Polymers and light-controlling elements

Abstract

To provide a polymer capable of suitably using in a light control element useful in a wavelength band shorter than a C band.SOLUTION: There is provided a polymer represented by formula (1). [In formula (1), RA1 and RA2 each independently represent an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 12 carbon atoms, or an alkylaryl group having 7 to 15 carbon atoms; the hydrogen atom that the alkyl group, the aryl group, and the alkylaryl group have, may be substituted with a halogen atom, and RA1 and RA2 may be linked to each other to form a saturated 3- to 12-membered ring together with the carbon atom to which they are attached. Po represents the polymer structure.]SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to polymers and light control elements. [Background technology]

[0002] Inorganic ferroelectric materials such as lithium niobate (LiNbO3) are known to be used as electro-optical materials (EO materials) that can be used in optical control elements such as optical modulators, optical switches, optical interconnects, optoelectronic circuits, wavelength converters, electric field sensors, THz wave generators and detectors, and optical phased arrays. Inorganic ferroelectric materials have limitations in terms of the speed, miniaturization, and integration of optical control elements, and it has also been difficult to hybridize them with semiconductor materials, which are advantageous for miniaturization and integration.

[0003] On the other hand, organic electro-optic polymers (organic EO polymers) exhibit a larger electro-optic effect than inorganic ferroelectric materials. Furthermore, organic EO polymers are capable of high-speed operation and can be easily hybridized with semiconductors, ferroelectrics, and their microstructures. As such, organic EO polymers are expected to be the materials that will support next-generation optical communications, due to their high speed and power-saving capabilities, as well as their potential for miniaturization and integration. [Prior art documents] [Non-patent literature]

[0004] [Non-Patent Document 1] "Organic Materials for Nonlinear Optics," Chemical Society of Japan, Quarterly Chemistry Review No. 15 (1992) [Non-patent document 2] "Organic Nonlinear Optical Materials", Ch. Bosshard, et al., Gordon and Breach Publishers(1995) [Non-patent document 3] "Latest Technology of Optical Organic Materials for Information and Communications," edited by Toshikuni Kaino, CMC Publishing, 2007 [Non-patent document 4] "Organic Electro-Optics and Photonics", Larry R. Dalton, et. al., Cambridge University Press(2015) Summary of the Invention [Problem to be solved by the invention]

[0005] Previous development of organic EO polymers has been carried out on the assumption that they will be used in the C-band, which is the wavelength band used for long-distance communications. In recent years, there has been a demand for the development of optical control elements that are useful (highly efficient) in wavelength bands shorter than the C-band.

[0006] The present invention provides a novel polymer that can be suitably used as an electro-optical material in a light control element useful in a wavelength band shorter than the C band, and a light control element. [Means for solving the problem]

[0007] The present invention provides the following polymers: [1] A polymer represented by formula (1). [ka] [In formula (1), R A1 and R A2 are each independently an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 12 carbon atoms, or an alkylaryl group having 7 to 15 carbon atoms, and a hydrogen atom in the alkyl group, aryl group, or alkylaryl group may be substituted with a halogen atom; R A1 and R A2 may be linked to each other to form a 3- to 12-membered saturated alicyclic structure together with the carbon atom to which they are bonded. X represents a phenylene group, an ethylene group, or a phenylenevinylene group. R D1 represents an alkanediyl group having 1 to 10 carbon atoms, and R D2 represents an alkyl group having 1 to 10 carbon atoms, and RD1 and R D2 means that any carbon atoms contained therein are bonded to each other, and R D1 and R D2 may form a 3- to 12-membered saturated heterocyclic structure together with the nitrogen atom to which it is bonded. Y represents a linking group. Po represents a polymer structure. [2] In the formula (1), R A1 represents an alkyl group having 1 to 10 carbon atoms, R A2 represents a halogenated aryl group having 6 to 12 carbon atoms or an alkylaryl group having 7 to 15 carbon atoms, at least one hydrogen atom of which has been substituted with a halogen atom, The polymer according to [1], wherein X represents a phenylene vinylene group. [3] In the formula (1), R A1 and R A2 each independently represents an alkyl group having 1 to 10 carbon atoms, and R A1 and R A2 may be linked to each other to form a 3- to 12-membered saturated alicyclic structure together with the carbon atoms to which they are bonded, The polymer according to [1], wherein X represents a phenylene group. [4] The polymer according to any one of [1] to [3], wherein Y in the formula (1) represents a urethane bond. [5] The polymer according to any one of [1] to [4], wherein Po in the formula (1) represents a (meth)acrylic polymer structure. [6] An optical control element having an optical waveguide formed from the polymer according to any one of [1] to [5]. [Effects of the Invention]

[0008] The polymer of the present invention can be suitably used as an electro-optical material in a light control element that is useful in a wavelength band shorter than the C band. [Brief explanation of the drawings]

[0009] [Figure 1] FIG. 1 is a schematic diagram of a Mach-Zehnder interferometer type waveguide that can be provided in an optical control element. [Figure 2] FIG. 2 is a schematic diagram of the x-x' cross section of FIG. [Figure 3] 10 is an image showing a cross section of a light incident end surface of an optical modulator obtained in a comparative example. [Figure 4] 10 is a graph showing a time waveform of the optical modulation of the optical modulator obtained in the comparative example. [Figure 5] 10 is an image showing a cross section of a light incident end face of an optical modulator obtained in an example. [Figure 6] 10 is a graph showing the time waveform of the optical modulation of the optical modulator obtained in the example. DETAILED DESCRIPTION OF THE INVENTION

[0010] Hereinafter, embodiments of the present invention will be described, but the present invention is not limited to the following embodiments.

[0011] <Polymer> The polymer of this embodiment is a polymer represented by formula (1) (hereinafter, sometimes referred to as "polymer (1)"). [ka] [In formula (1), R A1 and R A2 each independently represents an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 12 carbon atoms, or an alkylaryl group having 7 to 15 carbon atoms, and a hydrogen atom in the alkyl group, aryl group, or alkylaryl group may be substituted with a halogen atom; R A1 and R A2 may be linked to each other to form a 3- to 12-membered saturated alicyclic structure together with the carbon atom to which they are bonded. X represents a phenylene group, an ethylene group, or a phenylenevinylene group. R D1 represents an alkanediyl group having 1 to 10 carbon atoms, and R D2represents an alkyl group having 1 to 10 carbon atoms, and R D2 may be bonded to Po, and R D1 and R D2 means that any carbon atoms contained therein are bonded to each other, and R D1 and R D2 may form a 3- to 12-membered saturated heterocyclic structure together with the nitrogen atom to which it is bonded. Y represents a linking group. Po represents a polymer structure.

[0012] The structure to the right of Y in formula (1) is a structure possessed by an electro-optic molecule (hereinafter, sometimes referred to as an "EO molecular structure"). The EO molecular structure is a structure to the right of X in formula (1) (hereinafter, sometimes referred to as an "acceptor structure") and -R between X and Y. D1 (R D2 )N- (hereinafter sometimes referred to as "donor structure") is connected via X. The donor structure of the EO molecular structure is connected to the polymer structure via Y.

[0013] R A1 and R A2 Examples of the alkyl group having 1 to 10 carbon atoms represented by the formula (I) include a methyl group, an ethyl group, a normal propyl group, an isopropyl group, a normal butyl group, a tert-butyl group, a normal pentyl group, a normal hexyl group, a normal heptyl group, and a 2-ethylhexyl group. The alkyl group is preferably an alkyl group having 1 to 5 carbon atoms. The alkyl group may be linear or branched, but is preferably linear. R A1 and R A2 The alkyl group represented by the formula (I) may be an alkyl group having 1 to 5 carbon atoms, and is preferably a methyl group. R A1 and R A2 Examples of the aryl group having 6 to 12 carbon atoms represented by the formula (I) include a phenyl group, a 1-naphthyl group, a 2-naphthyl group, and a biphenyl group, and a phenyl group is preferred. R A1 and R A2As the alkylaryl group having 7 to 15 carbon atoms represented by the formula: A1 and R A2 In the present invention, at least one hydrogen atom of an aryl group represented by the following formula is substituted with an alkyl group: The substituted alkyl group includes the alkyl groups described above, and is preferably an alkyl group having 1 to 5 carbon atoms.

[0014] R A1 and R A2 Examples of the halogen atom with which at least one hydrogen atom in the alkyl group, aryl group, and alkylaryl group represented by the formula (I) may be substituted include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. The number of hydrogen atoms that may be substituted with a halogen atom may be one or more, and when two or more hydrogen atoms are substituted with halogen atoms, the halogen atoms may be the same or different. The hydrogen atom in the alkylaryl group may be a hydrogen atom in the alkyl group of the alkylaryl group, or may be a hydrogen atom in the aromatic ring. Examples of the halogenated alkyl group in which at least one hydrogen atom of the alkyl group has been substituted with a halogen atom include a fluoromethyl group, a difluoromethyl group, a trifluoromethyl group, a 2-fluoroethyl group, a 1,2-difluoroethyl group, a chloromethyl group, a 2-chloroethyl group, a 1,2-dichloroethyl group, a bromomethyl group, a 2-bromoethyl group, a 1-bromopropyl group, a 2-bromopropyl group, a 3-bromopropyl group, and an iodomethyl group, and a trifluoromethyl group is preferred. The halogenated aryl group in which at least one hydrogen atom of the aryl group is substituted with a halogen atom is preferably a halogenated phenyl group, such as a fluorophenyl group, a difluorophenyl group, a trifluorophenyl group, a pentafluorophenyl group, a chlorophenyl group, a dichlorophenyl group, a bromophenyl group, and a chlorofluorophenyl group. Examples of the alkylaryl group in which at least one hydrogen atom has been substituted with a halogen atom include a trifluoromethylphenyl group and a chloro(trifluoromethyl)phenyl group.

[0015] R A1 and R A2 R may have the same structure as each other, or may have different structures from each other. A1 and R A2 If and have the same structure, R A1 and R A2 R preferably represents an alkyl group having 1 to 10 carbon atoms, and more preferably represents a methyl group. A1 and R A2 When and have different structures, they preferably represent the following [a1] or [a2]. [a1]R A1 represents an alkyl group having 1 to 10 carbon atoms, and R A2 represents a group in which at least one hydrogen atom of a halogenated aryl group having 6 to 12 carbon atoms or an alkylaryl group having 7 to 15 carbon atoms has been substituted with a halogen atom. [a2]R A1 represents a halogenated alkyl group having 1 to 10 carbon atoms, and R A2 represents an aryl group having 6 to 12 carbon atoms.

[0016] R A1 and R A2 As a 3- to 12-membered saturated alicyclic structure formed by combining these with the carbon atoms to which they are bonded, R A1 The terminal carbon atom of R A2 Examples of the saturated alicyclic structure include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group, a cyclononyl group, and a cyclodecyl group, and a cyclopentyl group or a cyclohexyl group is preferred.

[0017] Examples of the acceptor structure in formula (1) include the structures shown below: In the following formula, *1 represents a bond to X. [ka]

[0018] R D1 Examples of the alkanediyl group having 1 to 10 carbon atoms represented by the formula (I) include a methylene group, an ethylene group, a propane-1,3-diyl group, a butane-1,3-diyl group, a butane-1,4-diyl group, a pentane-1,5-diyl group, a hexane-1,6-diyl group, a heptane-1,7-diyl group, an octane-1,8-diyl group, and a decane-1,10-diyl group. The alkanediyl group is preferably an alkanediyl group having 1 to 5 carbon atoms. The alkanediyl group may be linear or branched, but is preferably linear.

[0019] R D2 As the alkyl group having 1 to 10 carbon atoms represented by the formula A1 and R A2 Examples of the alkyl group include the alkyl groups described above as the alkyl group having 1 to 10 carbon atoms and represented by the following formula: The alkyl group is preferably an alkyl group having 1 to 5 carbon atoms. The alkyl group may be linear or branched, but is preferably linear.

