as the lower and upper limits, respectively. In this disclosure, the term "process" includes not only independent processes but also processes that cannot be clearly distinguished from other processes, as long as their objectives are achieved. In numerical ranges described in stages within this disclosure, the upper or lower limit of one numerical range may be replaced by the upper or lower limit of another numerical range described in stages. In numerical ranges described within this disclosure, the upper or lower limit of that range may be replaced by the values ​​shown in the examples.

[0020] (1) Polarization film with substrate The substrate-mounted polarization film of 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 the following formula (I) (hereinafter also referred to as "compound (I)").

[0021] [ka]

[0022] In formula (I), Z, A 1 , A 2 , X 1 and X 2 This is either the first combination or the second combination, and does not contain a fluorine atom. In the first combination described above, Z represents a divalent polar functional group that imparts a bent structure to the compound, A 1 and A 2 However, each independently represents a single bond or a divalent linking group, X 1 and X 2 However, each independently represents a monovalent organic group, The monovalent organic group represents an alkyl group having 5 to 24 carbon atoms, a cycloalkyl group having 5 to 20 carbon atoms, or an alkylcycloalkyl group having 5 to 30 carbon atoms. Some or all of the carbon atoms constituting the alkyl group, the cycloalkyl group, and the alkylcycloalkyl group may be substituted with heteroatoms. In the second combination mentioned above, Z represents a divalent organic group that imparts a bent structure to the compound, and the divalent organic group represents a cycloalkylene group having 7 to 20 carbon atoms, an alkylcycloalkylene group having 7 to 30 carbon atoms, or a divalent aromatic hydrocarbon group having 7 to 80 carbon atoms. A 1 and A 2 However, each independently represents a single bond or a divalent linking group, X 1 and X 2 However, each independently represents a monovalent polar functional group. Some or all of the carbon atoms constituting the cycloalkylene group, the alkylcycloalkylene group, and the aromatic hydrocarbon group may be substituted with heteroatoms.

[0023] In this disclosure, "polarized film" refers to a film that maintains polarization semi-permanently in the film thickness direction. In other words, "polarized film" refers to a film that has a surface potential. "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 (0V). Surface potential is also called giant surface potential (GSP). "A divalent organic group that confers a bent structure to the compound" indicates that the bond angle is not 180°. "Bond angle" refers to A of Z in formula (I). 1 The atom that bonds with (if Z is a sulfonyl atom, then a sulfur atom) and X 1 A 1 The first straight line connecting the atom to which it bonds (for example, a carbon atom), and A in Z 2 The atom that bonds with X 2 A 2 This shows the angle formed by the second line connecting the atom to which it bonds (for example, a carbon atom). A "polar functional group" refers to a functional group that exhibits electron-withdrawing properties. More specifically, a "polar functional group" refers to a functional group that has a permanent dipole moment of 1.0 Debye or greater, as determined by quantum chemical calculations (for example, using the quantum chemical calculation software Gaussian16 with DFT B3LYP / 6-31G(d)). 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. "Aromatic hydrocarbon group" refers to a hydrocarbon group having at least one aromatic ring. "Aromatic ring" refers to a cyclic conjugated compound having 4n+2 π electrons. The aromatic ring may be monocyclic (e.g., benzene) or polycyclic (e.g., naphthalene, anthracene, or phenanthrene). The aromatic hydrocarbon group may contain alkyl groups or cycloalkyl groups.

[0024] Because the substrate-mounted polarization film of this disclosure has the above-described structure, it has a high surface charge density and a high degree of molecular orientation even without containing fluorine atoms. As a result, the environmental impact of the substrate-mounted polarization film of this disclosure is reduced. In addition, when forming a substrate-mounted polarization film with a constant surface potential, if the substrate-mounted polarization film of this disclosure is used, the thickness of the polarization film can be thinner than when using conventional polarization films. As a result, the substrate-mounted polarization film of this disclosure can reduce the manufacturing cost of, for example, vibration power generation elements. This effect is presumed to be due to, but is not limited to, the following reasons. In this disclosure, in equation (I), Z and X 1 and X 2 One of these is a polar functional group. For example, when a polarization film is formed on a substrate by vacuum deposition, the compound tends to be deposited on the substrate such that the polar functional groups with high electron density are on the substrate side. Furthermore, the intramolecular charge distribution of compound (I) is biased towards the vicinity of the polar functional groups of compound (I). As a result, the overall degree of polarization of the polarization film is greater than in conventional designs. Consequently, it is presumed that the substrate-mounted polarization film of this disclosure has a high surface charge density and a high degree of molecular orientation, even without containing fluorine atoms.

[0025] The configuration of the substrate-mounted polarization film is appropriately selected according to the application of the substrate-mounted polarization film. The polarization film may be formed directly on the two main surfaces of the substrate, or it may be formed indirectly on the two main surfaces of the substrate. When the polarization film is formed indirectly on the two main surfaces of the substrate, other layers, as described later, may be interposed between the polarization film and the substrate.

[0026] (1.1) Polarization film A polarization film with a substrate comprises a polarization film. The polarization film contains compound (I). The polarization film may consist only of compound (I). The polarization film may also be a film formed by vacuum deposition (i.e., a vacuum-deposited film).

[0027] The thickness of the polarization film is appropriately selected depending on the application of the substrate-mounted polarization film. The thickness of the polarization film is preferably 100 nm or more, but may also be 500 nm or more, or 1000 nm or more, from the viewpoint of generating a sufficient surface potential. The film thickness may also be 10000 nm or less, 1000 nm or less, or 500 nm or less. The thickness of the polarization film 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 thickness of the polarization film is the same as described in the examples.

[0028] The polarization film exhibits a positive or negative surface potential on its surface due to the structure and polarization of the compound represented in (I) above. Z, A 1 , A 2 , X 1 and X 2 In the case of the first combination, the surface potential of the polarization film tends to be positive. Z, A 1 , A 2 , X 1 and X 2 In the case of the second combination, the surface potential of the polarization film tends to be negative. It is preferable that the surface potential of the polarization film changes depending on the thickness of the polarization film.

[0029] The absolute value of the surface potential of the polarization film is not particularly limited and may be between 100V and 1000V, between 1000V and 10000V, or between 10000V and 100000V. One method for adjusting the absolute value of the surface potential of the polarization film to within the range described above is to form the polarization film by vacuum deposition of compound (I). The method for measuring the surface potential of the polarization film is the same as that described in the examples.

