Electro-optical polymer

Abstract

This electro-optical polymer comprises a structure having electro-optical properties on a side chain of a main chain that is a polynorbornene chain.

Description

[Technical Field]

[0001] The present invention relates to electro-optic polymers. [Background technology]

[0002] Electro-optic polymers are attracting attention as materials for next-generation optical and wireless communications. Electro-optic polymers are known as optical materials capable of exhibiting second-order nonlinear optical effects. The second-order nonlinear optical effect of electro-optic polymers makes it possible to convert the frequency of electromagnetic waves in various frequency bands and control the phase of electromagnetic waves using electric fields.

[0003] An example of such an electro-optic polymer is disclosed in US Pat. No. 5,649,999. [Prior art documents] [Patent documents]

[0004] [Patent Document 1] International Publication No. 2018 / 003842 Summary of the Invention [Problem to be solved by the invention]

[0005] One application of next-generation optical communication and wireless communication devices is in-vehicle devices used for autonomous driving and other applications. In-vehicle devices require higher heat resistance than communication devices used for other purposes. The required level of heat resistance varies, but one example is the ability to be stable in continuous use tests at 120°C and to withstand temporary use at 150°C. In addition, devices must be able to temporarily withstand the solder reflow temperature (e.g., 260°C) during device manufacturing.

[0006] Patent Document 1 also recognizes that heat resistance is an issue with electro-optical polymers, and that electro-optical polymers are required to have a high Tg. Therefore, Patent Document 1 proposes "a polymer in which a base polymer (a) having a reactive group (A) and an electro-optic molecule (b) having a plurality of reactive groups (B) form a bond (C) by a reaction between the reactive group (A) and the plurality of reactive groups (B), wherein the bond (C) is at least one selected from the group consisting of a (thio)ester bond, a (thio)urethane bond, a (thio)urea bond, and a (thio)amide bond." However, the heat resistance of the above polymers is not sufficient to meet the ever-increasing demand for higher heat resistance, and electro-optical polymers with even higher heat resistance have been desired.

[0007] The present invention has been made to solve the above problems, and an object of the present invention is to provide an electro-optic polymer having high heat resistance. [Means for solving the problem]

[0008] A first aspect of the electro-optic polymer of the present invention is characterized in that it has an electro-optic structure in a side chain of the main chain, which is a polynorbornene chain.

[0009] A second aspect of the electro-optical polymer of the present invention is characterized in that it has an electro-optical structure in a side chain of a main chain that is a (meth)acrylic chain having a constituent unit represented by the following general formula (B1), and further has a constituent unit represented by the following general formula (B2) that becomes a crosslinking site when copolymerized with a monomer that becomes the constituent unit represented by the general formula (B1): [ka] [In general formula (B1), 3 is the bonding site between the (meth)acrylic chain and the electro-optical structure. 2 is a hydrogen atom or a methyl group. B1 is an integer greater than or equal to 1.] [ka] [In general formula (B2), R 3 and R 4 is a hydrogen atom or a methyl group.B2 is an integer greater than or equal to 1.]

[0010] A third aspect of the electro-optic polymer of the present invention is characterized in that it has an electro-optic structure in a side chain of the main chain, which is a polyimide chain.

[0011] A fourth aspect of the electro-optical polymer of the present invention is characterized in that it has an electro-optical structure in a side chain of a main chain having a triazine ring. [Effects of the Invention]

[0012] According to the present invention, an electro-optic polymer having high heat resistance can be provided. [Brief explanation of the drawings]

[0013] [Figure 1] FIG. 1 is a schematic perspective view showing an example of an optical laminate, which is an example of a device in which an electro-optical polymer is used. [Figure 2] FIG. 2 is a cross-sectional view schematically illustrating an example of a cross section taken along line a1-a2 of the optical laminate shown in FIG. DETAILED DESCRIPTION OF THE INVENTION

[0014] The electro-optical polymer of the present invention will be described below. Note that the present invention is not limited to the following configurations, and may be modified as appropriate within the scope of the present invention. Furthermore, a combination of multiple individual preferred configurations described below also falls within the scope of the present invention.

[0015] Hereinafter, unless a distinction is made between the first, second, third and fourth aspects of the electro-optical polymer of the present invention, they will simply be referred to as "the electro-optical polymer of the present invention."

[0016] The electro-optic polymers of the present invention each have a main chain with a highly heat-resistant structure and an electro-optical side chain, and can be used in devices for optical communication, wireless communication, etc. First, examples of devices using electro-optic polymers will be described as common features of each embodiment. Next, the electro-optic structure will be described. After that, the main chain structure of each embodiment and the overall structure of the electro-optic polymer will be described. In the description of this specification, a formula referred to as a "general formula" may be simply referred to as a "formula."