[0020] R D1 and R D2 The 3- to 12-membered saturated heterocyclic structure formed by combining these with the nitrogen atom is represented by R D1 and any carbon atom in R D2 and any of the carbon atoms contained in R D1 and any carbon atom in R D2 and the terminal carbon atoms of R are preferably linked to each other to form a 3- to 12-membered saturated heterocyclic structure. D1 and any carbon atom in R D2and the terminal carbon atoms of the saturated heterocyclic group are bonded to each other to form a 6-membered saturated heterocyclic structure. The saturated heterocyclic structure may contain a heteroatom other than the nitrogen atom, but preferably contains one heteroatom. Examples of the saturated heterocyclic structure include a group in which one hydrogen atom has been removed from the ring structure of a saturated heterocyclic group such as an aziridine group, a pyrrolidine group, a piperidine group, or an azocane group; and a group in which an alkanediyl group is located on an atom (preferably a carbon atom) forming the ring skeleton of a saturated heterocyclic group such as an aziridine group, a pyrrolidine group, a piperidine group, or an azocane group. The number of carbon atoms in the alkanediyl group is preferably 1 to 5, and may be 1 to 3.

[0021] Examples of the donor structure in formula (1) include the structures shown below: In the following formula, *2 represents a bond to Y. [ka]

[0022] The phenylene vinylene group represented by X is bonded to the nitrogen atom in the formula (1) at the phenylene group side, and the polymer (1) is -YR D1 (R D2 It is preferred that the alkyl group forms the structure N-C6H4-(CH)2-.

[0023] Polymer (1) is R D1 represents the above-mentioned alkanediyl group, and R D2 represents the above alkyl group, and R D1 and R D2 and may form the above-mentioned saturated heterocyclic structure, R A1 , R A2 and X is preferably any one of the following [e1] to [e3]. [e1]R A1 represents an alkyl group having 1 to 10 carbon atoms, and R A2 represents a halogenated aryl group having 6 to 12 carbon atoms or a group in which at least one hydrogen atom of an alkylaryl group having 7 to 15 carbon atoms has been substituted with a halogen atom, and X represents a phenylenevinylene group. [e2]R A1 and R A2 each independently represents an alkyl group having 1 to 10 carbon atoms, and R A1 and R A2 may be linked to each other to form a 3- to 12-membered saturated alicyclic structure together with the carbon atom to which they are bonded, and X represents a phenylene group. [e3](i)R A1 and R A2 each independently represents an alkyl group having 1 to 10 carbon atoms; (ii) R A1 represents an alkyl group having 1 to 10 carbon atoms, and R A2 represents a halogenated aryl group having 6 to 12 carbon atoms, or (iii) R A1 represents a halogenated alkyl group having 1 to 10 carbon atoms, and R A2 represents an aryl group having 6 to 12 carbon atoms, and X represents an ethylene group.

[0024] Examples of the EO molecular structure of polymer (1) include structures (1) to (9) shown in Table 1. In Table 1, structure (1) represents that in formula (1), the donor structure is any of the structures represented by formulas (d-1) to (d-14) above, X is a structure represented by *3-C6H4-(CH)2-, and the acceptor structure is a structure represented by formula (a-19) or formula (a-20) above. *3 in the formula representing X represents a bond to the N atom. [Table 1]

[0025] The linking group represented by Y is a group that links the donor structure of the EO molecular structure with the polymer structure represented by Po. Examples of the linking group include a (thio)urethane bond, a (thio)urea bond, and a (thio)amide bond. The term "(thio)urethane" refers to at least one selected from urethane and thiourethane. The same applies to (thio)urea and (thio)amide. The linking group is preferably a urethane bond. When Y represents a urethane bond, Po-YR in formula (1) can be used. D1- is the structure Po-HNC(O)OR D1 - is preferred.

[0026] Examples of the polymer structure represented by Po include (meth)acrylic polymer structures such as PMMA, polyimide structures, polycarbonate structures, olefin polymer structures, cycloolefin polymer structures, vinyl polymer structures, polyester structures, polyalkylsiloxane structures, and epoxy resin structures. The polymer structure may be a homopolymer structure or a copolymer structure obtained by polymerizing two or more types of monomers. (Meth)acrylic means at least one selected from acrylic and methacrylic. The same applies to (meth)acrylates, etc.

[0027] The polymer structure represented by Po preferably has a (meth)acrylic polymer structure, and more preferably has a (meth)acrylic polymer structure having at least one group selected from a (thio)urethane bond, an alkyl group, a monocyclic or polycyclic saturated alicyclic hydrocarbon group, and an iso(thio)cyanato group in the side chain. A1 and R A2 Examples of the alkyl group include the alkyl groups described above as alkyl groups having 1 to 10 carbon atoms and represented by the following formula: The monocyclic or polycyclic saturated alicyclic hydrocarbon group is preferably a saturated alicyclic hydrocarbon group having 3 to 12 carbon atoms, and examples thereof include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a t-butylcyclohexyl group, a cycloheptyl group, a cyclooctyl group, an adamantyl group, and a dicyclopentanyl group. The (meth)acrylic polymer structure refers to a repeating unit formed by polymerizing a (meth)acrylic acid ester as a monomer. The (meth)acrylic acid ester used to form the (meth)acrylic polymer structure may be one type or two or more types.

[0028] Examples of the monomer component used to obtain the (meth)acrylic polymer structure include one or more selected from the group consisting of alkyl (meth)acrylates such as methyl (meth)acrylate; (meth)acrylates having an iso(thio)cyanato group such as 2-(isocyanatoethyl) methacrylate and 2-(2-methacryloyloxyethyloxy)ethyl isocyanate; and (meth)acrylates having a polycyclic saturated alicyclic hydrocarbon group such as adamantyl methacrylate, dicyclopentanyl methacrylate and isobornyl methacrylate.

[0029] Examples of the (meth)acrylic polymer structure include the structures shown below. [ka] [In the formula, R P1 represents an alkyl group or a monocyclic or polycyclic saturated alicyclic hydrocarbon group, k, p, and r represent integers of 1 or more, and *4 represents a bond to Y.]

[0030] Polymer (1) is a polymer that exhibits second-order nonlinear optical effects. Polymer (1) has a figure of merit (FOM1) of 1.2 (V·cm) at wavelengths of 1259 nm or less, which is shorter than the C-band. -1 or greater, and / or the figure of merit FOM2 is 0.20 (V·dB) -1 It is preferable that the figure of merit FOM1 and FOM2 are values ​​calculated by the following formulas (I) and (II), respectively. In this specification, the figures of merit FOM1 and FOM2 of a specific light control element can be determined using heteroscedastic analysis (Gaussian dispersion equation), as will be explained in the examples described later.

number

[0031] The figure of merit (FOM1) of polymer (1) is 1.2 (V·cm) -1 or greater, and / or the figure of merit FOM2 is 0.20 (V·dB) -1The wavelength that is equal to or greater than 1100 nm may be equal to or less than 1000 nm, may be equal to or less than 900 nm, may be equal to or less than 800 nm, may be equal to or less than 680 nm, may be equal to or less than 650 nm, and is usually equal to or greater than 200 nm, may be equal to or greater than 300 nm, may be equal to or greater than 400 nm, or may be equal to or greater than 500 nm.

[0032] The figure of merit (FOM1) of polymer (1) is 1.4 (V·cm) in any of the above wavelength ranges. -1 May be more than 1.5 (V cm) -1 May be more than 1.8 (V cm) -1 It can be more than 48 (V cm) -1 The polymer (1) figure of merit FOM2 is 0.25 (V·dB) in any of the above wavelength ranges. -1 May be greater than 0.30 (V·dB) -1 It can be more than 8 (V·dB) -1 The following is the result.

[0033] Polymer (1) can be obtained, for example, by reacting a polymer (Po1) containing the polymer structure and reactive groups of the polymer represented by formula (1) with a compound (EO1) containing the EO molecular structure and reactive groups of the polymer represented by formula (1). [ka] [In the formula, R A1 , R A2 , X, R D1 , R D2 , and Y have the same meaning as above, Z P1 and Z D1 each independently represents a reactive group.

[0034] Z represents the reactive group in the polymer (Po1) P1 and Z, which represents a reactive group in the compound (EO1). D1is a functional group that can form a linking group represented by Y in formula (1) by reacting these two reactive groups. P1 and Z D1 can be each independently selected from the group consisting of an iso(thio)cyanato group, a hydroxyl group, a thiol group, an amino group, a carboxyl group, and an acid anhydride group. P1 and Z D1 Preferably, one of Z is an iso(thio)cyanato group and the other is a hydroxyl group; P1 is an isocyanato group, and Z D1 is preferably a hydroxyl group. The polymer (Po1) usually contains a plurality of reactive groups Z P1 In the polymer (1), the reactive group Z contained in the polymer (Po1) is P1 The compound (EO1) is bonded to a part of the compound (EO1), and a part of the compound (EO1) is bonded to a reactive group Z. P1 It may remain as such.

[0035] Compound (EO1) may be obtained, for example, by reacting compound (DX1) containing a donor structure and an X structure with compound (A1) containing an acceptor structure, or by reacting compound (AX2) containing an X structure and an acceptor structure with compound (D2) containing a donor structure. [ka] [In the formula, R A1 , R A2 , X, R D1 , R D2 , and Z D1 means the same as above, and Z D2 , Z D3 , Z A1 , and Z A2 each independently represents a reactive group.

[0036] Z, which represents a reactive group in compound (DX1), D2 and Z, which represents a reactive group in compound (A1). A1The reactive group Z in the compound (AX2) is not particularly limited as long as it is a functional group that can form a linking group represented by X in the compound (EO1) by reacting these two reactive groups. A2 and Z, which represents a reactive group in compound (D2). D3 is not particularly limited as long as it is a functional group that can form a linking group represented by X in the compound (EO1) by reaction of these two reactive groups.

[0037] <Light control element> The polymer (1) can be used as an electro-optical material applied to an optical control element. The optical control element of this embodiment can have, for example, an optical waveguide formed of the polymer (1). Examples of optical control elements include optical modulators, optical switches, optical transceivers, optical phased arrays, LiDAR, smart glasses, optical interconnects, optoelectronic circuits, wavelength converters, electric field sensors, and THz wave generators and detectors.

[0038] The light control element can be suitably used in wavelength bands shorter than the C band. The wavelength band in which the light control element is used is typically 1259 nm or less, but may be 1100 nm or less, 1000 nm or less, 900 nm or less, 800 nm or less, 680 nm or less, or 650 nm or less, and is typically 200 nm or more, 300 nm or more, 400 nm or more, or 500 nm or more. For example, among the light control elements using polymer (1) having the EO molecular structures (1) to (9) shown in Table 1 above, a light control element in which the EO molecular structure of polymer (1) is structure (1) is considered to be suitably used in the longest wavelength region of the above wavelength bands. The wavelength ranges in which structures (2), (3), (4), (5), (6), (7), (8), and (9) are most suitable for use are shorter wavelengths. It is believed that a light control element in which the EO molecular structure of polymer (1) is structure (9) can be used most effectively in the shortest wavelength ranges. For example, a light control element using polymer (1) having the EO molecular structure of structure (2) shown in Table 1 above can be used effectively in the wavelength range of 780 nm to 1000 nm. A light control element using polymer (1) having the EO molecular structure of structure (6) shown in Table 1 above can be used effectively in the wavelength range of 630 nm to 700 nm. A light control element using polymer (1) having the EO molecular structure of structure (9) shown in Table 1 above can be used effectively in the wavelength range of 530 nm to 600 nm.

[0039] FIG. 1 is a schematic diagram of an MZ-type waveguide that can be included in an optical control element. FIG. 2 is a schematic diagram of the x-x' cross section of FIG. 1. For example, as shown in FIG. 1, the optical control element may have an optical waveguide that is a single-arm driven Mach-Zehnder interferometer type waveguide (hereinafter, sometimes referred to as an "MZ-type waveguide"). In an MZ-type waveguide, light input from the left side of FIG. 1 propagates through the optical waveguide. As shown in FIG. 2, an optical waveguide generally comprises a core 11 through which light mainly propagates and a cladding 12 provided around the core 11, and the core 11 is formed of a polymer (1). Light input into the optical waveguide of the MZ-type waveguide propagates through two branched arms 10a and 10b as shown in FIG. 1, and then recombines to interfere with each other and is output. An upper electrode 15 for phase modulation is disposed on the cladding 12 of one of the two arms 10a and 10b. In this specification, phase modulation refers to shifting the phase of input light. In the case of an MZ waveguide, phase modulation refers to shifting the phase of light propagating through one of the arms 10a, and the phase shift can be achieved by applying an electric field using the upper electrode 15 arranged on the arm 10a.