[0030] The absolute value of the surface potential per unit thickness of the polarization film is preferably 50 mV / nm to 1500 mV / nm. The fact that the absolute value of the surface potential per unit thickness of the polarization film is 50 mV / nm to 1500 mV / nm indicates that the absolute value of the surface potential per unit thickness of the polarization film is higher than that of conventional polarization films. As a result, the substrate-mounted polarization film of this disclosure can achieve a higher output of the vibration power generation element. The absolute value of the surface potential per unit thickness of the polarization film is more preferably 100mV / nm to 1500mV / nm, and even more preferably 300mV / nm to 1500mV / nm, from the viewpoint of the performance of the vibration power generation element and the manufacturing cost. One method for adjusting the absolute value of the surface potential per unit thickness of the polarization film to within the range described above is to form the polarization film by vacuum deposition of compound (I). The method for measuring the surface potential per unit thickness of the polarization film is the same as that described in the examples.

[0031] (1.1.1) Compound (I) Compound (I) is represented by the following formula (I). The polarization film may contain one compound (I) or two or more compounds.

[0032] [ka]

[0033] In formula (I), Z, A 1 , A 2 , X 1 and X 2This is either the first combination or the second combination, and does not contain a fluorine atom.

[0034] (1.1.1.1) First combination In the first combination described above, Z represents a divalent polar functional group that confers a bent structure to the compound. 1 and A 2 Each of these independently represents a single bond or a divalent linking group. 1 and X 2 Each of these independently represents a monovalent organic group. The monovalent organic group represents an alkyl group having 5 to 24 carbon atoms, a cycloalkyl group having 5 to 20 carbon atoms, or an alkylcycloalkyl group having 5 to 30 carbon atoms. Some or all of the carbon atoms constituting the alkyl group, the cycloalkyl group, and the alkylcycloalkyl group may be substituted with heteroatoms.

[0035] 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 polarization film, it is preferably 400 to 2000, more preferably 600 to 1500, even more preferably 700 to 1300, and most preferably 800 to 1200.

[0036] (1.1.1.1.1) Divalent polar functional groups Examples of "divalent polar functional groups" represented by Z include sulfonyl groups, monocyclic to tricyclic arylphosphine oxide groups, benzonitrile groups, phthalimide groups, and pyridine groups.

[0037] Z_A 1 , A 2 , X 1 and X 2 However, the first combination is preferable, in which the divalent polar functional group is a sulfonyl group, a 1-15 ring arylphosphine oxide group, a benzonitrile group, a phthalimide group, or a pyridine group. As a result, the absolute value of the surface potential per unit thickness of the polarization film is higher than in the case where the divalent polar functional group is not one of the above.

[0038] As for the "divalent polar functional group," from the viewpoint of increasing the absolute value of the surface potential per unit thickness of the polarization film, it is preferable that it be a group represented by the following equations (z1-1~) to (z1-5).

[0039] [ka]

[0040] In equations (z1-1) to (z1-5), * indicates the bonding position.

[0041] (1.1.1.1.2) Divalent linking group A 1 and A 2 The term "divalent linking group" is represented by -O-, -S-, -CO-, -N-, a divalent hydrocarbon group having 1 to 80 carbon atoms, or a combination thereof. A 1 and A 2 The "divalent hydrocarbon group having 1 to 80 carbon atoms" represented by can be linear, branched, or cyclic. A 1 and A 2 The "divalent hydrocarbon group having 1 to 80 carbon atoms" represented by may be a saturated hydrocarbon group or an unsaturated hydrocarbon group. A 1 and A 2 The number of carbon atoms in the "divalent hydrocarbon group having 1 to 80 carbon atoms" represented by may be 1 to 10, 11 to 40, or 41 to 80. A 1 and A 2 Examples of heteroatoms that may be substituted for "some or all of the carbon atoms constituting the hydrocarbon group" include oxygen atoms, nitrogen atoms, sulfur atoms, phosphorus atoms, or boron atoms. A 1 and A 2 Some or all of the carbon atoms constituting the "divalent hydrocarbon group having 1 to 80 carbon atoms" represented by may be substituted with heteroatoms (for example, nitrogen, oxygen, sulfur, or halogens (for example, fluorine, chlorine, bromine, or iodine)).

[0042] The aforementioned 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 It is preferable that it contains an aromatic ring. As a result, A 1 and A 2 Compound (I) exhibits greater steric hindrance than when it consists only of single bonds (alkyl groups). In other words, compound (I) has superior rigidity. Therefore, when a polarization film is deposited by vacuum deposition, compound (I) tends to align more regularly on the substrate. The glass transition temperature indicates the temperature at which the physical properties of the object being measured (e.g., viscosity or fluidity) change abruptly when the temperature is continuously varied. Therefore, the glass transition temperature of a polarization film is higher. Depending on their application, substrate-mounted polarization films may be exposed to high-temperature atmospheres after fabrication. If the temperature of the high-temperature atmosphere exceeds the glass transition temperature of the substrate-mounted polarization film, the molecular arrangement of compound (I) in the polarization film may be disrupted, potentially decreasing the absolute value of the surface potential of the polarization film. A higher glass transition temperature of the polarization film allows for a higher lower limit on the temperature at which the surface potential of the polarization film decreases. In other words, the surface potential of the polarization film can be maintained even at relatively high ambient temperatures. As a result, substrate-mounted polarization films can be applied to a wide range of processing processes. Therefore, the applications of substrate-mounted polarization films are broadened.

[0043] Examples of the divalent linking group include a C1 methylene group (-CH2-), a group represented by formula (a-1), a group represented by formula (a-2), a group represented by formula (a-3), a group represented by formula (a-4), or a group represented by formula (a-5).

[0044] [ka]

[0045] In equations (a-1) to (a-5), * indicates the bonding position.

[0046] A 1 and A 2 Preferably, this is a methylene group having 1 carbon atom, a group represented by formula (a-1), a group represented by formula (a-2), a group represented by formula (a-3), a group represented by formula (a-4), or a group represented by formula (a-5). As a result, A 1 and A 2 The glass transition temperature of the polarization film tends to be higher than when the substrate is not a C1 methylene group, a group represented by formula (a-1), a group represented by formula (a-2), a group represented by formula (a-3), a group represented by formula (a-4), or a group represented by formula (a-5). As a result, the substrate-mounted polarization film can be applied to a wider range of processing processes. Therefore, the applications of substrate-mounted polarization films are broader.

[0047] (1.1.1.1.3) Monovalent organic group X 1 and X 2 The "monovalent organic group" represented by represents an alkyl group having 5 to 24 carbon atoms, a cycloalkyl group having 5 to 20 carbon atoms, or an alkylcycloalkyl group having 5 to 30 carbon atoms. Some or all of the carbon atoms constituting the alkyl group, the cycloalkyl group, and the alkylcycloalkyl group may be substituted with heteroatoms.

[0048] The "alkyl group having 5 to 24 carbon atoms" may be linear, branched, or cyclic. The number of carbon atoms in the "alkyl group with 5 to 24 carbon atoms" may be 5 to 10 or 11 to 24. Examples of "alkyl groups having 5 to 24 carbon atoms" include pentyl, hexyl, heptyl, octyl, nonyl, and decyl groups.