[0017] [Devices using electro-optic polymers] Fig. 1 is a schematic perspective view showing an example of an optical laminate, which is an example of a device using an electro-optical polymer. Fig. 2 is a schematic cross-sectional view showing an example of a cross section of the optical laminate shown in Fig. 1 taken along line a1-a2.

[0018] The optical laminate 1A shown in FIGS. 1 and 2 has a support 10 and an electro-optical section 20 in the Z direction (stacking direction).

[0019] In the following description, the Z direction will also be referred to as the stacking direction Z. Note that the X direction, Y direction, and Z direction are perpendicular to one another.

[0020] Examples of materials that can be used to form the support 10 include silicon, glass, polynorbornene, transparent polyimide, (meth)acrylic polymer, cycloolefin polymer, cycloolefin copolymer, cyanate ester polymer, etc. The support 10 may contain only one or more of these materials.

[0021] A material that has low terahertz wave absorption is preferred as the constituent material of the support 10. Such a material is preferably one that can ensure surface smoothness and adhesion.

[0022] In this specification, terahertz waves refer to electromagnetic waves in a frequency band of 0.1 THz or more and 10 THz or less, and include microwaves, millimeter waves, infrared light, etc. Hereinafter, a signal formed from terahertz waves will be referred to as a terahertz signal.

[0023] The electro-optical section 20 is provided on the main surface of the support 10. That is, the electro-optical section 20 is in contact with the support 10 in the stacking direction Z.

[0024] The electro-optical section 20 includes a cladding layer 21 , a lower electrode 22 , an upper electrode 23 , and an electro-optical polymer layer 24 .

[0025] The cladding layer 21 is provided to prevent electromagnetic waves (for example, light) propagating through the electro-optic polymer layer 24 from leaking out to the outside from unintended locations.

[0026] 1 and 2, the cladding layer 21 is composed of a first cladding layer 21a, a second cladding layer 21b, a third cladding layer 21c, and a fourth cladding layer 21d. The first cladding layer 21a, the second cladding layer 21b, the third cladding layer 21c, and the fourth cladding layer 21d are stacked in stacking direction Z in this order from the support 10 side.

[0027] Constituent materials of the cladding layer 21, here the first cladding layer 21a, the second cladding layer 21b, the third cladding layer 21c, and the fourth cladding layer 21d, include, for example, silica, silicon dioxide, titanium oxide, magnesium oxide, etc. Each cladding layer may contain only one type of these materials or may contain multiple types of materials.

[0028] The lower electrode 22 is provided on the support 10 side of the cladding layer 21 in the stacking direction Z. In other words, the lower electrode 22 is provided between the support 10 and the cladding layer 21 in the stacking direction Z.

[0029] 1 and 2, the lower electrode 22 is provided between the support 10 and the first clad layer 21a in the stacking direction Z. Furthermore, the lower electrode 22 is in contact with the support 10 and the first clad layer 21a in the stacking direction Z.

[0030] Examples of materials that can be used for the lower electrode 22 include gold, silver, copper, tin, chromium, aluminum, titanium, alloys containing at least one of these metals, and oxides containing at least one of these metals (e.g., indium tin oxide, indium zinc oxide, aluminum-doped zinc oxide, etc.). Among these, gold, silver, copper, aluminum, etc. are preferred because they have low loss at high frequencies including terahertz waves. The lower electrode 22 may contain only one or more of these materials.

[0031] The upper electrode 23 is provided on the opposite side of the cladding layer 21 from the support 10 in the stacking direction Z so as to face the lower electrode 22 in the stacking direction Z.

[0032] In the example shown in FIGS. 1 and 2, the upper electrode 23 is in contact with the fourth cladding layer 21d in the stacking direction Z.

[0033] 1 and 2, the upper electrode 23 is composed of a first upper electrode 23a and a second upper electrode 23b. In the example shown in FIG. 1, the first upper electrodes 23a and the second upper electrodes 23b are lined up in the Y direction, with four of each being lined up in the X direction. In the example shown in FIG. 1, the first upper electrodes 23a and the second upper electrodes 23b are spaced apart in the Y direction, the first upper electrodes 23a are spaced apart from each other in the X direction, and the second upper electrodes 23b are spaced apart from each other in the X direction. Thus, in the example shown in FIG. 1, the upper electrode 23 is composed of eight electrodes.

[0034] The first upper electrode 23a and the second upper electrode 23b are in contact with the fourth cladding layer 21d in the stacking direction Z, respectively.