[0040] In optical control devices, the index used to evaluate high speed is the half-wave voltage (the voltage when the intensity of the output light becomes zero) in the MZ-type waveguide, V π [V], and the length of the phase modulation region of the MZ waveguide is L (Figure 1), then the half-wave voltage V π and the length L (formula (i-1)). The phase modulation region is the region where the above-mentioned phase modulation is performed, and in the MZ type waveguide shown in FIG. 1, it is the region where the upper electrode 15 of one arm portion 10a is arranged. Therefore, the length L of the phase modulation region is the length of the upper electrode 15 (length in the direction of light propagation). Also, in an optical control element, the index for evaluating power saving is expressed as the half-wave voltage V π [V], and the propagation loss in the phase modulation region is Loss [dB], then the half-wave voltage V π and the propagation loss (equation (ii-1)).

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[0041] V in formula (i-1) π The value of L and V in formula (ii-1) π The smaller the Loss value, the better the optical control element's high speed and power saving. Therefore, to obtain an optical control element with excellent high speed, it is preferable to reduce the distance d in formula (i-1). Furthermore, to obtain an optical control element with excellent power saving, it is preferable to reduce the distance d in formula (ii-1) (FIGS. 1 and 2).

[0042] The shape (structure) of the optical waveguide may be a channel waveguide as shown in FIG. 2, or may be a ridge waveguide, an inverted ridge waveguide, a photonic crystal waveguide, or the like.

[0043] The cladding 12 is not particularly limited and may be made of any known material as long as it is made of a material having a refractive index lower than that of the core 11. Examples of materials constituting the cladding 12 include glass such as quartz glass and multi-component glass, fluororesin, silicone resin, organic silica (inorganic silica to which an organic component is bonded), (meth)acrylic polymers such as PMMA, polyimide, polycarbonate, olefin polymers, and cycloolefin polymers.

[0044] When the upper electrode 15 and the lower electrode 16 are provided in the phase modulation region as shown in FIGS. 1 and 2, the upper electrode 15 and the lower electrode 16 may be formed of a known conductive material such as a metal material.

[0045] The optical control element may be a Mach-Zehnder (MZ) optical modulator in which an MZ interferometer is configured using an optical waveguide as shown in Figure 1, a nested MZ optical modulator in which an MZ interferometer is integrated on two branch paths of an MZ interferometer, a single phase modulator without a branch structure, or an optical phased array configured with multiple branches and phase modulators. [Example]

[0046] The present invention will be explained in more detail below by showing examples, but the present invention is not limited to these examples.

[0047] Comparative Example 1 An EO polymer (EO-1) in which a compound represented by formula (E-1) (hereinafter, sometimes referred to as "compound (E-1)") was bonded to a base polymer was obtained by the following procedure.

[0048] (Preparation of Compound (E-1)) Compound (E-1) was prepared according to the procedure described in Example 57 of WO 2011 / 024774. [ka]

[0049] (Synthesis of base polymer (A-1)) 24.15 g (241.2 mmol) of methyl methacrylate (MMA), 10.65 g (68.64 mmol) of 2-(isocyanatoethyl) methacrylate (MOI), and 1.53 g (9.32 mmol) of azobisisobutyronitrile (AIBN) were dissolved in 57 mL of dehydrated toluene, and the mixture was then filled with argon and stirred in an oil bath at 60°C for 2 hours. After cooling to room temperature, the reaction solution was added dropwise to 1420 mL of dehydrated diisopropyl ether (IPE), and the precipitate was collected by filtration. After washing with dehydrated IPE, the mixture was dried under reduced pressure at 70°C to obtain 24.1 g of base polymer (A-1).

[0050] (Derivatization of base polymer (A-1) (methyl carbamate derivative)) Under Ar gas, 7.0 g of base polymer (A-1) was dissolved in 245 mL of dehydrated tetrahydrofuran, and 15 mL of dehydrated methanol and 280 μL of dibutyltin dilaurate (DBTDL) were added, followed by stirring for 2 hours in an oil bath at 60°C. After cooling, the reaction solution was poured into 2.8 L of diisopropyl ether (IPE) and stirred. The precipitated powder was collected by filtration, washed with IPE, and then dried under reduced pressure at 70°C to obtain a derivative of base polymer (A-1).

[0051] The resulting derivative was measured using a differential scanning calorimeter (Rigaku Thermo plus DSC 8230, manufactured by Rigaku Corporation) under conditions of a 10 mg sample and a reference sample in an empty Al container under a nitrogen atmosphere at a heating rate of 10°C / min, and the glass transition temperature Tg was found to be 97°C. The molecular weight was also determined by GPC using an Alliance e2695 (manufactured by Nihon Waters) (column: Shodex GPC KF-804L (8 mmφ × 300 mm), developing solvent: THF, column temperature: 40°C), and the weight-average molecular weight Mw was 76,300 and the number-average molecular weight Mn was 35,500.

[0052] (Production of EO polymer (EO-1)) 4.70 g of the base polymer (A-1) obtained above was dissolved in 190 mL of dehydrated tetrahydrofuran (THF). 2.10 g (3.04 mmol) of compound (E-1) and 150 μL of dibutyltin dilaurate (DBTDL) were added and stirred in an oil bath at 60°C for 2 hours. 10 mL of dehydrated methanol and 60 μL of DBTDL were then added and stirred at 60°C for 30 minutes. After cooling, the reaction solution was poured into 1500 mL of diisopropyl ether (IPE) and stirred. The precipitated powder was collected by filtration, washed with 1 L of IPE, and then dried under reduced pressure at 70°C. 2.83 g of EO polymer (EO-1) was obtained as a black powder (glass transition temperature Tg: 131°C).

[0053] Examples 1 and 2 In the following procedure, EO polymers (EO-4) and (EO-5) in which the compounds represented by the following formulas (E-4) and (E-5) (hereinafter sometimes referred to as "compound (E-4)", etc.) are bonded to the base polymer were obtained.

[0054] (Preparation of Compound (E-4)) Compound (E-4) ((E)-2-(4-(4-(butyl(4-hydroxybutyl)amino)styryl)-3-cyano-5-methyl-5-(perfluorophenyl)furan-2(5H)-ylidene)malononitrile) was synthesized in the following procedure.

[0055] (Synthesis of 4-t-butyldiphenylsilyloxybutylbutylamine (E4-1))

Chemical formula

[0056] (Synthesis of N-butyl-N-(4-(t-butyldiphenylsilyl)oxy)butylaniline (E4-2))

Chemical formula

[0057] <Synthesis of 4-(butyl(phenyl)amino)butan-1-ol (E4-3)> [ka] To a solution of compound (E4-2) (54.7 g, 0.12 mmol)) and THF (500 mL) was added 1.0 M TBAF-THF (151 mL, 0.15 mol) under an Ar stream, and the mixture was stirred at 22-23°C for 1 hour. The reaction mixture was dispersed in water (1 L) and extracted with ethyl acetate. The mixture was washed with water (twice) and saturated brine, dried over anhydrous sodium sulfate, and the solvent was concentrated under reduced pressure to obtain 56.5 g of a residue. This residue was purified by silica gel chromatography (silica gel 600 g, n-Hex / AcOEt: 3 / 1, 1 / 2) to obtain 26.5 g of a compound represented by formula (E4-3) (hereinafter sometimes referred to as "compound (E4-3)") (yield: 100%).

[0058] <Synthesis of 4-(butyl(phenyl)amino)butyl acetate (E4-4)> [ka] A mixture of compound (E4-3) (26.5 g (0.12 mol)), triethylamine (24.2 g (0.24 mol)), and dry methylene chloride (200 mL) was ice-cooled under an Ar stream, and acetyl chloride (12.3 g (0.16 mol)) was added dropwise over 25 minutes at 3 to 8°C. After stirring at the same temperature for 1 hour, water (200 mL) was added dropwise to quench the reaction mixture. After separation, the mixture was washed with water and saturated brine, dried over anhydrous sodium sulfate, and the solvent was concentrated under reduced pressure to obtain 31 g of residue. This residue was purified by silica gel chromatography (silica gel 230 g, n-Hex / AcOEt: 10 / 1, 9 / 1) to obtain 28.2 g of the compound represented by formula (E4-4) (hereinafter sometimes referred to as "compound (E4-4)") (yield: 89%).

[0059] <Synthesis of (N,N-4-acetoxybutylbutyl)-4-formylaminobenzene (E4-5)> [ka] Dry DMF (160 mL) was ice-cooled under an Ar stream, and phosphorus oxychloride (19.8 g (128.8 mol)) was added dropwise at a temperature of 5 to 7° C. over 15 minutes, then the temperature was raised to room temperature and the mixture was stirred for 30 minutes. Subsequently, 28.2 g (107.1 mol) of compound (E4-4) and 85 mL of dry DMF were added dropwise at 18 to 30°C over 15 minutes, and the mixture was then heated to 85 to 90°C and stirred for 2.5 hours. After cooling on ice, 240 mL of 20% aqueous NaOAc was added dropwise. The mixture was stirred at room temperature for 1 hour and then extracted with ethyl acetate. The organic layer obtained by extraction was washed twice with water and then with saturated brine, dried over anhydrous sodium sulfate, and the solvent was concentrated under reduced pressure to obtain a residue (29.4 g). This residue was purified by silica gel chromatography (250 g of silica gel, n-Hex / AcOEt: 5 / 1, 1 / 1) to obtain 26.4 g of a compound represented by formula (E4-5) (hereinafter sometimes referred to as "compound (E4-5)") (yield: 85%).

[0060] <Synthesis of (N,N-4-hydroxybutylbutyl)-4-formylaminobenzene (E4-6)> [ka] Under an Ar stream, 2N aqueous NaOH (152 mL (304 mmol)) was added dropwise to a solution of compound (E4-5) (26.4 g (90.6 mmol)) and EtOH (165 mL) over 30 minutes at 21 to 25°C, followed by stirring for 1 hour. The reaction mixture was dispersed in water (1 L) and extracted with ethyl acetate. The organic layer obtained by extraction was washed twice with water and then with saturated brine, dried over anhydrous sodium sulfate, and the solvent was concentrated under reduced pressure to obtain a residue (21.8 g). This residue was purified by silica gel chromatography (silica gel 220 g, n-Hex / AcOEt: 1 / 1 → 1 / 2) to obtain 20.8 g of a compound represented by formula (E4-6) (hereinafter sometimes referred to as "compound (E4-6)") (yield: 92%).

[0061] Preparation of 2-[3-cyano-4,5-dimethyl-5-(perfluorophenyl)furan-2(5H)-ylidene]malononitrile (E4-7) The compound represented by formula (E4-7) (hereinafter sometimes referred to as "compound (E4-7)") was prepared according to the procedure described in Example 1 of EO Molecule Synthesis in WO 2019 / 151318.

[0062] <Synthesis of compound (E-4)> [ka] A solution of compound (E4-6) (3.24 g (13.0 mmol)), compound (E4-7) (3.51 g (10.0 mmol)), and EtOH (100 mL) was mixed under an Ar stream and heated to a temperature of 37 to 45°C, stirred for 5 hours, and then cooled on ice. The precipitated crystals were collected by filtration, washed with IPE, and dried under reduced pressure at 50°C to obtain 3.51 g of compound (E-4) (yield: 93%).