[0049] The number of carbon atoms in the "cycloalkyl group with 5 to 20 carbon atoms" may be 5 to 10 or 11 to 20. Examples of "cycloalkyl groups having 5 to 20 carbon atoms" include cyclopentyl group, cyclohexyl group, cycloheptyl group, cyclooctyl group, norbornyl group, 1-adamantyl group, and 2-adamantyl group.

[0050] The valence of all carbon atoms in the aliphatic group of the "alkylcycloalkyl group having 5 to 30 carbon atoms" is satisfied. In other words, the aliphatic group does not contain any double or triple bonds. The aliphatic group of the "alkylcycloalkyl group having 5 to 30 carbon atoms" may be linear or branched. The number of carbon atoms in "alkylcycloalkyl group having 5 to 30 carbon atoms" may be 1 to 15 or 16 to 30. Examples of "alkylcycloalkyl groups having 5 to 30 carbon atoms" include methylcyclobutyl group, dimethylcyclobutyl group, ethylcyclobutyl group, methylcyclopentanyl group, dimethylcyclopentanyl group, ethylcyclopentanyl group, methylcyclohexyl group, dimethylcyclohexyl group, ethylcyclohexyl group, methylcyclopentyl group, dimethylcyclopentyl group, and ethylcyclopentyl group.

[0051] Examples of "heteroatoms" in which some or all of the carbon atoms constituting the alkyl group, cycloalkyl group, and alkylcycloalkyl group may be substituted include oxygen atoms, nitrogen atoms, sulfur atoms, phosphorus atoms, or boron atoms.

[0052] The monovalent organic group preferably represents an alkyl group having 5 to 8 carbon atoms, a cycloalkyl group having 5 to 10 carbon atoms (preferably 5 to 8 carbon atoms, more preferably 7 to 10 carbon atoms), or an alkylcycloalkyl group having 5 to 8 carbon atoms. As a result, the absolute value of the surface potential per unit thickness of the polarization film is higher than when the monovalent organic group is not one of the above cases.

[0053] Examples of "monovalent organic groups" include the groups represented by the following formulas (X1-1) to (X1-8).

[0054] [ka]

[0055] In formulas (X1-1) to (X1-8), * indicates the bonding position.

[0056] (1.1.1.1.4) Specific examples Z, A 1 , A 2 , X 1 and X 2 When Z, A, and X are in the first combination, examples of the compound (I) include compounds represented by the following formulas (I-1) to (I-13).

[0057] [Chemical formula]

[0058] (1.1.1.2) The second combination In the second combination, Z represents a divalent organic group that imparts a bent structure to the compound. The divalent organic group represents a cycloalkylene group having 7 to 20 carbon atoms, an alkylcycloalkylene group having 7 to 30 carbon atoms, or a divalent aromatic hydrocarbon group having 7 to 80 carbon atoms. A 1 and A 2 each independently represents a single bond or a divalent linking group. X 1 and X 2 each independently represents a monovalent polar functional group. Some or all of the carbon atoms constituting the cycloalkylene group, the alkylcycloalkylene group, and the aromatic hydrocarbon group may be substituted with heteroatoms.

[0059] The molecular weight of the compound (I) is not particularly limited, but from the viewpoint of further increasing the absolute value of the surface potential of the polarization film, it is preferably 400 to 2000, more preferably 600 to 1500, still more preferably 700 to 1300, and particularly preferably 800 to 1200.

[0060] (1.1.1.2.1) Divalent organic group The "divalent organic group" represented by Z represents a divalent cycloalkylene group with 7 to 20 carbon atoms, a divalent alkylcycloalkylene group with 7 to 30 carbon atoms, or a divalent aromatic hydrocarbon group with 7 to 80 carbon atoms.

[0061] The number of carbon atoms in the "cycloalkylene group with 7 to 20 carbon atoms" may be 7 to 14 or 15 to 20. Examples of "cycloalkylene groups having 7 to 20 carbon atoms" include cycloheptylene, cyclooctylene, norbornylene, and adamantylene.

[0062] "Alkylcycloalkylene groups with 7 to 30 carbon atoms" do not contain double or triple bonds. The number of carbon atoms in the "alkylcycloalkylene group having 7 to 30 carbon atoms" may be 7 to 18 or 19 to 30. Examples of "alkylcycloalkylene groups having 7 to 30 carbon atoms" include methylcyclohexylene, dimethylcyclohexylene, ethylcyclohexylene, methylcyclopentylene, dimethylcyclopentylene, and ethylcyclopentylene.

[0063] The "divalent aromatic hydrocarbon group having 7 to 80 carbon atoms" may be linear, branched, or cyclic. The number of carbon atoms in the "divalent aromatic hydrocarbon group with 7 to 80 carbon atoms" may be 7 to 30 or 31 to 80. Examples of "divalent aromatic hydrocarbon groups having 7 to 80 carbon atoms" include fluorylene, phenylene, biphenylylene, terphenylylene, naphthylene, anthrylene, phenanthrylene, acenaphthenediyl, and triphenylenediyl groups.

[0064] The divalent organic group preferably represents a cycloalkylene group having 7 to 10 carbon atoms, an alkylcycloalkylene group having 7 to 10 carbon atoms, or a divalent aromatic hydrocarbon group having 7 to 22 carbon atoms. As a result, the absolute value of the surface potential per unit thickness of the polarization film is higher than when the divalent organic group is not one of the above cases.

[0065] From the viewpoint of increasing the absolute value of the surface potential per unit thickness of the polarization film, the "divalent organic group" is preferably a group represented by the following equations (z2-1) to (z2-12).

[0066] [ka]

[0067] In equations (Z2-1) to (Z2-11), * indicates the bonding position.

[0068] (1.1.1.2.2) Divalent linking group A 1 and A 2 The "divalent linking group" represented by this symbol is the same as the example given for the "divalent linking group" in the first combination.

[0069] Examples of the divalent linking group include a one-carbon methylene group, a group represented by formula (a-1), a group represented by formula (a-2), a group represented by formula (a-3), a group represented by formula (a-4), or a group represented by formula (a-5).

[0070] [ka]

[0071] In equations (a-1) to (a-5), * indicates the bonding position.

[0072] A 1 and A 2is preferably a methylene group having 1 carbon atom, a group represented by the above formula (a-1), a group represented by formula (a-2), a group represented by formula (a-3), a group represented by formula (a-4), or a group represented by formula (a-5). Thereby, A 1 and A 2 When they are not a methylene group having 1 carbon atom, a group represented by the formula (a-1), a group represented by the formula (a-2), a group represented by the formula (a-3), a group represented by the formula (a-4), or a group represented by the formula (a-5), the glass transition temperature of the polarization film tends to be higher. As a result, the polarization film with a substrate can be applied to a wider range of processing processes. Therefore, the uses of the polarization film with a substrate are more extensive.