[0035] Examples of materials constituting the upper electrode 23, here the first upper electrode 23a and the second upper electrode 23b, include gold, silver, copper, tin, chromium, aluminum, titanium, alloys containing at least one of these metals, and oxides containing at least one of these metals (e.g., indium tin oxide, indium zinc oxide, aluminum-doped zinc oxide, etc.). Among these, gold, silver, copper, aluminum, etc. are preferred because they have low loss with respect to high frequencies including terahertz waves. Each upper electrode may contain only one type of these materials, or may contain multiple types.

[0036] The electro-optical polymer layer 24 is composed of a first electro-optical polymer layer 24a and a second electro-optical polymer layer 24b.

[0037] The first electro-optical polymer layer 24a and the second electro-optical polymer layer 24b may each be composed of a single layer, or may each be composed of a plurality of layers.

[0038] 2, the first electro-optic polymer layer 24a is composed of a first layer 24aa and a second layer 24ab. The first layer 24aa and the second layer 24ab are stacked in the stacking direction Z in this order from the support 10 side. In other words, the first layer 24aa and the second layer 24ab are in contact with each other in the stacking direction Z.

[0039] In the example shown in FIG. 2, the second electro-optic polymer layer 24b is made up of only the first layer 24ba.

[0040] The electro-optic polymer layer 24 is composed of an electro-optic polymer containing electro-optic structures.

[0041] Electro-optic polymers are polymers that can exhibit second-order nonlinear optical effects.

[0042] Examples of second-order nonlinear optical effects include second-order harmonic generation, optical rectification, sum harmonic generation, difference frequency generation, optical parametric oscillation, optical parametric amplification, and electro-optic effect (Pockels effect).

[0043] In FIG. 2, the polarization direction of the electro-optic molecules contained in the electro-optic polymer layer 24 is indicated by the direction of the solid arrow.

[0044] The electro-optic polymer (electro-optic molecules) constituting the electro-optic polymer layer 24 exhibits a second-order nonlinear optical effect, making it possible to convert the frequency of electromagnetic waves in various frequency bands and control the phase of electromagnetic waves using an electric field. For example, terahertz waves can be generated by frequency-converting laser light containing two or more frequencies using the second-order nonlinear optical effect. Frequency-converting laser light containing one or more frequencies and terahertz waves using the second-order nonlinear optical effect changes the frequency of the laser light, and terahertz waves can be detected by detecting the frequency-changed laser light. Terahertz waves and electric fields can be detected by using refractive index changes due to the electro-optic effect, which is included in the second-order nonlinear optical effect. Phase modulation of electromagnetic waves can be performed by using refractive index changes due to the electro-optic effect, which is included in the second-order nonlinear optical effect.

[0045] By providing an integrated circuit on the upper electrode of the optical laminate described above, an optical element can be formed. The optical laminate is used as a converter that directly converts an optical signal into a terahertz signal. Furthermore, the optical laminate is also used as a transmitter that transmits the terahertz signal converted from the optical signal to the integrated circuit.

[0046] Furthermore, an optical element may be formed by mounting an antenna on the upper electrode of the optical laminate described above. The optical laminate is used as a converter that directly converts a terahertz signal received by the antenna into an optical signal. Furthermore, the optical laminate is also used as a transmitter that transmits an optical signal converted from a terahertz signal to various devices.

[0047] [Electro-optical structure] The electro-optical structure can be the same as the electro-optical molecule (EO molecule) described in Patent Document 1. For example, it can be a structure represented by a donor structure-bridge structure-acceptor structure (a structure in which the donor structure and the acceptor structure are bonded via a bridge structure).

[0048] The donor structure is a moiety having an electron-donating group, and examples of the electron-donating group include an amino group which may be substituted with an alkyl group, an aryl group, or an acyl group, an alkoxy group, an aryloxy group, and a thioether group.

[0049] The acceptor structural portion is a moiety having an electron-withdrawing group, and examples of the electron-withdrawing group include a nitro group, a cyano group, a dicyanovinyl group, a tricyanovinyl group, a halogen atom, a carbonyl group, a sulfone group, a perfluoroalkyl group, a tricyanovinylfuranyl group, and a tricyanofuranyl group.

[0050] The bridge structure is a moiety having a conjugated chemical structure, and examples of the conjugated chemical structure include aromatic compounds such as benzene, naphthalene, anthracene, perylene, biphenyl, indene, and stilbene; heterocyclic compounds such as furan, pyran, pyrrole, imidazole, pyrazole, thiophene, thiazole, pyridine, pyridazine, pyrimidine, pyrazine, quinoline, and coumarin; and structures in which these compounds form a carbon-carbon unsaturated bond or a nitrogen-nitrogen unsaturated bond.