[0063] Compound (E-4) 1 H-NMR analysis and 13 C-NMR analysis was performed. 1 H-NMR DMSO-d6 0.97(t 3H), 1.34-1.42(m 3H), 1.57-1.65(m 4H), 1.70-1.77(m 2H), 2.19(s 3H), 3.36-3.43(m 2H), 3.43-3.49(m 2H), 3.71(d 2H), 6.65(d 2H), 6.68(d 1H), 7.25(d 1H), 7.41(d 2H) 13 C-NMR analysis DMSO-d6 13.67, 19.40, 23.72, 26.12, 29.09, 29.40, 50.11, 50.30, 51.58, 60.27, 89.82, 94.17, 107.05, 109.87, 111.80, 112.19, 112.46, 112.93, 121.49, 134.30, 137.58, 141.80, 145.47, 149.74, 152.92, 171.44, 176.74

[0064] (Preparation of Compound (E-5)) Compound (E-5) (4-[4-(N,N-butyl-4-hydroxybutyl)aminophenyl]3-cyano-5,5-dimethylfuran-2(5H)-ylidene]malononitrile) was synthesized according to the following procedure.

[0065] <Synthesis of 2-methyl-trimethylsilyloxypropionitrile (E5-1)> [ka] 1,5,7-Triazabicyclo[4,4,0]5-decenepolystyrene (PS-TBD) (100 mg (0.121 mmol)) was added to acetone (100 mL), and trimethylsilyl cyanide (10.0 g (101 mmol)) was added dropwise with stirring at room temperature. After stirring at room temperature for 3 hours, PS-TBD was filtered off, and the acetone was concentrated under reduced pressure to obtain 14.4 g of the compound represented by formula (E5-1) (hereinafter sometimes referred to as "compound (E5-1)") (yield: 100%).

[0066] Compound (E5-1)1 H-NMR analysis and 13 C-NMR analysis was performed. 1 H-NMR CDCl3:0.24(s 9H), 1.60(s 6H) 13 C-NMR CDCl3:1.32, 30.89, 66.17, 122.79

[0067] Synthesis of 1-(4-fluorophenyl)-2-hydroxy-2-methylpropan-1-one (E5-2) [ka] THF (18 mL) was added to magnesium (3.22 g (132 mmol)), and several drops of 1,2-dibromoethane were added thereto. Then, a solution of 4-bromofluorobenzene (20.1 g (115 mmol)) diluted with THF (10 mL) was added dropwise to the mixture under stirring and cooling with water. After stirring for 3 hours at room temperature, a solution of compound (E5-1) (14.4 g (101 mmol)) diluted with THF (20 mL) was added dropwise under water-cooled stirring. After stirring for 16 hours at room temperature, the mixture was cooled to below 10°C, and 6 mol / L aqueous hydrochloric acid solution (110 mL) was slowly added dropwise. After stirring for 2.5 hours at room temperature, sodium bicarbonate (40 g) was dispersed and added to neutralize the mixture. Ethyl acetate (300 mL) and 10% brine (300 mL) were added for extraction. The ethyl acetate extract was washed with 10% brine, dried over anhydrous sodium sulfate, and the solvent was concentrated under reduced pressure to obtain a crude compound represented by formula (E5-2) (hereinafter sometimes referred to as "compound (E5-2)"). Purification by silica gel column chromatography (chloroform / ethyl acetate: 10 / 1) gave 10.6 g of compound (E5-2) (yield: 58%).

[0068] Synthesis of 3-cyano-2-dicyanomethylene-4-(4-fluorophenyl)-5,5-dimethyl-2,5-dihydrofuran (E5-3) [ka] Compound (E5-2) (10.6 g (58.1 mmol)) and malononitrile (11.5 g (174 mmol)) were dissolved in pyridine (45 mL), and acetic acid (0.2 g) was added and stirred at room temperature for 5 days. The reaction solution was dispersed in water (900 mL), and the precipitated crystals were collected by filtration. The obtained crystals were washed with water and then with methanol, and dried under reduced pressure at 70°C to obtain a compound represented by formula (E5-3) (hereinafter sometimes referred to as "compound (E5-3)") (12.0 g (43.0 mmol)).

[0069] Compound (E5-3) 1 H-NMR analysis, 13 C-NMR analysis and melting point measurement were carried out using a differential scanning calorimeter. 1 H-NMR DMSO-d6:1.75(s 6H), 7.53(dd 2H), 7.91(dd 2H) 13 C-NMR DMSO-d6 24.50, 55.61, 100.60, 103.24, 110.99, 111.32, 112.19, 116.87, 123.91, 131.32, 163.69, 165.37, 177.01 DSC:mp 273℃

[0070] <Synthesis of (E-5)> [ka] Compound (E5-3) (7.20 g (25.8 mmol)) and N,N-butyl 4-hydroxybutylamine (11.3 g (77.8 mmol)) were added to a mixture of pyridine (130 mL) and acetonitrile (90 mL) and stirred for 22 hours in an oil bath at 50 °C. The solvent was concentrated under reduced pressure at 50 °C. The concentrate was dissolved in THF (450 mL) and ethyl acetate (450 mL). The solution was washed with 10% brine (600 mL) containing potassium carbonate (60 g), dried over anhydrous sodium sulfate, and the solvent was concentrated under reduced pressure to obtain crude compound (E-5). The crude product was purified by silica gel short column chromatography to obtain red crystals. The crystals were washed with ethyl acetate and then methanol and dried under reduced pressure at 70 °C to obtain compound (E-5) (6.01 g (14.8 mmol)) (yield: 57%).

[0071] Compound (E-5) 1 H-NMR analysis, 13 C-NMR analysis, melting point measurement by differential scanning calorimetry, and mass spectrometry were performed. 1 H-NMR DMSO-d6 0.93(t 3H), 1.35(m 2H), 1.48(m 2H), 1.53-1.65(m 4H), 1.81(s 6H), 3.43-3.49(m 6H), 4.49(t 1H), 6.92(d 2H), 8.05(d 2H) 13 C-NMR DMSO-d6 13.67, 19.41, 23.61, 26.60, 28.95, 29.41, 50.04, 50.21, 50.38, 60.27, 88.90, 98.12, 112.12, 112.35, 112.57, 113.63, 113.69, 132.60, 152.77, 173.98, 177.81 DSC:mp 249.8℃ ESI-MS: M+1=405.2

[0072] (Synthesis of base polymer (A-4)) 7.50 g (74.9 mmol) of methyl methacrylate (MMA), 3.00 g (19.3 mmol) of 2-(isocyanatoethyl) methacrylate (MOI), and 0.464 g (2.83 mmol) of azobisisobutyronitrile (AIBN) were dissolved in 15 mL of dehydrated toluene, and after argon was sealed in, the mixture was stirred in an oil bath at 60-61°C for 3 hours. After cooling the reaction solution to room temperature, it was added dropwise to 450 mL of dehydrated diisopropyl ether (IPE), and the precipitate was collected by filtration. After washing with dehydrated IPE, it was dried under reduced pressure at 50°C to obtain 8.48 g of base polymer (A-4).

[0073] A derivative of base polymer (A-4) was obtained and analyzed in the same manner as in the derivatization of base polymer (A-1) described above. The glass transition temperature Tg was 99°C, the weight average molecular weight Mw was 76,900, and the number average molecular weight Mn was 32,100.

[0074] (Synthesis of base polymer (A-5)) 7.90 g (78.9 mmol) of methyl methacrylate (MMA), 3.32 g (21.4 mmol) of 2-(isocyanatoethyl) methacrylate (MOI), and 0.497 g (3.03 mmol) of azobisisobutyronitrile (AIBN) were dissolved in 15 mL of dehydrated toluene, argon was introduced, and the mixture was stirred in an oil bath at 60 °C for 2 hours. After cooling to room temperature, the reaction mixture was diluted with 8 mL of dehydrated toluene and added dropwise to 450 mL of dehydrated diisopropyl ether (IPE). The precipitate was collected by filtration. After washing with dehydrated IPE, the mixture was dried under reduced pressure at 70 °C to obtain 8.325 g of base polymer (A-5).

[0075] A derivative of base polymer (A-5) was obtained and analyzed in the same manner as in the derivatization of base polymer (A-1) described above. The glass transition temperature Tg was 99°C, the weight average molecular weight Mw was 83,400, and the number average molecular weight Mn was 36,900.

[0076] (Production of EO polymer (EO-4)) 1.05 g of the base polymer (A-4) obtained above was dissolved in 65 mL of dehydrated tetrahydrofuran (THF). 0.90 g (0.77 mmol) of compound (E-4) and 30 μL of dibutyltin dilaurate (DBTDL) were added and stirred in an oil bath at 60°C for 2 hours. 3 mL of dehydrated methanol was then added and stirred at 60°C for 45 minutes. After cooling, the reaction solution was poured into 650 mL of diisopropyl ether (IPE) and stirred. The precipitated powder was collected by filtration, washed twice with IPE (100 mL), and then dried under reduced pressure at 50°C. 1.29 g of EO polymer (EO-4) was obtained as a black powder (glass transition temperature Tg: 146°C).

[0077] (Production of EO polymer (EO-5)) 1.754 g (3.35 mmol) of the base polymer (A-5) obtained above was dissolved in 105 mL of dehydrated tetrahydrofuran (THF). 0.754 g (1.86 mmol) of compound (E-5) and 100 μL of dibutyltin dilaurate (DBTDL) were added and stirred in an oil bath at 55°C for 2 hours. 5 mL of dehydrated methanol was then added and stirred at 60°C for 120 minutes. After cooling, the reaction solution was poured into 1050 mL of diisopropyl ether (IPE) and stirred. The precipitated powder was collected by filtration, washed three times with IPE (100 mL), and then dried under reduced pressure at 70°C. 1.66 g of EO polymer (EO-5) was obtained as an orange-red powder (glass transition temperature Tg: 120°C).

[0078] [Determination of figures of merit FOM1 and FOM2] To calculate the figures of merit (FOM1) and (FOM2), EO polymer films were formed using the following procedure, and the propagation loss per unit length α, refractive index n, and electro-optic coefficient r of the EO polymers (EO-1), (EO-4), and (EO-5) were measured.

[0079] [EO polymer film formation method] Each EO polymer (EO-1), (EO-4), and (EO-5) was added to cyclohexanone to prepare a solution with a concentration of 1 to 20 wt%. The solution was then applied to a cleaned quartz glass substrate at 500 to 6,000 rpm using a Mikasa spin coater 1H-DX2, and then vacuum dried for 1 hour at a temperature near the glass transition temperature (Tg). The concentration of the polymer solution and the rotation speed of the spin coater were appropriately selected to obtain the desired film thickness.

[0080] [Absorbance spectrum of thin film of EO polymer] The absorbance spectra of thin films of each of the EO polymers (EO-1), (EO-4), and (EO-5) formed on quartz glass with a thickness of approximately 0.15 μm were measured using a spectrophotometer UH-4150 manufactured by Hitachi High-Tech Science Corp. The absorption coefficient a(ω) per unit length was calculated by dividing the absorbance by the film thickness.

[0081] [Absorbance spectrum of thick EO polymer film] Three different thicknesses of EO polymer thick films were fabricated for each EO polymer (EO-1), (EO-4), and (EO-5) by forming recesses of three different depths in the range of 40–350 μm on a quartz glass substrate, filling them with EO polymer, and polishing the surface. The absorbance spectra of the EO polymer thick films were measured using a Hitachi High-Tech Science UH-4150 spectrophotometer. A graph plotting the absorbance versus film thickness at each wavelength (frequency ω) was fitted with a linear function, and the absorption coefficient per unit length at frequency ω, a(ω), was calculated from the slope of the function.

[0082] [Propagation loss per unit length of EO polymer α] The propagation loss per unit length of the optical waveguide, 0.4 dB / cm, calculated by simulation was added to the absorption coefficient a(ω) to obtain the propagation loss per unit length α(ω). The absorption coefficient a(ω) was calculated by adding 1 × 10 -3 Values ​​below 1 × 10 are subject to the limits of the measuring instrument and have a large error. -3At wavelengths (frequencies) above ω, the absorption coefficient a(ω) calculated from the absorbance of the thin film is used, and the absorbance of the thin film is 1×10 -3 For wavelengths (frequencies ω) less than 1000 kHz, the value of the absorption coefficient a(ω) calculated from the absorbance of the thick film was used.