[0073] (1.1.1.2.3) Monovalent polar functional group X 1 and X 2 Specific examples of the "monovalent polar functional group" represented by include, for example, a monocyclic arylsulfonyl group, a bicyclic arylphosphine oxide group, a nitrile group, a phthalimide group, and a pyridine group.

[0074] Z, A 1 , A 2 , X 1 and X 2 are the second combination, the monovalent polar functional group is preferably a monocyclic arylsulfonyl group, a bicyclic arylphosphine oxide group, a nitrile group, a phthalimide group, or a pyridine group. Thereby, the absolute value of the surface potential per unit film thickness of the polarization film is higher than when the divalent polar functional group is not the above case.

[0075] The "divalent polar functional group" is preferably a group represented by the following formulas (X2-1) to (X2-5) from the viewpoint of increasing the absolute value of the surface potential per unit film thickness of the polarization film.

[0076]

Chemical formula

[0077] In equations (X2-1) to (X2-5), * indicates the bond position.

[0078] (1.1.1.2.4)Specific Examples Z_A 1 , A 2 , X 1 and X 2 If this is the second combination, examples of compound (I) include compounds represented by the following formulas (I-14) to (I-30).

[0079] [ka]

[0080] (1.1.1.3) Physical properties of compound (I) It is preferable that compound (I) has a permanent dipole moment of 1.0 Debye to 30.0 Debye in absolute value. Having a permanent dipole moment of 1.0 Debye to 30.0 Debye in absolute value of compound (I) indicates that the absolute value of the compound's permanent dipole moment is high. As a result, the absolute value of the surface potential per unit thickness of the substrate-mounted polarization film is greater than when the compound has a permanent dipole moment of less than 1.0 Debye in absolute terms. The absolute value of the permanent dipole moment of compound (I) may be 1.0 Debye to 5.0 Debye, 5.1 Debye to 10.0 Debye, or 10.1 Debye to 30.0 Debye, from the viewpoint of forming a polarized film with a large surface potential. The method for calculating the absolute value of the permanent dipole moment is the same as the calculation method described in the examples. Note that if conformational isomers exist for compound (I), the magnitude of the permanent dipole moment differs for each isomer; therefore, the permanent dipole moment of the structure with the highest probability of existence was used as the permanent dipole moment of compound (I).

[0081] The direction of the permanent dipole moment of compound (I) is usually from the region where negative charges are concentrated to the region where positive charges are concentrated, in the charge distribution within the molecule of the compound represented by formula (I) (hereinafter also referred to as "compound (I-1)"). For example, Figure 1 shows the direction of the permanent dipole moment of compound (I-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 polarization film using compound (I-1) tends to be positive. The direction of the permanent dipole moment of a compound depends on the bonding position and type of the polar functional group. The direction of the permanent dipole moment of compounds represented by formulas (I-2) to (I-12) shows the same tendency as the direction of the permanent dipole moment of compound (I-1). The direction of the permanent dipole moment of the compounds represented by equations (I-13) to (I-29) is opposite to the direction of the permanent dipole moment of compound (I-1).

[0082] (1.1.2) Other ingredients The polarization film may contain other components different from compound (I), or it may not contain other components, depending on the application of the substrate-mounted polarization film.

[0083] Other components include, for example, host materials. The "host material" is a matrix material that holds compound (I) in a certain orientation in the polarization film, is solid at room temperature, and is an organic material consisting of molecules with a permanent dipole moment of 1 Debye or less. Specifically, examples of host materials 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), or TCTA (4,4',4"-Tris(carbazol-9-yl)triphenylamine).

[0084] When the polarization film contains a host material, the content of compound (I) is not particularly limited, but is preferably 10% to 99% by mass, more preferably 50% to 99% by mass, and even more preferably 70% to 95% by mass, relative to the total amount of the polarization film.

[0085] (1.2) Substrate A polarization film with a substrate comprises a substrate. The substrate holds the polarization film. The material of the substrate is appropriately selected according to the application of the polarization film with the substrate, and examples include glass, silicon, resin, and metal. The size of the substrate is appropriately selected according to the application of the polarization film with the substrate.

[0086] (1.3) Other layers The substrate-mounted polarization film may or may not have other layers. The other layers may be interposed between the polarization film and the substrate, or they may be formed directly on regions of the two main surfaces of the substrate where the polarization film is not formed. The other layers are appropriately selected depending on the application of the substrate-mounted polarization film, and examples include conductive layers (e.g., electrode layers).

[0087] (1.4) Purpose Applications of substrate-mounted polarization films include, for example, power supplies for wireless communication (e.g., Bluetooth, etc.) (i.e., vibration power supplies) and organic electroluminescent (i.e., organic EL) displays.

[0088] (2) Vibration power generation element The vibration power generation element of this disclosure comprises a polarization film with a substrate of this disclosure.

[0089] Since the vibration power generation element of this disclosure has the above configuration, the output of the vibration power generation element is higher than that of conventional elements.

[0090] A vibration power generation element converts vibration energy into electrical power. A vibration power generation element typically comprises a substrate-mounted polarization film according to the present disclosure and an electrode (hereinafter also referred to as the "counter electrode") facing the polarization film across an air layer. The configuration of the vibration power generation element may be the same as that of a known vibration power generation element, except that it comprises a substrate-mounted polarization film according to the present disclosure. The polarity of the substrate-mounted polarization film according to the present disclosure may be negative or positive.

[0091] Preferred applications of the vibration power generation element are vibration generators or vibration sensors. In a vibration generator, by vibrating at least one of the substrate-mounted polarization film and the counter electrode of the present disclosure, an electric charge is induced on the counter electrode, and this induced charge is output as an electric current. In a vibration sensor, when the object to be detected vibrates, at least one of the substrate-mounted polarization film and the counter electrode of the present disclosure vibrates in conjunction with the vibration, and the vibration of the object to be detected is detected by the electric current caused by the electric charge induced on the counter electrode by this vibration as a detection signal.

[0092] (2.1) First to Third Embodiments The vibration power generation 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 denoted by the same reference numerals and will not be repeated in the description.

[0093] (2.1.1) First Embodiment As shown in Figure 2, the vibration power generation element 1A of the first embodiment comprises a polarization film 10 with a substrate, an electrode substrate 20A, and a load resistor 30.

[0094] The substrate-mounted polarization film 10 comprises a polarization film 11, a substrate 12, and an electrode 13. The polarization film 11 is formed on the main surface S12 of the substrate 12. The electrode 13 is interposed between the polarization film 11 and the substrate 12. The substrate-mounted polarization film 10 is the same as the substrate-mounted polarization film exemplified in this disclosure.