[0051] The ends of the electro-optical structure have bonding sites with the main chain. The electro-optical structure and the main chain are preferably bonded to each other via at least one bonding site selected from the group consisting of a (thio)ester bond, a (thio)urethane bond, a (thio)urea bond, and a (thio)amide bond. It is preferable that the bonding site of the electro-optical structure and the bonding site of the main chain are bonded to form a bonding site consisting of at least one bond selected from the group consisting of a (thio)ester bond, a (thio)urethane bond, a (thio)urea bond, and a (thio)amide bond. Therefore, the bonding sites of the electro-optical structure and the bonding sites of the main chain in the electro-optical polymer are the residues of the substituents located at the bonding sites of the electro-optical molecules that form the electro-optical structure and the substituents located at the bonding sites of the main chain, respectively.

[0052] A preferred example of the electro-optical structure is a structure represented by the following general formula (Ea).

[0053] [ka] [In general formula (Ea), R D 1a , R D 2a and R D 3a are each independently a hydrogen atom, an alkyl group, an alkoxy group, an aryloxy group, an aralkyloxy group, a silyloxy group, an alkenyloxy group, an alkynyloxy group, a hydroxy group, -Rd 1 -OH(wherein, Rd 1 is a hydrocarbon group), -ORd 2 -OH(wherein, Rd 2 is a hydrocarbon group), -OC(=O)Rd 3 (In the formula, Rd 3 is a hydrocarbon group), amino group, -Rd 4 -NH2(wherein, Rd 4 is a hydrocarbon group), a thiol group, -Rd 5 -SH (wherein Rd 5 is a hydrocarbon group), -NCO or -Rd 6 -NCO(in the formula, Rd 6 indicates a hydrocarbon group). R D 4a and R D 5a At least one of the groups is a structure containing a bonding site with the main chain, and is an acyloxyalkyl group, a silyloxyalkyl group, -Rd 1 -OH(wherein, Rd 1 is a hydrocarbon group), -Rd 4 -NH2(wherein, Rd 4 is a hydrocarbon group), -Rd 5-SH (wherein Rd 5 is a hydrocarbon group) or -Rd 6 -NCO(in the formula, Rd 6 indicates a residue in which a hydrocarbon group is bonded to the main chain binding site. R D 4a and R D 5a The structures that are not bonded to the main chain are alkyl groups, haloalkyl groups, acyloxyalkyl groups, silyloxyalkyl groups, -Rd 1 -OH(wherein, Rd 1 is a hydrocarbon group), -Rd 4 -NH2(wherein, Rd 4 is a hydrocarbon group), an aryl group, -Rd 5 -SH (wherein Rd 5 is a hydrocarbon group) or -Rd 6 -NCO(in the formula, Rd 6 indicates a hydrocarbon group). B represents a linking group, and R A 1a and R A 2a are each independently a hydrogen atom, an alkyl group, an alkenyl group, a cycloalkyl group, a cycloalkenyl group, an alkoxy group, a halogenated hydrocarbon group, an aryl group, a hydroxy group, -Ra 1 -OH(in the formula, Ra 1 is a hydrocarbon group), -ORa 2 -OH(in the formula, Ra 2 is a hydrocarbon group), amino group, -Ra 4 -NH2(wherein, Ra 4 is a hydrocarbon group), thiol group, -Ra 5 -SH(in the formula, Ra 5 represents a hydrocarbon group), -NCO or -Ra 6 -NCO(in the formula, Ra 6 represents a hydrocarbon group). R A 1a and R A 2a When R is a halogenated hydrocarbon group, the halogen is preferably fluorine, and R A 1a and R A2a is preferably a trifluoromethyl group.

[0054] R D 4a and R D 5a At least one of the groups is a structure containing a binding site to the main chain, and represents a residue bound to the binding site of the main chain. When the terminal of the structure containing the bonding site with the main chain is an OH group, the residue structure is an -O- group, and when the terminal of the structure containing the bonding site with the main chain is an NH2 group, the residue structure is an -NH- group, and R D 4a When the terminal of is an SH group, the structure of the residue is an -S- group.

[0055] In the general formula (Ea), examples of B include those that form a conjugated system and those that are a direct bond (-).