[0083] [Refractive index of EO polymer] The refractive index n of each EO polymer (EO-1), (EO-4), and (EO-5) was measured using a Metricon Prism Coupler 2010 / M for an EO polymer film approximately 3 μm thick formed on a quartz glass substrate.

[0084] [Electro-optic coefficient r of EO polymer] The EO coefficient was measured using the same method as described in the reference paper, "Transmission ellipsometric method without an aperture for simple and reliable evaluation of electro-optic properties," Toshiki Yamada and Akira Otomo, Optics Express, vol. 21, pages 29240-48 (2013)). The laser light sources used were the Agilent Technologies DFB laser 81663A (wavelengths 1308 nm and 1550 nm), the Toptica Photonics DFBpro laser (wavelength 976 nm), and the Coherent OBIS LX laser (wavelength 640 nm).

[0085] [Calculation of performance indices FOM1 and FOM2 based on heteroscedastic analysis (Gaussian variance formula)] Based on heteroscedasticity analysis (Gaussian dispersion formula), the linear susceptibility χ (1) (ω), and second-order nonlinear susceptibility χ (2) The following formula was used as the model formula for (ω,ω,0): where ω is the frequency, m is the ordinal number of the resonance, and ω m0 is the resonant frequency and Γ m0 is the uniform dispersion width, and Δω m0 is the heteroscedasticity range, and χ m(1) is the magnitude of the linear susceptibility, and χ m (2) is the magnitude of the second-order nonlinear susceptibility. The resonance ordinal m can be selected appropriately depending on the degree of reproducibility of the absorbance spectrum (the difference between the measured value and the calculated value), but here we used m = 4 for the analysis.

number

[0086] The values ​​measured in the [Absorbance spectrum of the thin film of the EO polymer] above were fitted with the above equations (Q3) and (Q4) to obtain the magnitude of the linear susceptibility χ m (1) , resonance frequency ω m0 , uniform dispersion width Γ m0 , non-uniform dispersion width Δω m0 It was decided that:

number

[0087] Next, the values ​​measured at wavelengths of 1308 nm and 1532 nm in the [Refractive index of EO polymer] above were fitted with the above equation (Q5) to obtain the background term χ of the linear susceptibility. b (1) It was decided that:

number

[0088] The fitting of the absorption spectrum and the fitting of the refractive index are calculated as χ b (1) The change in -6 Repeat until you get: m (1) , ω m0 , Γ m0 , Δω m0 , χ b (1) was finalized.

[0089] Next, the values ​​measured at wavelengths of 1308 nm and 1550 nm using the above [Electro-optic coefficient r of EO polymer] for the EO polymer (EO-1), the values ​​measured at wavelengths of 976 nm, 1308 nm, and 1550 nm for the EO polymer (EO-4), and the values ​​measured at wavelengths of 640 nm, 976 nm, 1308 nm, and 1550 nm for the EO polymer (EO-5) were each fitted with the above equation (Q6) to obtain the magnitude of the second-order nonlinear susceptibility χ m (2) The fitting was performed using the nonlinear least squares method (Levenberg-Marquardt method).

number

[0090] For the EO polymers (EO-1), (EO-4), and (EO-5) obtained above, the refractive index n and electro-optic coefficient r were determined from the relational equation obtained above, and the propagation loss per unit length α was measured, and the figures of merit FOM1 and FOM2 were calculated. Note that when calculating the figure of merit FOM2, α≦α c If α is α, then c Using α>α c The results are shown in Table 2. Table 3 shows the results when the figure of merit FOM1 calculated above is 1.2 (V cm). -1 The maximum wavelength (λmax) and minimum wavelength (λmin) are equal to or greater than 0.20 (V·dB), and the figure of merit (FOM2) is 0.20 (V·dB). -1 The maximum value (λmax) and minimum value (λmin) of the wavelength above this value are shown.

[0091] [Table 2]

[0092] [Table 3]

[0093] Comparative Example 2 An optical modulator for a wavelength of 1550 nm was fabricated as an optical control element in the following procedure. (Preparation of EO polymer (E-1a)) The EO polymer (E-1a) represented by the following formula was prepared according to the procedure described in Example 2 of WO 2018 / 003842. The figure of merit (FOM1) of the EO polymer (E-1a) at a wavelength of 1550 nm calculated based on heterogeneous dispersion analysis (Gaussian dispersion equation) was 1.33 (V·cm). -1 and the figure of merit FOM2 is 0.22 (V dB). -1 It was. [ka] [In the formula, k, p, q, and r represent integers of 1 or more.]

[0094] (Preparation of Cladding Material Composition) 0.67 g of 3-methacryloyloxypropyltrimethoxysilane (manufactured by Tokyo Chemical Industry Co., Ltd.) and 0.06 g of zirconium propoxide (manufactured by Tokyo Chemical Industry Co., Ltd.) were added to a mixed solution of 0.41 g of ethanol and 0.05 g of 0.1 N aqueous hydrochloric acid solution and stirred. This mixture was stored at a temperature of 5°C or below for 12 hours or more, and then 0.071 g of Omnirad819 (manufactured by IGM Resins) was added and stirred for 30 minutes to obtain a clad material composition.

[0095] (Fabrication of the lower electrode) A lower electrode was fabricated by forming an IZO (100 nm) film on a silicon substrate with a thermally oxidized film of 2 μm thickness by sputtering.

[0096] (Production of the lower cladding) The cladding material composition prepared above was spin-coated (3,500 rpm x 30 seconds) onto the lower electrode, heated at 95°C for 30 minutes and at 120°C for 15 minutes, irradiated with LED light of 365 nm wavelength at 100°C, and then heated at 190°C for 16 hours. The film thickness of the fabricated lower cladding was 2.21 μm.

[0097] (Creation of core layer) A 15% by mass solution of EO polymer (E-1a) in cyclohexanone was spin-coated (1,300 rpm x 30 seconds) onto the lower clad prepared above, and then heated in vacuum at 180°C for 1 hour. The thickness of the core layer thus prepared was 1.40 µm.

[0098] (Preparation of poling electrodes and poling treatment) An IZO (100 nm) film was formed on the core layer prepared above by sputtering, forming a poling electrode and obtaining a structure for poling treatment. After heating this structure to 176°C, a voltage of 420 V was applied between the lower electrode and the poling electrode for 3 minutes to perform poling treatment. After cooling to room temperature with the voltage still applied, the voltage was turned off. The poling electrode was then removed using an etching solution (ITO-06N, manufactured by Kanto Chemical Co., Inc.).

[0099] (Formation of optical waveguide) On the core layer of the structure that had undergone poling treatment, an IZO (50 nm) film was formed by sputtering as a processing mask. A mask pattern was then created by photolithography, and the core layer was processed into a rectangular structure (1.32 μm × 1.40 μm) by dry etching using a reactive ion etching device, which became the optical waveguide (core). The optical waveguide formed a Mach-Zehnder (MZ) type optical modulator structure.

[0100] (Fabrication of upper cladding) The cladding material composition prepared above was spin-coated (3,500 rpm x 30 seconds) onto the optical waveguide formed above, and after heating at 90°C for 10 minutes, it was irradiated with LED light with a wavelength of 365 nm for 5 minutes at 100°C. The film thickness of the fabricated upper cladding was 1.65 μm from the top surface of the optical waveguide (core).

[0101] (Fabrication of the upper electrode) An IZO (100 nm) film was formed on the upper cladding layer by sputtering. A mask pattern was then created by photolithography, and the upper electrode was formed by patterning with an etching solution (ITO-06N, manufactured by Kanto Chemical Co., Ltd.). The length (L) of the upper electrode was 1 cm.

[0102] (Fabrication of optical modulator) By cutting both end faces of the optical waveguide with a dicing saw to form light input and output end faces, an optical modulator with a structure corresponding to that shown in Figure 1 was completed. Figure 3 is an image showing a cross section of the light input end face of the fabricated optical modulator. Figure 4 is a graph showing the time waveform of the optical modulation of the fabricated optical modulator. As shown in Figure 4, channel Ch2 is the applied voltage, and channel Ch1 is the 1550 nm output light intensity of the MZ optical modulator. This shows a typical optical output waveform of an MZ optical modulator relative to a voltage change in a triangular waveform, and the above-mentioned V π is 4.4V, the above V π L was 4.4 V·cm.

[0103] Example 3 An optical modulator for a wavelength of 640 nm was fabricated as an optical control element in the following procedure. (Preparation of EO polymer (E-5a)) The EO polymer (E-5a) represented by the following formula was prepared using the following procedure. The figure of merit (FOM1) of the EO polymer (E-5a) at a wavelength of 640 nm calculated based on heterogeneous dispersion analysis (Gaussian dispersion equation) was 3.61 (V·cm). -1 and the figure of merit FOM2 is 0.60 (V dB). -1 It was. [ka] [In the formula, k, p, and r represent integers of 1 or more.]

[0104] (Synthesis of base polymer (A-5a)) Adamantyl methacrylate (AdMA) 7.00 g (31.8 mmol), 2-(isocyanatoethyl) methacrylate (MOI) 2.60 g (16.8 mmol), and azobisisobutyronitrile (AIBN) 0.266 g (1.62 mmol) were dissolved in 18 mL of dehydrated toluene, purged with argon, and stirred in an oil bath at 70 °C for 2 hours. After cooling to room temperature, the reaction mixture was diluted with 15 mL of dehydrated toluene and added dropwise to a mixture of 450 mL of dehydrated diisopropyl ether (IPE) and 15 mL of dehydrated toluene. The precipitate was collected by filtration. The mixture was washed sequentially with dehydrated IPE and dehydrated hexane and then dried under reduced pressure at 45 °C to obtain 8.70 g of base polymer (A-5a).

[0105] (Derivatization of base polymer (A-5a) (methyl carbamate derivative)) Under Ar gas, 1.0 g of base polymer (A-5a) was dissolved in 35 mL of dehydrated tetrahydrofuran, 3 mL of dehydrated methanol and 40 μL of dibutyltin dilaurate (DBTDL) were added, and the mixture was stirred for 2 hours in an oil bath at 55°C. After cooling, the reaction mixture was poured into 350 mL of diisopropyl ether (IPE) and stirred. The precipitated powder was collected by filtration, washed with 100 mL of IPE and 100 mL of hexane, and then dried under reduced pressure at 65°C to obtain a derivative of base polymer (A-5a).

[0106] The derivative of base polymer (A-5a) was analyzed in the same manner as the above-mentioned analysis of the derivative of base polymer (A-1). The glass transition temperature Tg was 155°C, the weight average molecular weight Mw was 78,600, and the number average molecular weight Mn was 31,300.

[0107] (Production of EO polymer (EO-5a)) 6.842 g (11.2 mmol) of the base polymer (A-5a) obtained above was dissolved in 300 mL of dehydrated tetrahydrofuran (THF). 3.430 g (8.48 mmol) of compound (E-5) and 100 μL of dibutyltin dilaurate (DBTDL) were added and stirred in an oil bath at 55°C for 2 hours. 40 mL of dehydrated methanol was then added and stirred at 55°C for 1 hour. After cooling, the reaction solution was poured into 3.6 L of diisopropyl ether (IPE) and stirred. The precipitated powder was collected by filtration, washed twice with IPE (100 mL), washed twice with methanol (100 mL), and then dried under reduced pressure at 70°C. 9.10 g of EO polymer (EO-5a) was obtained as an orange-red powder (glass transition temperature Tg: 164°C).

[0108] (Production of the lower cladding) The cladding material composition prepared by the procedure described in Comparative Example 2 was spin-coated (3,000 rpm x 30 seconds) onto the lower electrode prepared by the procedure described in Comparative Example 2, and the resultant was heated at 95°C for 30 minutes, 120°C for 15 minutes, and then 190°C for 16 hours, after which it was irradiated with 365 nm LED light at 100°C. The film thickness of the produced lower cladding was 1.27 μm.

[0109] (Creation of core layer) A 12% by mass solution of EO polymer (E-5a) in cyclohexanone was spin-coated (3,200 rpm x 30 seconds) onto the lower clad prepared above, and then heated in vacuum at 170°C for 1 hour. The thickness of the core layer thus prepared was 0.52 μm.