[0095] The electrode substrate 20A has a counter electrode 21 and a substrate 22. The counter electrode 21 is formed on the main surface S22 of the substrate 22. The counter electrode 21 faces the polarization film 11 of the substrate-attached polarization film 10. The electrode substrate 20A is supported such that the polarization film 11 and the counter electrode 21 are spaced apart. The electrode substrate 20A is configured to vibrate in the thickness direction 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.

[0096] The load resistor 30 is electrically connected to the electrode 13 and the counter electrode 21. The load resistor 30 can be any known type.

[0097] In the vibration power generation element 1A, when the electrode substrate 20A vibrates in the thickness direction V, the counter electrode 21 is displaced relative to the polarization film 11. As a result, the charge induced in the counter electrode 21 is output as an electric current.

[0098] In the first embodiment, the electrode substrate 20A is configured to vibrate due to external stress. The disclosure is not limited thereto, and the polarization film 10 with substrate may be configured to vibrate due to external stress, or the polarization film 10 with substrate and the electrode substrate 20A may each be configured to vibrate due to external stress.

[0099] (2.1.2) Second Embodiment The vibration power generation element 1B of the second embodiment is the same as the vibration power generation element 1A of the first embodiment, except that it includes a spacer 40. The vibration power generation element 1B includes a polarization film 10 with a substrate, an electrode substrate 20A, a load resistor 30, and a spacer 40.

[0100] The spacer 40 separates the polarization film 10 with substrate and the electrode substrate 20A. The spacer 40 supports the electrode substrate 20A such that the electrode substrate 20A vibrates in the thickness direction V of the electrode substrate 20A due to external stress. The material of the spacer 40 is an electrically insulating material (for example, resin).

[0101] In the second embodiment, the electrode substrate 20A is configured to vibrate due to external stress. The disclosure is not limited thereto, and the polarization film 10 with substrate may be configured to vibrate due to external stress, or the polarization film 10 with substrate and the electrode substrate 20A may each be configured to vibrate due to external stress.

[0102] (2.1.3) Third Embodiment The vibration power generation element 1C of the third embodiment is the same as the vibration power generation element 1A of the first embodiment, except that the electrode substrate further has a polarization film. The vibration power generation element 1C comprises a polarization film 10 with a substrate, an electrode substrate 20B, and a load resistor 30.

[0103] The electrode substrate 20B has a counter electrode 21, a substrate 22, and a polarization film 23. The polarization film 23, the counter electrode 21, and the substrate 22 are stacked in this order. The counter electrode 21 faces the polarization film 11 of the substrate-mounted polarization film 10 via the polarization film 23. The electrode substrate 20B is supported such that the polarization film 11 and the polarization film 23 are separated. The electrode substrate 20B is configured to vibrate in the thickness direction V due to external stress. The polarity of the surface potential of the polarization film 23 is opposite to the polarity of the surface potential of the polarization film 11 of the substrate-mounted polarization film 10. The electrode substrate 20B is the same as the substrate-mounted polarization film exemplified in this disclosure.

[0104] In the vibration power generation element 1C, when the electrode substrate 20B vibrates in its thickness direction V, the counter electrode 21 is displaced relative to the polarization film 11, and the polarization 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 generation element 1C can generate more power than the vibration power generation element 1A.

[0105] In the third embodiment, the electrode substrate 20B is configured to vibrate due to external stress. The disclosure is not limited thereto, and the polarization film 10 with substrate may be configured to vibrate due to external stress, or the polarization film 10 with substrate and the electrode substrate 20B may each be configured to vibrate due to external stress.

[0106] (3) Organic light-emitting element The organic light-emitting element of this disclosure comprises a polarization film separated from the substrate-mounted polarization film of this disclosure (hereinafter also referred to as the "separation film of this disclosure").

[0107] Since the organic light-emitting element of this disclosure has the above configuration, by inserting the polarization film into the stacked interface, 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 can be reduced, and the driving voltage of the organic light-emitting element can be reduced.

[0108] Organic light-emitting devices emit light when an electric field is applied. The configuration of an organic light-emitting device may be the same as that of a known organic light-emitting device, except that it includes the polarization film of this disclosure.

[0109] Preferred applications for organic light-emitting elements are organic photoluminescent elements (i.e., organic PL elements) or organic electroluminescent elements (i.e., organic EL elements).

[0110] An organic electroluminescent element comprises an anode, a cathode, and an organic layer formed between the anode and the cathode. The organic layer includes a light-emitting layer and a polarization film according to this disclosure.

[0111] The organic layer may consist of an emissive layer and a polarization film of this disclosure, or it may further include other organic layers different from the emissive layer and the polarization film of this disclosure. Examples of other organic layers include hole transport layers, hole injection layers, electron blocking layers, hole blocking layers, electron injection layers, electron transport layers, or exciton blocking layers. 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. The materials for these organic layers can be selected from known materials.

[0112] The film of this disclosure may be positioned at any location in the organic light-emitting element. When the surface potential polarity of the separation film of this disclosure is negative, it is preferable that the separation film of this disclosure be provided between the anode and the light-emitting layer, and more preferably in contact with the anode or in contact with the hole injection layer between the hole injection layer and the light-emitting layer. This allows the separation film of this disclosure to facilitate hole injection from the anode to the organic layer.

[0113] A laminate (hereinafter also simply referred to as "laminated layer") of a polarization film having a negative surface potential and a polarization film having a positive surface potential may be provided between the light-emitting layer and the cathode such that the film having the positive surface potential is on the cathode side. Preferably, the laminate is provided such 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.

[0114] (4) Method for manufacturing a polarization film with a substrate The method for manufacturing a substrate-mounted polarization film according to the present disclosure is a method for manufacturing a substrate-mounted polarization film according to the present disclosure. The manufacturing method includes preparing raw materials containing the compound (hereinafter also referred to as the "preparation step") and forming the polarization film on at least one of the two main surfaces of the substrate using the raw materials by vacuum deposition or a wet process (hereinafter also referred to as the "forming step"). The preparation step and the forming step are carried out in this order.

[0115] Since the manufacturing method of the present disclosure has the above configuration, a polarization film with a substrate of the present disclosure can be obtained.

[0116] (4.1) Preparation process In the preparation step, raw materials containing compound (I) are prepared. The raw materials are appropriately selected according to the composition of the polarization film and the method of forming the polarization film. The raw materials may consist only of compound (I), or they may contain the other components mentioned above, or they may contain a known solvent. The method of preparing the raw materials is not particularly limited and is appropriately selected according to the composition of the polarization film and the method of forming the polarization film. Compound (I) may be a compound obtained by synthesis.