[0056] For example, an example of a structure forming a conjugated system is a structure represented by the following general formula (Ba). [ka] (In general formula (Ba), π 1 and π 2 each independently represents the same or different carbon-carbon conjugated π bond, each of which may have the same or different substituent; R B 1 and R B 2 are each independently a hydrogen atom, an alkyl group, an alkoxy group, an aryl group, an alkenyl group, a cycloalkyl group, a cycloalkenyl group, a haloalkyl group, an aralkyl group, an aryloxy group, an aralkyloxy group, a hydroxy group, -Rb 1 -OH(wherein, Rb 1 is a hydrocarbon group), -ORb 2 -OH(wherein, Rb 2 is a hydrocarbon group), amino group, -Rb 4 -NH2(wherein, Rb 4 is a hydrocarbon group), thiol group, -Rb 5 -SH(wherein, Rb5 represents a hydrocarbon group), -NCO or -Rb 6 -NCO(in the formula, Rb 6 represents a hydrocarbon group), each of which may have the same or different substituents, and R B 1 and R B 2 may form a ring together with the two carbon atoms to which it is attached)

[0057] In the electro-optical structure, the position of the bonding site to the main chain is not particularly limited. For example, in a compound having a structure represented by donor structural part-bridge structural part-acceptor structural part, the position of the binding site may be any of the donor structural part, bridge structural part, and acceptor structural part, and it is preferable that the donor structural part has two or more binding sites.

[0058] In the electro-optical structure represented by the general formula (Ea), the position of the bonding site is not particularly limited. In the electro-optical structure represented by the general formula (Ea), the bonding site can be, for example, R D 1a , R D 2a , R D 3a , R D 4a , R D 5a , R A 1a and R A 2a and R D 1a , R D 2a , R D 3a , R D 4a and R D 5a It is preferable that at least two of the above R A 1a and R A 2a It is also preferred that at least one of them has a binding site. The electro-optical structure represented by the general formula (Ea) has an OH group, -R B1 -OH, amino group, and -R B4 -NH2 (wherein R B1 , R B4 is a hydrocarbon group). Also, R D 4a and / or R D 5a OH group, -R B1 -OH, amino group, and -R B4 It may also be a residue in which a group selected from the group consisting of -NH2 is attached to the main chain.

[0059] Specific embodiments having a binding site include the following.

[0060] R D 4a and R D 5a is a bonding site [e.g., a hydroxyalkyl group (e.g., a hydroxy C such as a hydroxymethyl group, a hydroxyethyl group, a hydroxypropyl group, a hydroxybutyl group, etc.] 1-10 alkyl group, etc.), aminoalkyl group (for example, amino C such as aminomethyl group, aminoethyl group, aminopropyl group, aminobutyl group, etc. 1-10 alkyl group, etc.)]

[0061] Also, R D 1a , R D 2a , R D 3a , R D 4a , R D 5a , R A 1a , R A 2a When is not a binding site (i.e., is a non-reactive group), the group is not particularly limited. When these are non-reactive groups, specific examples of the groups include the following groups.

[0062] R D 1a : Hydrogen atom, alkoxy group (e.g., methoxy group, ethoxy group, butoxy group, etc.) 1-10 alkoxy groups), aryloxy groups (e.g., phenoxy groups, etc. 6-10 aryloxy group), aralkyloxy group (e.g., benzyloxy group, phenethyloxy group, etc. 6-10 Aryl C 1-10 alkyloxy groups), etc.

[0063] R D 2a and R D 3a : Hydrogen atoms, etc.

[0064] R D 4a and R D 5a : Alkyl groups (e.g., methyl, ethyl, butyl, etc.) 1-10 alkyl groups), aryl groups (e.g., C 6-10 aryl group), aralkyl group (e.g., benzyl group, phenethyl group, etc.) 6-10 Aryl C 1-10 alkyloxy groups), etc.

[0065] R A 1a and R A 2a : Alkyl groups (e.g., methyl, ethyl, butyl, etc.) 1-10 alkyl groups), aryl groups (e.g., C 6-10 aryl group), cycloalkylaryl group (e.g., C 3-10 Cycloalkyl C 6-10 aryl group), arylaryl group (e.g., C such as biphenylyl group) 6-10 Aryl C 6-10 aryl group), aralkyl group (e.g., benzyl group, phenethyl group, etc.) 6-10 Aryl C 1-10alkyloxy group), halogenated hydrocarbon group [e.g., haloalkyl group (e.g., halo C such as trifluoromethyl group] 1-10 alkyl groups), haloaryl groups (e.g., halo C groups such as pentafluorophenyl groups) 6-10 aryl groups, etc.]