[0110] (Preparation of poling electrodes and poling treatment) An IZO (100 nm) film was formed on the core layer prepared above by sputtering, forming a poling electrode and obtaining a structure for poling treatment. After heating this structure to 164°C, a voltage of 240 V was applied between the lower electrode and the poling electrode for 1 minute to perform poling treatment. After cooling to room temperature with the voltage still applied, the voltage was turned off. The poling electrode was then removed using an etching solution (ITO-06N, manufactured by Kanto Chemical Co., Inc.).

[0111] (Formation of optical waveguide) On the core layer of the structure that had undergone poling treatment, an IZO (50 nm) film was formed by sputtering as a processing mask. A mask pattern was then created by photolithography, and the core layer was processed into a ridge structure (protruding part width 0.99 μm x height 0.27 μm) by dry etching using a reactive ion etching device, which became the optical waveguide (core). The optical waveguide formed a Mach-Zehnder (MZ) type optical modulator structure.

[0112] (Fabrication of upper cladding) The cladding material composition prepared by the procedure described in Comparative Example 2 was spin-coated (2,000 rpm x 30 seconds) onto the optical waveguide formed above, heated at 90°C for 10 minutes, and then irradiated with LED light having a wavelength of 365 nm for 5 minutes at 100°C. The film thickness of the fabricated upper cladding was 1.55 μm from the top surface of the optical waveguide (core).

[0113] An IZO (100 nm) film was formed on the upper cladding layer by sputtering. A mask pattern was then created by photolithography, and the upper electrode was formed by patterning with an etching solution (ITO-06N, manufactured by Kanto Chemical Co., Ltd.). The length (L) of the upper electrode was 0.5 cm.

[0114] (Fabrication of optical modulator) By cutting both end faces of the waveguide with a dicing saw to form light input and output end faces, an optical modulator with a structure corresponding to that shown in Figure 1 was completed. Figure 5 is a cross-sectional image of the light input end face of the fabricated optical modulator. Figure 6 is a graph showing the time waveform of the optical modulation of the fabricated optical modulator. In Figure 6, channel Ch1 is the 640 nm output light intensity of the MZ optical modulator, and channel Ch2 is the applied voltage. This shows a typical optical output waveform of an MZ optical modulator relative to a voltage change in a triangular waveform, and the above-mentioned V π is 2.48V, the V π L was 1.24 V·cm.

[0115] V calculated in Comparative Example 2 π The V calculated in Example 3 is used instead of the L value. π Since the value of L is smaller, it is understood that the optical modulator fabricated in Example 3 has excellent high speed performance in the wavelength band around 640 nm, and is useful (highly efficient) in that wavelength band.

[0116] Examples 4 to 14 The following procedure was used to obtain EO polymers (EO-5(4)) to (EO-5(14)) in which compounds represented by the following formulas (E-5(4)) to (E-5(14)) (hereinafter sometimes referred to as "compound (E-5(4))") were bonded to the base polymer. [ka] [ka] [ka] [ka] [ka] [ka] [ka] [ka] [ka] [ka] [ka] [In the formula, k, p, and r represent integers of 1 or more.]

[0117] (Synthesis of Compounds (E-5(4)) to (E-5(14))) Compound (E5-3) and the compounds shown in Table 4 were used to carry out the reaction treatment in the same manner as described in the synthesis of (E-5) above, to obtain compounds (E-5(4)) to (E-5(14)). The yields are shown in Table 4. [Table 4]

[0118] Compounds (E-5(4)) to (E-5(14)) 1 H-NMR analysis, 13 C-NMR analysis and melting point measurement were performed using a differential scanning calorimeter. <Compound (E-5(4)): 2-(3-cyano-4-(4-(ethyl(4-hydroxybutyl)amino)phenyl)-5,5-dimethylfuran-2(5H)-ylidenemalononitrile> 1 H-NMR DMSO-d6 1.58(t 3H), 1.48(m 2H), 1.63(m 2H), 1.81(s 6H), 3.43(m 2H), 3.49(m 2H), 3.55(m 2H), 4.48(t 1H), 6.92(d 2H), 8.05(d 2H) 13 C-NMR DMSO-d6 12.20, 23.76, 26.60, 29.45, 44.78, 49.69, 50.40, 60.27, 88.94, 98.12, 112.05, 112.35, 112.57, 113.62, 113.69, 132.63, 152.58, 174.02, 177.81 DSC:mp 221℃

[0119] <Compound (E-5(5)): 2-(3-cyano-4-(4-((4-hydroxybutyl)(methyl)amino)phenyl)-5,5-dimethylfuran-2(5H)-ylidene)malononitrile> 1 H-NMR DMSO-d6 1.45 (m 2H), 1.60 (m 2H), 1.81 (s 6H), 3.13 (s 3H), 3.43 (t 2H), 3.55 (t 2H), 4.47 (t 1H), 6.94 (d 2H), 8.06 (d 2H) 13 C-NMR DMSO-d6 23.26, 26.57, 29.44, 38.18, 50.56, 51.46, 60.30, 89.29, 98.20, 112.12, 112.53, 112.53, 113.60, 113.64, 132.43, 153.52, 174.21, 177.80 DSC: mp 221 °C

[0120] <Compound (E-5(6)): 2-(4-(4-(butyl(3-hydroxypropyl)amino)phenyl)-3-cyano-5,5-dimethylfuran-2(5H)-ylidene)malononitrile> 1 H-NMR DMSO-d6 0.93 (t 3H), 1.35 (m 2H), 1.56 (m 2H), 1.73 (m 2H), 1.81 (s 6H), 3.49 (m 4H), 3.55 (m 2H), 4.66 (t 1H), 6.94 (d 2H), 8.05 (d 2H) 13 C-NMR DMSO-d6 13.67, 19.42, 26.59, 28.91, 29.94, 47.44, 50.03, 50.41, 57.82, 88.96, 98.14, 112.10, 112.38, 112.57, 113.62, 113.69, 132.57, 152.82, 174.03, 177.81 DSC: mp 265 °C

[0121] <Compound (E-5(7)): 2-(3-Cyano-4-(4-((3-hydroxypropyl)(methyl)amino)phenyl)-5,5-dimethylfuran-2(5H)-ylidene)malononitrile> 1 H-NMR DMSO-d6 1.73 (m 2H), 1.81 (s 6H), 3.14 (s 3H), 3.46 (dd 2H), 3.60 (t 2H), 4.64 (t 1H), 6.94 (d 2H), 8.06 (d​​​​​​​​​​​​​​​​​​​​​​​​​​<Compound (E-5(9)): 2-(3-Cyano-4-(4-((2-Hydroxyethyl)(propyl)amino)phenyl)-5,5-dimethylfuran-2(5H)-ylidene)malononitrile> 1 H-NMR DMSO-d6 0.91 (t 3H), 1.60 (m 2H), 1.81 (s 6H), 3.48 (t 2H), 3.60 (m 4H), 4.88 (t 1H), 6.96 (d 2H), 8.03 (d 2H) 13 C-NMR DMSO-d6 10.86, 19.78, 26.58, 50.46, 52.34, 52.44, 58.22, 89.06, 98.14, 112.31, 112.46, 112.55, 113.61, 113.67, 132.47, 153.31, 174.05, 177.81 DSC: mp 234 °C

[0124] <Compound (E-5(10)): 2-(3-Cyano-4-(4-(ethyl(2-hydroxyethyl)amino)phenyl)-5,5-dimethylfuran-2(5H)-ylidene)malononitrile> 1 H-NMR DMSO-d6 [[ID=二十一]]1.17 (t 3H), 1.81 (s 6H), 3.60 (m 6H), 4.89 (t 1H), 6.96 (d 2H), 8.04 (d 2H) 13 C-NMR DMSO-d6 11.86, 26.58, 45.34, 50.47, 51.99, 58.33, 89.08, 98.15, 112.24, 112.46, 112.55, 113.61, 113.67, 132.47, 153.09, 174.10, 177.81 DSC: mp 216 °C

[0125] <Compound (E-5(11)): 2-(Cyanide-4-(4-((2-Hydroxyethyl)(methyl)amino)phenyl-5,5-dimethylfuran-2(5H)-ylidene)malononitrile> 1 [End]] It should be noted that there is an error in the original text for item . I have corrected it to the correct chemical name expression in the translation. If this is not what you want, please provide more accurate information.H-NMR Acetone-d6 1.91(s 6H), 3.27 (s 3H), 3.75(t 2H), 3.85(t 2H), 7.00 (d 2H), 8.13(d 2H) 13 C-NMR Acetone-d6 29.72, 39.59, 53.24, 55.18, 60.07, 91.63, 98.91, 112.98, 113.14, 113.94, 114.18, 114.29, 133.23, 155.31, 175.53, 178.55 DSC: mp 258℃

[0126] <Compound (E-5(12)): 2-(3-Cyano-4-(4-(4-Hydroxypiperidin-1-yl)phenyl)-5,5-dimethylfuran-2(5H)-ylidene)malononitrile> 1 H-NMR DMSO-d6 1.42(m 2H), 1.81(s 6H), 1.83(m 2H), 3.35(m 2H), 3.80(m 1H), 3.90(m 2H), 4.82(d 1H), 7.13(d 2H), 8.03(d 2H) 13 C-NMR DMSO-d6 26.47, 33.62, 43.97, 50.97, 65.08, 90.22, 98.35, 112.43, 113.08, 113.17, 113.48, 113,48, 132.53, 153.68, 174.17, 177.78 DSC: mp 280℃ (decomposition point)

[0127] <Compound (E-5(13)): 2-(3-Cyano-4-(4-(3-Hydroxymethyl)piperidin-1-yl)phenyl)-5,5-dimethylfuran-2(5H)-ylidene)malononitrile> 1 H-NMR DMSO-d6 1.32(m 1H), 1.47(m 1H), 1.67(m 1H), 1.73(m 2H), 1.807(s 3H), 1.814(s 3H), 2.96(dd 1H), 3.15(t 1H), 3.30(m 1H), 3.35(m 1H), 4.04(d 1H), 4.09(d 1H), 4.66(t 1H), 7.10(d 2H), 8.04(d 2H) 13 C-NMR DMSO-d6 24.10, 26.48, 26.51, 26.67, 38.50, 47.34, 49.82, 50.78, 63.11, 89.82, 98.29, 112.48, 112.93, 113.54, 132.62, 153.77, 174.03, 177.78 DSC:mp 275℃

[0128] <Compound (E-5(14)):2-(3-シアノ-4-(2-ヒドロキシメチル)ピペリジン-1-イル)フェニル)-5,5-ジメチルフラン-2(5H)-イリデン)マロノニトリル> 1 H-NMR DMSO-d6 1.43-1.68(m 4H), 1.69-1.79(m 1H, 1.81(s 6H), 1.83-1.92(m 1H), 3.13(td 1H), 3.61(t 2H), 3.98(d 1H), 4.26(d 1H), 4.85(t 1H ), 7.11(d 2H), 8.02(d 2H) 13 C-NMR DMSO-d6 18.27, 24.71 (24.83), 26.50 (26.56), 39.93, 41.59, 50.60, 55.04, 58.77, 89.45, 98.21, 112.52, 112.80, 113.10, 113.59, 113.61, 132.42, 154.84, 173.92, 177.80 DSC: mp 238℃

[0129] (Manufactured by EOポリマー(EO-5(4))~(EO-5(14))) Using the base polymer (A-5a) and the compounds (E-5(4)) to (E-5(14)) obtained above, the reaction was carried out in the same manner as described for the production of the EO polymer (EO-5a) described above, to obtain EO polymers (EO-5(4)) to (EO-5(14)) in which compounds (E-5(4)) to (E-5(14)) were bonded to the base polymer, respectively. Table 5 shows the glass transition temperatures (Tg) of each EO polymer. [Table 5]

[0130] Example 15 The following procedure was used to obtain an EO polymer (EO-5(15)) in which a compound represented by the following formula (E-5(15)) (hereinafter referred to as "compound (E-5(15))") was bonded to a base polymer. [ka] [In the formula, k, p, and r represent integers of 1 or more.]