[0117] (4.2) Forming process In the formation process, the polarization film is formed on at least one of the two main surfaces of the substrate using the raw materials by vacuum deposition or a wet process method. Examples of wet process methods include spin coating or dip coating. Among these, vacuum deposition is preferred for forming the polarization film. When the polarization film is formed by vacuum deposition, it is easier to obtain a polarization film in which multiple compounds (I) are arranged such that the permanent dipole moments of compound (I) are in the same direction, compared to the wet process method. In other words, it is easier to obtain a polarization film in which the absolute value of the surface potential per unit thickness is greater. [Examples]

[0118] 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, proportions, processing procedures, etc., shown in the following examples can be modified as appropriate without departing from the spirit of the present disclosure.

[0119] [1]Measurement method The physical properties and other values ​​in the examples were measured by the following method.

[0120] [1.1] Permanent dipole moment and molecular density of compounds The ground state of the compound molecule was optimized using the electronic structure program "Gaussian 16". In this case, the computational-level density functional theory (DFT) model B3LYP 6-31G(d) was used. The calculation result of the permanent dipole moment of the compound molecule with the ground state optimized was defined as the "permanent dipole moment of the compound." The calculation result of the molecular density of the compound molecule with the ground state optimized was defined as the "molecular density of the compound."

[0121] [1.2] Thickness of the polarization film The film thickness of organic thin films deposited by vacuum deposition was measured using an optical non-contact film thickness measuring instrument (ThetaMetrisis FR-ES).

[0122] [1.3] Surface potential of the polarization film Using an ultra-high vacuum Kelvin probe system (KP Technology: UHVKP020), the surface potential of the film attached to the substrate was measured in a dark, vacuum environment using the Kelvin probe method with the ITO (indium tin oxide) potential as the origin.

[0123] [1.4] Absolute value of surface potential per unit film thickness The absolute value of the surface potential per unit thickness was calculated from the measurement results of the polarization film thickness and the measurement results of the polarization film surface potential.

[0124] [1.5] Glass transition temperature A differential scanning calorimeter (Hitachi High-Tech Corporation: DSC7000X) was used to measure the glass transition temperature of the compound powder that is the raw material for the polarization film (hereinafter also referred to as "raw material powder"). The glass transition temperature of the raw material powder was defined as the "glass transition temperature of the polarization film." This is because the glass transition temperature of the raw material powder and the glass transition temperature of the polarization film, which has a nanoscale thickness, can be considered equivalent.

[0125] [2] Synthesis of compounds Compounds (I-1), (I-2), and (CE) were synthesized as follows.

[0126] [2.1] Synthesis example (I-1) In a round-bottom flask, 5,5'-sulfonylbis(isobenzofuran-1,3-dione), cyclohexylamine, benzoic acid, 1,3-dimethyl-2-imidazolidinone, and well-dried molecular sieves (4A) were added and stirred at room temperature with a magnetic stirrer for 5 hours. Then, the mixture was heated in an oil bath to 100°C and stirred for 10 hours. After stopping the heating, 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 the developing solvent to obtain a solid. 1 The measurement was performed by 1H-NMR (solvent: CDCl3). The measurement results are shown in Figure 5. From the measurement results, the obtained solid was identified as compound (I-1) represented by the following formula (I-1). The permanent dipole moment of compound (I-1) was 3.66 Debye.

[0127] [ka]

[0128] [2.2] Synthesis example (I-2) In a round-bottom flask, 1-adamantylamine, 4,4'-sulfonyl diphthalic anhydride, benzoic acid, 1,3-dimethyl-2-imidazolidinone, and well-dried molecular sieves (4A) were added and stirred at room temperature with a magnetic stirrer for 5 hours. Then, the mixture was heated in an oil bath to 150°C and stirred for 10 hours. After stopping the heating, 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 and ethyl acetate as the developing solvent to obtain a solid. 1 The measurement was performed by 1H-NMR (solvent: CDCl3). The measurement results are shown in Figure 6. From the measurement results, the obtained solid was identified as compound (I-2), represented by the following formula (I-2). The permanent dipole moment of compound (I-2) was 4.01 Debye.

[0129] [ka]

[0130] [2.3] Synthesis example (CE) In a round-bottom flask, 4-tert-butylphthalic anhydride, bis(4-aminophenyl)sulfone, benzoic acid, 1,3-dimethyl-2-imidazolidinone, and well-dried molecular sieves (4A) were added and stirred at room temperature with a magnetic stirrer for 2 hours. Then, the mixture was heated in an oil bath to 150°C and stirred for 20 hours. After stopping the heating, 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 the developing solvent to obtain a solid. 1 The measurement was performed by 1H-NMR (solvent: CDCl3). The measurement results are shown in Figure 7. Based on the measurement results, the obtained solid was identified as the following compound (CE). The permanent dipole moment of compound (CE) was 10.5 Debye.

[0131] [ka]

[0132] [3] Examples and Comparative Examples [3.1] Example 1 A glass substrate was prepared on which a layer of indium tin oxide (ITO) with a thickness of 100 nm (hereinafter also referred to as the "electrode") was formed. On this electrode, a vacuum deposition method was used to create a layer at a vacuum of 1 × 10⁻⁶. -4 A polarization film was formed by depositing compound (I-1) under conditions below Pa. This resulted in a substrate-mounted polarization film. The thickness of the polarization film was 28.0 nm. The surface potential of the obtained substrate-mounted polarization film was measured. The measured values ​​are shown in Figure 8.

[0133] [3.2] Example 2 A substrate-mounted polarization film was obtained in the same manner as in Example 1, except that the thickness of the polarization film was changed to 56.0 nm. The surface potential of the obtained substrate-mounted polarization film was measured. The measurement results are shown in Figure 8.

[0134] [3.3] Example 3 A substrate-mounted polarization film was obtained in the same manner as in Example 1, except that the thickness of the polarization film was changed to 84.0 nm. The surface potential of the obtained substrate-mounted polarization film was measured. The measurement results are shown in Figure 8.

[0135] [3.4] Example 4 A substrate-mounted polarization film was obtained in the same manner as in Example 1, except that the thickness of the polarization film was changed to 112.1 nm. The surface potential of the obtained substrate-mounted polarization film was measured. The measurement results are shown in Figure 8.

[0136] [3.5] Comparative Example 1 A substrate-mounted polarization film was obtained in the same manner as in Example 1, except that compound (I-1) was changed to compound (CE) and the thickness of the polarization film was changed to 34.5 nm. The surface potential of the obtained substrate-mounted polarization film was measured. The measured values ​​are shown in Figure 8.

[0137] [3.6] Comparative Example 2 A substrate-mounted polarization film was obtained in the same manner as in Example 1, except that compound (I-1) was changed to compound (CE) and the thickness of the polarization film was changed to 69.0 nm. The surface potential of the obtained substrate-mounted polarization film was measured. The measured values ​​are shown in Figure 8.

[0138] [3.7] Comparative Example 3 A substrate-mounted polarization film was obtained in the same manner as in Example 1, except that compound (I-1) was changed to compound (CE) and the thickness of the polarization film was changed to 103.5 nm. The surface potential of the obtained substrate-mounted polarization film was measured. The measured values ​​are shown in Figure 8.