[0066] Specific preferred examples of electro-optical molecules used to form the electro-optical structure represented by (Ea) above include the molecules (E1) to (E4) below. The OH group located at the left end of formulas (E1) to (E3) and the NH2 group located at the left end of formula (E4) are the terminals of the bonding site with the main chain. In electro-optical polymers obtained from the electro-optical molecules of formulas (E1) to (E3), the residue structure is an -O- group, and in electro-optical polymers obtained from the electro-optical molecule of formula (E4), the residue structure is an -NH- group. [ka] [ka] [ka] [In formula (E3), Me is a methyl group.] [ka] [In formula (E4), Me is a methyl group.]

[0067] Furthermore, the electro-optical structure preferably includes, for example, a structure represented by the following general formula (Eb).

[0068] [ka] [In general formula (Eb), R D 4b , R D 5b , R 7a , R 7b , R 7c , R 7d , R 8a , R8b , R 8c and R 8d At least one of these structures contains a bonding site with the main chain. The structures containing the bonding sites to the main chain are each independently a hydroxy group, -Rd 1 -OH(wherein, Rd 1 is a hydrocarbon group), amino group, -Rd 4 -NH2(wherein, Rd 4 is a hydrocarbon group), a thiol group, -Rd 5 -SH (wherein Rd 5 is a hydrocarbon group), -NCO or -Rd 6 -NCO(in the formula, Rd 6 indicates a residue in which a hydrocarbon group is bonded to the main chain binding site. The structures that are not the bonding sites to the main chain are each independently a hydrogen atom, a hydrocarbon group, a hydroxyl group, -Rd 1 -OH(wherein, Rd 1 is a hydrocarbon group), amino group, -Rd 4 -NH2(wherein, Rd 4 is a hydrocarbon group), a thiol group, -Rd 5 -SH (wherein Rd 5 is a hydrocarbon group), -NCO or -Rd 6 -NCO(in the formula, Rd 6 is a hydrocarbon group). In the structure represented by general formula (Eb), R D 4b , R D 5b , R 7a , R 7b , R 7c , R 7d , R 8a , R 8b , R 8c and R 8d At least two of the -Rd 1 -OH(wherein, Rd 1 is a hydrocarbon group), amino group, -Rd 4 -NH2(wherein, Rd 4 is a hydrocarbon group), a thiol group, -Rd 5 -SH (wherein Rd 5is a hydrocarbon group), -NCO or -Rd 6 -NCO(in the formula, Rd 6 is a hydrocarbon group) or a structure which is a residue of such a group.

[0069] R D 4b , R D 5b , R 7a , R 7b , R 7c , R 7d , R 8a , R 8b , R 8c and R 8d In the above, examples of the hydrocarbon group include aliphatic groups [e.g., C 1-10 Alkyl groups (e.g., methyl, ethyl, propyl, butyl, etc.), C 2-10 Alkenyl groups (e.g., ethenyl, propenyl, butenyl, etc.), preferably C 1-6 Alkyl group, C 2-6 alkenyl groups, etc.], alicyclic groups [e.g., C 3-12 Cycloalkyl groups (e.g., cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, etc.), preferably C 3-7 cycloalkyl groups, etc.], aromatic groups {e.g., C 6-20 Aromatic groups [e.g., C 6-20 Aryl groups (e.g., phenyl, tolyl, xylyl, naphthyl, etc.), C 7-20 Aralkyl groups (e.g., benzyl groups, etc.)}. Among these, aliphatic groups are preferred, and C 1-10 Alkyl groups are preferred.

[0070] The electro-optical structure preferably includes at least the structure represented by the above general formula (Ea). In the electro-optical structure, when the structure represented by the general formula (Ea) and the structure represented by the general formula (Eb) are combined, the weight ratio of the structure represented by the general formula (Ea) / the structure represented by the general formula (Eb) is, for example, 3 / 1 to 1 / 1, and preferably 2 / 1 to 1 / 1. The molar ratio of the structure represented by general formula (Ea) / the structure represented by general formula (Eb) is, for example, 3 / 1 to 1 / 1, and preferably 2 / 1 to 1 / 1.

[0071] In the electro-optical structure, by combining the structure represented by the general formula (Ea) with the structure represented by the general formula (Eb), it is possible to increase the refractive index and electro-optical constant without decreasing the resistivity of the electro-optical polymer, compared to when the proportion of the electro-optical structure in the electro-optical polymer is increased using only the structure represented by the general formula (Ea).

[0072] The compound that becomes the electro-optical structure can be produced by a method known per se. For example, Ann.,580,44(1953), Angew.Chem.,92,671(1980), Chem.Ber.,95,581(1962), Macromolecules,2001,34,253, Chem.Mat er.,2007,19,1154, Org.Synth.,VI,901(1980), Chem.Mater.,2002,14,2393, J.Mater.Sci.,39,2335(2004), “Preparative Organic Chemistry”, John Wiley(1975), p.217, J.Org.Chem.,42,353 (1977), J. Org. Chem., 33, 3382 (1968), Synthesis, 1981, 165, WO 2011 / 024774, etc., as well as methods obtained by appropriately modifying these methods, or by combining these methods, can be used to produce a compound that forms an electro-optical structure. The introduction of a binding site may be carried out during the production process of the compound that forms the electro-optical structure.