[0131] <Synthesis of 1-((trimethylsilyl)oxy)cyclohexane-1-carbonitrile (E5-1(3))> [ka] To 30 mL of dehydrated acetonitrile, 103 mg (0.125 mmol) of 1,5,7-triazabicyclo[4.4.0]5-decene polystyrene (PS-TBD) was added, followed by 9.00 g (91.7 mmol) of cyclohexanone and 9.80 g (98.8 mmol) of trimethylsilyl cyanide. After stirring at room temperature for 2.5 hours, the PS-TBD was filtered off, and the solvent was concentrated under reduced pressure to obtain 18.0 g of the compound represented by formula (E5-1(3)) (yield: 99%).

[0132] The compound represented by formula (E5-1(3)) 1 H-NMR analysis and 13 C-NMR analysis was performed. 1 H-NMR CDCl3 0.24(s 9H), 1.20-1.30(m 1H), 1.52-1.68(m 5H), 1.69-1.80(m 2H), 2.02-2.10(m 2H) 13 C-NMR CDCl3 1.46, 22.67, 24.54, 39.37, 70.67, 122.01

[0133] Synthesis of (4-fluorophenyl)(1-hydroxycyclohexyl)methanone (E5-2(3)) [ka] To 2.93 g (123 mmol) of magnesium was added 18 mL of THF, and several drops of 1,2-dibromoethane were added. A solution of 18.3 g (105 mmol) of 4-bromofluorobenzene diluted with 9 mL of THF was then added dropwise with stirring and water cooling. Stirring was continued for 3 hours at room temperature, and a solution of 18.0 g (91.2 mmol) of the compound represented by formula (E5-1(3)) diluted with 20 mL of THF was added dropwise with stirring and water cooling. After stirring for 16 hours at room temperature, the mixture was cooled to below 10°C, and 100 mL of 6 mol / L aqueous hydrochloric acid solution was slowly added dropwise. After stirring for 2.5 hours at room temperature, the mixture was neutralized by dispersing 37 g of sodium bicarbonate in the mixture. Extraction was performed by adding 270 mL of ethyl acetate and 130 mL of 10% brine. The ethyl acetate extract was washed with 10% brine, dried over anhydrous sodium sulfate, and the solvent was concentrated under reduced pressure to obtain a crude product of the compound represented by formula (E5-2(3)) (hereinafter referred to as "compound (E5-2(3))"). This composition was purified by silica gel column chromatography (chloroform / ethyl acetate: 10 / 1) to obtain 4.12 g (18.5 mmol) of compound (E5-2(3)) (yield: 20%, purity: approximately 70% (NMR)).

[0134] Synthesis of 2-(3-cyano-4-(4-fluorophenyl)-1-oxaspiro[4,5]dec-3-en-2-ylidene)malononitrile (E5-3(3)) [ka] 10.2 g (45.9 mmol) of the compound (E5-2(3)) purified above and 14.0 g (212 mmol) of malononitrile were dissolved in 58 mL of pyridine, and approximately 0.1 g of acetic acid was added and stirred at room temperature for 91 hours. The reaction solution was dispersed in 1150 mL of water, and the precipitated crystals were collected by filtration. The obtained crystals were washed with water and then with methanol and dried under reduced pressure at 70 °C to obtain 8.53 g (26.7 mmol) of the compound represented by formula (E5-3(3)) (yield: 58%).

[0135] The compound represented by formula (E5-3(3)) 1 H-NMR analysis, 13 C-NMR analysis and melting point measurement were performed using a differential scanning calorimeter. 1 H-NMR CDCl3 1.96-2.05(m 2H), 2.13-2.21(m 2H), 2.22-2.28(m 2H), 2.28-2.37(m H), 7.31(dd 2H), 7.83(dd 2H) 13 C-NMR CDCl3 25.86, 39.58, 58.79, 102.00, 108.85, (110.48, 110.50), 111.35, (117.48, 117.63), (123.62, 123.60), (131.08, 131.15), 164.82, 166.54, 174.09, 175.08 DSC:mp 195℃

[0136] <Synthesis of Compound (E-5(15)) (2-(3-cyano-4-(4-((3-hydroxymethyl)piperidin-1-yl)phenyl)-1-oxaspiro[4,5]dec-3-en-2-ylidene)malononitrile)> The compound represented by formula (E5-3(3)) and piperidin-3-ylmethanol were reacted and treated in the same manner as described in the synthesis of (E-5) above to obtain compound (E-5(15)) (yield: 76%).

[0137] Compound (E-5(15)) 1 H-NMR analysis, 13 C-NMR analysis and melting point measurement were performed using a differential scanning calorimeter. 1 H-NMR DMSO-d6 1.33(m 1H), 1.41-1.84(m 10H), 1.92(d 2H), 2.16(m 2H), 2.97(dd 1H), 3.15(dd 1H), 3.29(m 1H), 3.35(m 1H), 4.03(d 1H), 4.08(d 1H), 4.65(t 1H), 7.09(d 2H), 8.08(d 2H) 13 C-NMR DMSO-d6 21.76, 23.05, 24.06, 26.67, 34.37, 38.47, 47.35, 49.84, 51.02, 63.11, 90.43, 99.74, 112.52, 112.88, 113.18, 113.37, 113.56, 132.59, 153.70, 173.98, 177.82 DSC:mp 268℃

[0138] (Production of EO polymer (EO-5(15))) Using the base polymer (A-5a) and the compound (E-5(15)) obtained above, a reaction treatment was carried out in the same manner as described in the production of the EO polymer (EO-5a) above, to obtain an EO polymer (EO-5(15)) in which the compound (E-5(15)) was bonded to the base polymer (glass transition temperature Tg: 202°C).

[0139] Examples 16 and 17 The following procedure was used to obtain EO polymers (EO-5(16)) and (EO-5(17)) in which compounds represented by the following formulas (E-5(16)) and (E-5(17)) (hereinafter referred to as "compound (E-5(16)")) were bonded to the base polymer. [ka] [ka] [In the formula, k, p, and r represent integers of 1 or more.]

[0140] (Synthesis of Compounds (E-5(16)) and (E-5(17))) Compound (E5-3(2)) and piperidin-2-ylmethanol were used in the same reaction procedure as described in the synthesis of (E-5) above to obtain compound (E-5(16)) (yield: 10%). Compound (E5-3(2)) and piperidin-4-ylmethanol were used in the same reaction procedure as described in the synthesis of (E-5) above to obtain compound (E-5(17)) (yield: 79%).

[0141] Compounds (E-5(16)) and (E-5(17)) 1 H-NMR analysis, 13 C-NMR analysis and melting point measurement were performed using a differential scanning calorimeter. <Compound (E-5(16)): 2-(3-cyano-4-(4-((2-hydroxymethyl)piperidin-1-yl)phenyl)-1-oxaspiro[4,5]dec-3-en-2-ylidene)malononitrile> 1 H-NMR DMSO-d6 1.42-1.69(m 7H), 1.70-1.83(m 4H), 1.83-1.96(m 3H), 2.12-2.23(m 2H), 3.12(td 1H), 3.61(t 2H), 3.97(d 1H), 4.24(m 1H), 4.83(t 1H), 7.11(d 2H), 8.06(d 2H) 13 C-NMR DMSO-d6 18.26, 21.76, 23.07, 24.71, 24.81, 34.37, 34.42, 39.95, 41.60, 50.86, 55.06, 58.77, 90.08, 99.66, 112.54, 113.03, 113.07, 113.41, 113.63, 132.38, 154.75, 173.87, 177.84 DSC:mp 229℃

[0142] <Compound (E-5(17)): 2-(3-cyano-4-(4-((4-hydroxymethyl)piperidin-1-yl)phenyl)-1-oxaspiro[4,5]dec-3-en-2-ylidene)malononitrile> 1 H-NMR DMSO-d6 1.12-1.30(m 2H), 1.45-1.56(m 1H), 1.56-1.68(m 2H), 1.69-1.83(m 6H), 1.92(d 2H), 2.16(td 2H), 3.06(td 2H ), 3.27(t 2H), 4.16(d 2H), 4.52(t 1H), 7.11(d 2H), 8.06(d 2H) 13 C-NMR DMSO-d6 21.75, 23.08, 28.12, 34.35, 38.09, 46.42, 51.08, 65.20, 90.62, 99.77, 112.49, 113.00, 113.30, 113.36, 113.54, 132.52, 153.66, 174.06, 177.83 DSC:mp 264℃

[0143] (Production of EO polymers (EO-5(16)) and (EO-5(17))) Using the base polymer (A-5a) and the compounds (E-5(16)) and (E-5(17)) obtained above, respectively, a reaction treatment was carried out in the same manner as described for the production of the EO polymer (EO-5a) described above, to obtain EO polymers (EO-5(16)) and (EO-5(17)) in which compounds (E-5(16)) and (E-5(17)) were bonded to the base polymer, respectively (glass transition temperatures Tg of 207°C and 209°C, respectively).

[0144] Example 18 An EO polymer (EO-5(18)) in which compound (E-5(17)) was bound to the base polymer was obtained by the following procedure. [ka] [In the formula, k, p, and r represent integers of 1 or more.]

[0145] (Synthesis of base polymer (A-5b)) 7.00 g (31.8 mmol) of dicyclopentanyl methacrylate (DCPMA), 2.60 g (16.8 mmol) of 2-(isocyanatoethyl) methacrylate (MOI), and 0.266 g (1.62 mmol) of azobisisobutyronitrile (AIBN) were dissolved in 18 mL of anhydrous toluene, and the solution was filled with argon and stirred in an oil bath at 74 °C for 2 hours. After cooling to room temperature, the solution was diluted with 10 mL of anhydrous toluene and added dropwise to 450 mL of anhydrous diisopropyl ether (IPE). The precipitate was collected by filtration. The solution was washed sequentially with anhydrous IPE and anhydrous hexane, and then dried under reduced pressure at 45 °C to obtain 7.14 g of base polymer (A-5b).

[0146] (Derivatization of base polymer (A-5b) (methyl carbamate derivative)) Under Ar gas, 1.0 g of base polymer (A-5b) was dissolved in 50 mL of dehydrated tetrahydrofuran, and 4 mL of dehydrated methanol and 40 μL of dibutyltin dilaurate (DBTDL) were added. The mixture was stirred for 2 hours in an oil bath at 55°C. After cooling, the reaction mixture was poured into 950 mL of diisopropyl ether (IPE) and stirred. The precipitated powder was collected by filtration, washed with 200 mL of IPE and 100 mL of hexane, and then dried under reduced pressure at 65°C to obtain a derivative of base polymer (A-5b).

[0147] The derivative of base polymer (A-5b) was analyzed in the same manner as the derivative of base polymer (A-1) described above. The glass transition temperature Tg was 155°C, the weight average molecular weight Mw was 64,700, and the number average molecular weight Mn was 26,900.

[0148] (Production of EO polymer (EO-5(18))) 0.354 g (0.854 mmol) of compound (E-5(17)) and 0.700 g (1.23 mmol) of base polymer (A-5b) were dissolved in 50 mL of tetrahydrofuran (THF). 100 μL of dibutyltin dilaurate (DBTDL) was added and stirred for 2 hours in a 55°C oil bath. 4 mL of dehydrated methanol was then added and stirred at the same temperature for 1 hour. After cooling, the reaction mixture was poured into 600 mL of diisopropyl ether (IPE) and stirred. The precipitated powder was collected by filtration and washed twice with 100 mL of a 10:1 IPE:THF mixture, then twice with 50 mL of IPE, and finally with 50 mL of n-hexane. The mixture was then dried under reduced pressure at 70°C. 0.753 g of EO polymer (EO-5(18)) was obtained as an orange-red powder (glass transition temperature Tg: 179°C).

[0149] Example 19 The following procedure was used to obtain an EO polymer (EO-5(19)) in which a compound represented by the following formula (E-5(19)) (hereinafter referred to as "compound (E-5(19))") was bonded to a base polymer. [ka]

[0150] Compound (E5-3(2)) and 2-(piperidin-4-yl)ethan-1-ol were used in the same reaction as described in the synthesis of (E-5) above to obtain compound (E-5(19)) (yield: 42%).