[0139] [3.8] Comparative Example 4 A substrate-mounted polarization film was obtained in the same manner as in Example 1, except that compound (I-1) was changed to compound (CE) and the thickness of the polarization film was changed to 133.5 nm. The surface potential of the obtained substrate-mounted polarization film was measured. The measured values ​​are shown in Figure 8.

[0140] [3.9] Example 5 A glass substrate was prepared on which a layer of indium tin oxide (ITO) with a thickness of 100 nm (hereinafter also referred to as the "electrode") was formed. On this electrode, a vacuum deposition method was used to create a layer at a vacuum of 1 × 10⁻⁶. -4 A polarization film was formed by depositing compound (I-2) under conditions below Pa. This resulted in a substrate-attached polarization film. The thickness of the polarization film was 25.0 nm. The surface potential of the obtained substrate-attached polarization film was measured. The measured values ​​are shown in Figure 9.

[0141] [3.10] Example 6 A substrate-mounted polarization film was obtained in the same manner as in Example 5, except that the thickness of the polarization film was changed to 50.0 nm. The surface potential of the obtained substrate-mounted polarization film was measured. The measurement results are shown in Figure 9.

[0142] [3.11] Example 7 A substrate-mounted polarization film was obtained in the same manner as in Example 5, except that the thickness of the polarization film was changed to 75.1 nm. The surface potential of the obtained substrate-mounted polarization film was measured. The measurement results are shown in Figure 9.

[0143] [3.12] Example 8 A substrate-mounted polarization film was obtained in the same manner as in Example 5, except that the thickness of the polarization film was changed to 100.1 nm. The surface potential of the obtained substrate-mounted polarization film was measured. The measurement results are shown in Figure 9.

[0144] [4] Results [4.1] Molecular orientation of the polarization film [4.1.1] Comparative Example 1 to Comparative Example 4 Using the measurement results from Comparative Examples 1 to 4 (see Figure 8), the absolute value of the surface potential per unit thickness was calculated by the least squares method. As a result, the absolute value of the surface potential per unit thickness of the polarization film made of compound (CE) was 284 mV / nm.

[0145] The surface charge density of the polarization film was calculated using the absolute value of the surface potential per unit thickness of the polarization film, according to equation (i) below. The surface charge density of the polarization film made of compound (CE) was 7.6 mC / m 2 That was the case.

[0146] Equation (i): Surface charge density of the polarizing film = Absolute value of the measured surface potential per unit thickness of the polarizing film (mV / nm) × Permittivity of vacuum ε0 × Relative permittivity of the polarizing film ε r In equation (i), the permittivity of vacuum ε0 is 8.85 × 10⁻⁶. -12 The ratio is F / m. r We assumed that it was 3.00.

[0147] The molecular orientation of the polarization film was calculated using the surface charge density of the polarization film and the following equation (ii). The closer the molecular orientation of the polarization film is to 1, the more orderedly the molecules (compounds) within the polarization film are oriented. The molecular orientation of the polarization film composed of compound (CE) was 0.16.

[0148] Equation (ii): Degree of molecular orientation of the polarization film = Surface charge density of the polarization film / (Permanent dipole moment of the compound × Molecular density of the compound) In equation (ii), the permanent dipole moment of the compound and the molecular density of the compound are calculated using the electronic structure program "Gaussian 16" as described above.

[0149] [4.1.2] Examples 1 to 4 Using the measurement results from Examples 1 to 4 (see Figure 8), the absolute value of the surface potential per unit thickness was calculated by the least squares method. As a result, the absolute value of the surface potential per unit thickness of the polarization film made of compound (I-1) was 159 mV / nm.

[0150] Using the absolute value of the surface potential per unit thickness of the polarization film, the surface charge density of the polarization film made of compound (I-1) was calculated using equation (i) above. The surface charge density of the polarization film was 4.3 mC / m 2 That was the case.

[0151] The molecular orientation of the polarization film was calculated using the surface charge density of the polarization film and equation (ii) above. The molecular orientation of the polarization film composed of compound (I-1) was 0.22.

[0152] [4.1.3] Examples 5 to 8 Using the measurement results from Examples 5 to 8 (see Figure 9), the absolute value of the surface potential per unit thickness was calculated by the least squares method. As a result, the absolute value of the surface potential per unit thickness of the polarization film made of compound (I-2) was 223 mV / nm.

[0153] The surface charge density of the polarization film was calculated using the absolute value of the surface potential per unit thickness of the polarization film, according to equation (i) above. The surface charge density of the polarization film composed of compound (I-2) was 6.0 mC / m 2 That was the case.

[0154] The molecular orientation of the polarization film was calculated using the surface charge density of the polarization film and equation (ii) above. The molecular orientation of the polarization film composed of compound (I-2) was 0.38.

[0155] [4.1.4] Summary It was found that the molecular orientation of the polarization film made of compound (I-1) and the molecular orientation of the polarization film made of compound (I-1) were both higher than that of the polarization film made of compound (CE). As a result, it was found that the substrate-mounted polarization films of Examples 1 to 8 are "substrate-mounted polarization films with a high molecular orientation."

[0156] The surface charge density of electrets based on CYTOP®, which are used as conventional polymer electret materials (hereinafter also referred to as "CYTOP films"), is approximately 2.0 mC / m². 2 This is the case (see Non-Patent Literature 1 below). The output of a vibration power generation element is proportional to the square of the surface charge density of the electret. Therefore, it can be expected that the power generation output of a vibration power generation element using a polarization film made of compound (I-1) will be 4.6 times or more that of a vibration power generation element using a CYTOP film. CYTOP® is represented by the following formula (Y). Non-patent document 1: Yuji Suzuki, IEEJ TRANSACTIONS ON ELECTRICAL AND ELECTRONIC ENGINEERING, 2011, 6, 101-111

[0157] [ka]

[0158] [4.2] Vibration power generation test A substrate-mounted polarization film was obtained by depositing a 100 nm thick vapor-deposited thin film (I-1) of compound (I-1) onto an ITO-coated glass substrate using vacuum deposition. A substrate-mounted polarization film was also obtained by depositing a 100 nm thick vapor-deposited thin film (6FDI-2oBN) represented by the following formula (Z) onto an ITO-coated glass substrate using vacuum deposition. The vapor-deposited thin film of 6FDI-2oBN is a thin film exhibiting a negative surface potential. The vapor-deposited thin film of compound (I-1) is a thin film exhibiting a positive surface potential.