[0073] [Structure of the main chain of the first embodiment of the electro-optic polymer] A first embodiment of the electro-optical polymer of the present invention has an electro-optical structure in a side chain of a main chain which is a polynorbornene chain.

[0074] The polynorbornene chain has a molecular structure with high heat resistance (high Tg), so by using a polynorbornene chain as the main chain of an electro-optic polymer, it is possible to obtain an electro-optic polymer with high heat resistance.

[0075] It is preferable that the main chain, which is a polynorbornene chain, and the electro-optical structure are bonded by at least one bonding site selected from the group consisting of a (thio)ester bond, a (thio)urethane bond, a (thio)urea bond, and a (thio)amide bond.

[0076] The polynorbornene chain preferably has a structural unit represented by the following general formula (A1). [ka] [In general formula (A1), X 1 is the bonding site between the polynorbornene chain and the electro-optical structure. A1 is an integer greater than or equal to 1.]

[0077] X 1 is preferably a residue of a substituent that, together with a substituent located at a bonding site of the electro-optical structure, generates a bonding site consisting of at least one bond selected from the group consisting of a (thio)ester bond, a (thio)urethane bond, a (thio)urea bond, and a (thio)amide bond. X 1 For example, -COO-R-NCO, -COO-R-NHCOOR 1 , -R-COOR 1 , -COOR 1 , -R-COOH or COOH is a residue bound to the binding site of the electro-optical structure.

[0078] R is an alkylene group which may have a substituent. Examples of the substituent include a halogen, an alkyl group, and an aryl group. The number of carbon atoms in the alkylene group is not limited, but is preferably 2 to 8, more preferably 2 or 3, and even more preferably 2.

[0079] R 1is an alkyl group which may have a substituent. The number of carbon atoms in the alkyl group is preferably 1 to 10. The alkyl group may be linear or branched, and examples of the substituent include halogen, aryl groups, etc. R 1 The alkyl group preferably has 1 or more and 12 or less carbon atoms, and more preferably has 1 or more and 4 or less carbon atoms. Specific examples include a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, an i-butyl group, a t-butyl group, an n-pentyl group, an n-hexyl group, an n-heptyl group, an n-octyl group, and a 2-ethylhexyl group. 1 is preferably a methyl group.

[0080] That is, R is an ethylene group, R 1 is preferably a methyl group, and X 1 is preferably a residue in which the end of -COO-C2H4-NCO, -COO-C2H4-NHCOOCH3, -C2H4-COOCH3, or -C2H4-COOH is bonded to the bonding site of the electro-optical structure.

[0081] X before bonding with the electro-optic structure 1 The structure is -COO-R-NCO or -COO-R-NHCOOR 1 If the terminal is NCO or NHCOOR 1 The end reacts with the OH group of the bonding site of the electro-optical structure to form a (thio)urethane bond. 1 is a residue that reacted with the OH group of the bonding site of the electro-optical structure to form a (thio)urethane bond. X 1 GA-R-COOR 1 , -COOR 1 If -R is a residue of -COOH or -COOR 1 The terminal or COOH terminal is a bonding site with the electro-optical structure, and X 1 may be a residue that reacts with the OH group of the bonding site of the electro-optical structure to form a (thio)ester bond. 1 GA-R-COOR 1 , -COOR 1, where X is a residue of -R-COOH or -COOH 1 may be a residue that reacts with the NH2 group of the binding site of the electro-optical structure to form a (thio)amide bond.

[0082] The polynorbornene chain may have only the structural unit represented by the general formula (A1). 1 An electro-optical structure may be bonded to the end of the X 1 The electro-optical structure may be bonded to only a portion of the substrate. Also, there are multiple X 1 The structures may all be the same or may be partially different.

[0083] The polynorbornene chain preferably has a structural unit represented by the following general formula (A2). [ka] [In general formula (A2), X 1 and X 2 At least one of X is a bonding site between the polynorbornene chain and the electro-optical structure. 1 is the binding site, X 2 is the binding site 、 -O- or -NH- R .X 2 is the binding site, X 1 teeth binding site, A hydrogen atom or an alkyl group which may have a substituent. R .n A2 is an integer greater than or equal to 1.]