[0151] Compound (E-5(19)) 1 H-NMR analysis, 13 C-NMR analysis and melting point measurement were performed using a differential scanning calorimeter. <Compound (E-5(19)): 2-(3-cyano-4-(4-(4-(2-hydroxyethyl)piperidin-1-yl)phenyl)-1-oxaspiro[4,5]dec-3-en-2-ylidene)malononitrile> 1 H-NMR DMSO-d6 1.10-1.20(m 2H), 1.35-1.42(m 2H), 1.43-1.68(m 3H), 1.72-1.81(m 6H), 1.92(d 2H), 2.16(td 2H), 3.06(t 2H), 3.45(t 2H), 4.14(d 2H), 4.40(t 1H), 7.11(d 2H), 8.06(d 2H) 13 C-NMR DMSO-d6 21.75, 23.08, 31.48, 31.95, 34.35, 38.71, 46.68, 51.09, 58.00, 90.62, 99.76, 112.49, 112.99, 113.30, 113.36, 113.54, 132.52, 153.66, 174.05, 177.82 DSC:mp 236℃

[0152] (Production of EO polymer (EO-5(19))) The base polymer (A-5b) and the compound (E-5(19)) obtained above were reacted in the same manner as described in the preparation of the EO polymer (EO-5(18)) to obtain an EO polymer (EO-5(19)) in which the compound (E-5(19)) was bonded to the base polymer (glass transition temperature Tg: 176°C).

[0153] [Synthesis Example 1] A compound represented by the following formula (E-5(20)) (hereinafter sometimes referred to as "compound (E-5(20))") was obtained by the following procedure. [ka]

[0154] <Synthesis of 1-((trimethylsilyl)oxy)cyclopentane-1-carbonitrile (E5-1(2))> [ka] To 50 mL of dehydrated acetonitrile, 41 mg (0.050 mmol) of 1,5,7-triazabicyclo[4.4.0]5-decene polystyrene (PS-TBD) was added, followed by 3.58 g (42.6 mmol) of cyclopentanone and 3.50 g (35.3 mmol) of trimethylsilyl cyanide. After stirring at room temperature for 3 hours, the PS-TBD was filtered off, and the solvent was concentrated under reduced pressure to obtain 6.05 g of the compound represented by formula (E5-1(2)) (yield: 94%).

[0155] The compound represented by formula (E5-1(2)) 1 H-NMR analysis and 13 C-NMR analysis was performed. 1 H-NMR CDCl3 0.24(s 9H), 1.73-1.88(m 4H), 1.94-2.03(m 2H), 2.05-2.19(m 2H) 13 C-NMR CDCl3 1.11, 22.62, 41.72, 74.47, 122.65

[0156] Synthesis of (4-fluorophenyl)(1-hydroxycyclopentyl)methanone (E5-2(2)) [ka] To 1.05 g (43.2 mmol) of magnesium was added 10 mL of THF, and two drops of 1,2-dibromoethane were added. A solution of 7.88 g (45.0 mmol) of 4-bromofluorobenzene diluted with 2 mL of THF was added dropwise with stirring and water cooling. After 90 minutes of stirring at room temperature, a solution of 6.05 g (33.0 mmol) of the compound represented by formula (E5-1(2)) diluted with 3 mL of THF was added dropwise with stirring and water cooling. After stirring at room temperature for 18 hours, the mixture was cooled to below 10°C, and 20 mL of 6 mol / L aqueous hydrochloric acid solution was slowly added dropwise. After stirring at room temperature for 2.5 hours, the mixture was neutralized by dispersing 40 g of sodium bicarbonate in the mixture. Extraction was performed by adding 150 mL of ethyl acetate and 100 mL of 10% brine. The ethyl acetate extract was washed with 10% brine, dried over anhydrous sodium sulfate, and the solvent was concentrated under reduced pressure to obtain a crude product of the compound represented by formula (E5-2(2)) (hereinafter referred to as "compound (E5-2(2))"). This composition was purified by silica gel column chromatography (chloroform / ethyl acetate: 10 / 1) to obtain 2.48 g (58.1 mmol) of compound (E5-2(2)) (yield: 36%).

[0157] Synthesis of 2-(3-cyano-4-(4-fluorophenyl)-1-oxaspiro[4,4]non-3-en-2-ylidene)malononitrile (E5-3(2)) [ka] 1.57 g (7.54 mmol) of compound (E5-2(2)) and 1.50 g (22.7 mmol) of malononitrile were dissolved in 12 mL of pyridine, and approximately 0.05 g of acetic acid was added and stirred at room temperature for 65 hours. The reaction solution was dispersed in 240 mL of water, and the precipitated crystals were collected by filtration. The obtained crystals were washed with water and then with methanol, and dried under reduced pressure at 70 °C to obtain 1.79 g (5.86 mmol) of the compound represented by formula (E5-3(2)) (yield: 78%).

[0158] The compound represented by formula (E5-3(2)) 1 H-NMR analysis, 13 C-NMR analysis and melting point measurement were performed using a differential scanning calorimeter. 1 H-NMR CDCl3 1.96-2.05(m 2H), 2.13-2.21(m 2H), 2.22-2.28(m 2H), 2.28-2.37(m 2H), 7.31(dd 2H), 7.83(dd 2H) 13 C-NMR CDCl3 25.86, 39.58, 58.79, 102.00, 108.85, (110.48, 110.50), 111.35, (117.48, 117.63), (123.62, 123.60), (131.08, 131.15), 164.82, 166.54, 174.09, 175.08 DSC:mp 205℃

[0159] <Synthesis of Compound (E-5(20)) (2-(3-cyano-4-(4-((2-hydroxyethyl)(methyl)amino)phenyl)-1-oxaspiro[4,4]non-3-en-2-ylidenemalononitrile)> Compound (E5-3(2)) and methyl-2-hydroxyethylamine were reacted and treated in the same manner as described in the synthesis of (E-5) above to obtain compound (E-5(20)) (yield: 25%).

[0160] Compound (E-5(20)) 1 H-NMR analysis, 13 C-NMR analysis and melting point measurement were performed using a differential scanning calorimeter. 1 H-NMR Acetone-d6 2.07-2.21(m 4H), 2.27-2.33(m 2H), 2.47-2.54(m 2H), 3.27(s 3H), 3.75(t 2H), 3.82(t 2H), 7.02(d 2H), 8.05(d 2H)) 13 C-NMR Acetone-d6 29.59, 39.59, 41.84, 53.05, 55.17, 59.94, 60.06, 91.78, 108.64, 113.05, 113.16, 113.95, 114.53, 132.93, 155.27, 173.18, 178.41 DSC:mp 265℃

[0161] [Synthesis Example 2] A compound represented by the following formula (E-5(21)) (hereinafter sometimes referred to as "compound (E-5(21))") was obtained by the following procedure. [ka]

[0162] <Synthesis of Compound (E-5(21)) (2-(4-(4-(butyl(4-hydroxybutyl)amino)phenyl)-3-cyano-1-oxaspiro[4,4]non-3-en-2-ylidenemalononitrile)> Compound (E5-3(2)) and butyl-4-hydroxybutylamine were reacted and treated in the same manner as described in the synthesis of (E-5) above to obtain compound (E-5(21)) (yield: 43%).

[0163] Compound (E-5(21)) 1 H-NMR analysis, 13 C-NMR analysis and melting point measurement were performed using a differential scanning calorimeter. 1 H-NMR Acetone-d6 0.99(t 3H), 1.41(td 2H), 1.45(t 1H), 1.64(m 4H), 1.75(m 2H), 2.06(m 2H), 2.16(m 2H), 2.23(m 2H), 2.37(m 2H), 3.42(t 2H), 3.47(t 2H), 3.74(t 2H), 6.71(d 2H), 7.93(d 2H) 13 C-NMR Acetone-d6 13.88, 20.22, 23.94, 26.29, 29.40, 29.66, 41.46, 51.10, 51.12, 53.65, 62.30, 91.09, 107.18, 111.92, 112.18, 113.13, 113.28, 113.58, 132.28, 152.67, 171.59, 177.10 DSC:mp 217℃ [Industrial Applicability]

[0164] The polymer of the present invention can be used as an electro-optical material applied to optical control elements such as optical modulators, optical switches, optical transceivers, optical phased arrays, LiDAR, smart glasses, optical interconnects, optoelectronic circuits, wavelength converters, electric field sensors, THz wave generators and detectors, etc. The polymer of the present invention can be suitably used for optical control elements with high efficiency in wavelength bands shorter than the C band. [Explanation of symbols]

[0165] 10a, 10b arm portion, 11 core, 12 cladding, 15 upper electrode, 16 lower electrode.

Claims

1. A polymer represented by formula (1): 【Chemical 1】 [In formula (1), X represents a phenylene group, an ethylene group, or a phenylenevinylene group; When X represents a phenylene group or an ethylene group, R Ａ１ and R Ａ２ each independently represents an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 12 carbon atoms, or an alkylaryl group having 7 to 15 carbon atoms, and a hydrogen atom in the alkyl group, aryl group, or alkylaryl group may be substituted with a halogen atom; R Ａ１ and R Ａ２ may be linked to each other to form a 3- to 12-membered saturated alicyclic structure together with the carbon atoms to which they are attached, When X represents a phenylene vinylene group, R A1 represents an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 12 carbon atoms, or an alkylaryl group having 7 to 15 carbon atoms, and a hydrogen atom contained in the alkyl group, aryl group, or alkylaryl group may be substituted with a halogen atom; R A2 represents an aryl group having 6 to 12 carbon atoms or an alkylaryl group having 7 to 15 carbon atoms, and a hydrogen atom in the aryl group or the alkylaryl group may be substituted with a halogen atom; R A1 and R A2 may be linked to each other to form, together with the carbon atom to which they are attached, a saturated alicyclic structure having 3 to 12 members. R Ｄ１ represents an alkanediyl group having 1 to 10 carbon atoms, and R Ｄ２ represents an alkyl group having 1 to 10 carbon atoms, and R Ｄ１ and R Ｄ２ means that any carbon atoms contained therein are bonded to each other, and R Ｄ１ and R Ｄ２ may form a 3- to 12-membered saturated heterocyclic ring structure together with the nitrogen atom to which it is bonded. Y represents a linking group. Po represents a polymer structure.

2. A polymer represented by formula (1). 【Chemistry 2】 [In formula (1), R Ａ１ represents an alkyl group having 1 to 10 carbon atoms. R Ａ２ represents a halogenated aryl group having 6 to 12 carbon atoms or an alkylaryl group having 7 to 15 carbon atoms in which at least one hydrogen atom has been substituted with a halogen atom. X represents a phenylene vinylene group. R D1 represents an alkanediyl group having 1 to 10 carbon atoms, R D2 represents an alkyl group having 1 to 10 carbon atoms, and any carbon atoms contained in R D1 and R D2 may be bonded to each other to form a 3- to 12-membered saturated heterocyclic structure together with the nitrogen atom to which R D1 and R D2 are bonded. Y represents a linking group. Po represents a polymer structure.

3. A polymer represented by formula (1): 【Chemistry 3】 [In formula (1), R Ａ１ and R Ａ２ each independently represents an alkyl group having 1 to 10 carbon atoms; R Ａ１ and R Ａ２ may be linked to each other to form a 3- to 12-membered saturated alicyclic structure together with the carbon atoms to which they are attached. X represents a phenylene group. R D1 represents an alkanediyl group having 1 to 10 carbon atoms, R D2 represents an alkyl group having 1 to 10 carbon atoms, and any carbon atoms contained in R D1 and R D2 may be bonded to each other to form a 3- to 12-membered saturated heterocyclic structure together with the nitrogen atom to which R D1 and R D2 are bonded. Y represents a linking group. Po represents a polymer structure.

4. The polymer according to any one of claims 1 to 3, wherein Y in the formula (1) represents a urethane bond.

5. The polymer according to any one of claims 1 to 4, wherein Po in the formula (1) represents a (meth)acrylic polymer structure.

6. An optical control element having an optical waveguide formed from the polymer according to any one of claims 1 to 5.

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