[0159] [ka]

[0160] Using an ultra-high vacuum Kelvin probe system (KP Technology: UHVKP020), induced currents were measured in a stainless steel electrode vibrating at a height of 1 mm above the surface of each thin film. The circular stainless steel electrode had a diameter of 4 mm and a vibration frequency of 59.2 Hz. A current was generated on each thin film in conjunction with the vibration of the electrode, and the polarity of the induced current reversed due to the different polarities of the surface potentials of the thin films. The surface potential of the deposited thin film (I-1) was higher than that of the deposited thin film (6FDI-2oBN). Therefore, the amplitude of the current was larger in the deposited thin film (I-1). The measurement results are shown in Figure 10.

[0161] The results of the vibration power generation test showed that the deposited thin film (I-1) can be used as an electret thin film exhibiting excellent properties.

[0162] [4.3] Experiments with organic light-emitting devices An organic light-emitting device (A) was fabricated by vacuum deposition in the following order on a cleaned ITO-coated glass substrate (thickness: 100 nm): an Al thin film (thickness: 0.5 nm), a Liq thin film represented by the following formula (Z2) (thickness: 2 nm), a compound (I-1) thin film (thickness: 3 nm), a co-deposited thin film of SF3-TRZ represented by the following formula (Z1) and Liq represented by the following formula (Z2) (thickness: 45 nm), a co-deposited thin film of DSA-Ph represented by the following formula (Z3) and MADN represented by the following formula (Z4) (thickness: 20 nm), a TAPC thin film represented by the following formula (Z5) (thickness: 20 nm), a deposited MoO3 thin film (composition: MoOx, thickness: 10 nm), and an Al thin film (thickness: 100 nm).

[0163] [ka]

[0164] An organic light-emitting element (B) was fabricated in the same manner as described above, except that a thin film of compound (I-1) was not formed.

[0165] Using a source meter, a positive voltage was applied to the upper electrode, an Al thin film (thickness: 100 nm), and the frontal brightness of the light emitted from the ITO side at each voltage was measured using a luminance meter. The emission voltage (luminance: 1 cd / m²) of the organic light-emitting element (B) was measured. 2 The voltage was 9.0V. The light emission voltage (luminance: 1 cd / m²) of the organic light-emitting element (A) 2 The voltage was 5.4V. The maximum current efficiency of organic light-emitting element (B) was 6.2 cd / A. The maximum current efficiency of organic light-emitting element (A) was 11 cd / A. The measurement results are shown in Figures 11 and 12. In Figures 11 and 12, "with thin film of compound (I-1)" refers to organic light-emitting element (A), and "without thin film of compound (I-1)" refers to organic light-emitting element (B).

[0166] Experimental results with organic light-emitting diodes showed that inserting a thin film of a polarized compound (I-1) into the organic light-emitting diode improved the electron injection characteristics of the diode and also improved the luminous efficiency of the diode. [Explanation of Symbols]

[0167] 1A, 1B, and 1C vibration power generation elements 10 and 110 polarization films with substrates 11 and 111 polarization films 12 and 112 substrates 13 and 113 electrodes 20A, 20B, and 120 electrode substrates 21 and 121 counter electrodes 22 and 122 substrates 23 polarization film 30 load resistor 40 and 140 spacers 100 evaluation vibration power generation element

Claims

1. The device comprises a substrate and a polarization film formed on at least one of the two main surfaces of the substrate, A substrate-mounted polarization film, wherein the polarization film contains a compound represented by the following formula (I). 【Chemistry 1】 (In formula (I), Z, A １ A ２ , X １ and X ２ This is either the first combination or the second combination, and does not contain a fluorine atom. In the first combination described above, Z represents a divalent polar functional group that imparts a bent structure to the compound. A １ and A ２ However, each independently represents a single bond or a divalent linking group, X １ and X ２ However, each independently represents a monovalent organic group, and the monovalent organic group represents an alkyl group having 5 to 24 carbon atoms, a cycloalkyl group having 5 to 20 carbon atoms, or an alkylcycloalkyl group having 5 to 30 carbon atoms. Some or all of the carbon atoms constituting the alkyl group, the cycloalkyl group, and the alkylcycloalkyl group may be substituted with heteroatoms. In the second combination described above, Z represents a divalent organic group that imparts a bent structure to the compound, and the divalent organic group represents a cycloalkylene group having 7 to 20 carbon atoms, an alkylcycloalkylene group having 7 to 30 carbon atoms, or a divalent aromatic hydrocarbon group having 7 to 80 carbon atoms. A １ and A ２ each independently represents a single bond or a divalent linking group, X １ and X ２ However, each independently represents a monovalent polar functional group, Some or all of the carbon atoms constituting the cycloalkylene group, the alkylcycloalkylene group, and the aromatic hydrocarbon group may be substituted with heteroatoms.

2. The polarization film with a substrate according to claim 1, wherein the divalent linking group is a C1 methylene group, a group represented by the following formula (a-1), a group represented by the following formula (a-2), a group represented by the following formula (a-3), a group represented by the following formula (a-4), or a group represented by the following formula (a-5). 【Chemistry 2】 (In equations (a-1) to (a-5), * indicates the bonding position.)

3. Z, A １ A ２ , X １ and X ２ However, this is the first combination, The polarization film with a substrate according to claim 2, wherein the divalent polar functional group is a sulfonyl group, a 1- to 15-ring arylphosphine oxide group, a benzonitrile group, a phthalimide group, or a pyridine group.

4. The polarization film with a substrate according to claim 3, wherein the monovalent organic group represents a C5-C8 alkyl group, a C5-C8 cycloalkyl group, or a C5-C8 alkylcycloalkyl group.

5. Z, A １ A ２ , X １ and X ２ However, this is the second combination, The polarization film with a substrate according to claim 2, wherein the monovalent polar functional group is a monocyclic arylsulfonyl group, a bicyclic arylphosphine oxide group, a nitrile group, a phthalimide group, or a pyridine group.

6. The polarization film with a substrate according to claim 5, wherein the divalent organic group represents a cycloalkylene group having 7 to 10 carbon atoms, an alkylcycloalkylene group having 7 to 10 carbon atoms, or a divalent aromatic hydrocarbon group having 7 to 22 carbon atoms.

7. The polarization film with a substrate according to claim 1, wherein the compound has a permanent dipole moment of 1.0 Debye to 30.0 Debye in absolute value.

8. A polarization film with a substrate according to claim 1, wherein the absolute value of the surface potential per unit thickness is 50 mV / nm to 1500 mV / nm.

9. A vibration power generation element comprising a polarization film with a substrate according to any one of claims 1 to 8.

10. An organic light-emitting element comprising a polarization film separated from a substrate-mounted polarization film according to any one of claims 1 to 8.

11. A method for manufacturing a substrate-mounted polarization film according to any one of claims 1 to 8, To prepare a raw material containing the aforementioned compound, Using the aforementioned raw materials, the polarization film is formed on at least one of the two main surfaces of the substrate by vacuum deposition or a wet process method. A method for manufacturing a polarization film with a substrate, including the method described above.

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