[0084] In the case of general formula (A2), as in the case of general formula (A1), X 1 X where is the binding site 1 is preferably a residue of a substituent that, together with a substituent located at a bonding site of the electro-optical structure, generates a bonding site consisting of at least one bond selected from the group consisting of a (thio)ester bond, a (thio)urethane bond, a (thio)urea bond, and a (thio)amide bond. X1 X where is the binding site 1 For example, -COO-R-NCO, -COO-R-NHCOOR 1 , -R-COOR 1 , -COOR 1 , -R-COOH or COOH is preferably a residue whose end is bonded to the bonding site of the electro-optical structure.

[0085] Also, X 2 X where is the binding site 2 is preferably a residue of a substituent located at a bonding site of the electro-optical structure, and which generates a bonding site consisting of at least one bond selected from the group consisting of an imide bond, a (thio)ester bond, a (thio)urethane bond, a (thio)urea bond, and a (thio)amide bond.

[0086] X 2 is, for example, -N(-)-, -CH(-)-COO-R-NCO, -CH(-)-COO-R-NHCOOR 1 , -CH(-)-R-COOR 1 , -CH(-)-COOR 1 , -CH(-)-R-COOH, -CH(-)-COOH, -N(-)-COO-R-NCO, -N(-)-COO-R-NHCOOR 1 , -N(-)-R-COOR 1 , -N(-)-COOR 1 , -N(-)-R-COOH, or -N(-)-COOH is preferably a residue bound to the binding site of the electro-optical structure.

[0087] X 2 If is the residue of an imide bond, X 2 is -N(-)-. X 2 When the starting structure of X is imidized with the NH2 group at the end of the electro-optic molecule as a maleic anhydride group, 2 is the residue of the imide bond.

[0088] X in general formula (A2) 1 and X 2 R, R contained in 1As the group, X in the general formula (A1) 1 R, R contained in 1 In addition, the structure can be the same as the structure exemplified as 1 and X 2 The structures may all be the same or may be partially different.

[0089] Also, X before bonding with the electro-optical structure 1 or X 2 The end of the structure is NCO or NHCOOR 1 If it is at the terminal, it reacts with the OH group of the bonding site of the electro-optical structure to form a (thio)urethane bond. 1 or X 2 is a residue that reacted with the OH group of the bonding site of the electro-optical structure to form a (thio)urethane bond. Also, X before bonding with the electro-optical structure 1 or X 2 The end of the structure is COOR 1 If the terminal or COOH terminal, X 1 or X 2 may be a residue that reacts with an OH group at the binding site of the electro-optical structure to form a (thio)ester bond. Also, X before bonding with the electro-optical structure 1 or X 2 The end of the structure is COOR 1 If the terminal or COOH terminal, X 1 or X 2 may be a residue that reacts with the NH2 group of the binding site of the electro-optical structure to form a (thio)amide bond.

[0090] The polynorbornene chain may have only the structural unit represented by the general formula (A2). 1 and X 2 An electro-optical structure may be bonded to the end of the X 1 and X 2 The electro-optical structure may be bonded to only a portion of the substrate. Also, there are multiple X 1 and X 2The structures may all be the same or may be partially different.

[0091] The polynorbornene chain may be a copolymer having a constitutional unit represented by the above general formula (A1) and a constitutional unit represented by the above general formula (A2). In this case, the proportion of the constitutional unit represented by the general formula (A1) and the constitutional unit represented by the general formula (A2) is not particularly limited.

[0092] The polynorbornene chain preferably further has a constituent unit represented by the following general formula (A3) in addition to the constituent unit represented by the above general formula (A1) or (A2). [ka] [In the general formula (A3), Z represents a hydrogen atom or an alkyl group which may have a substituent. A3 is an integer greater than or equal to 1.]

[0093] In general formula (A3), Z is an alkyl group which may have a substituent. The alkyl group may be linear or branched, and examples of the substituent include halogen, aryl, and the like. Since Z does not serve as a bonding site with the electro-optical structure, it is preferable that Z does not have a substituent having active hydrogen which may serve as a bonding site (such as an OH group, an NH group, an NCO group, a COOH group, or an SH group). The alkyl group of Z preferably has 1 or more and 12 or less carbon atoms, and more preferably has 4 or more and 8 or less carbon atoms. Specific examples include methyl, ethyl, propyl, isopropyl, n-butyl, i-butyl, t-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, 2-ethylhexyl, etc. Of these, n-butyl or 2-ethylhexyl is preferred.

[0094] The inclusion of a structural unit represented by general formula (A3) allows for adjustment of the physical properties of the electro-optic polymer. An electro-optic polymer in which the polynorbornene chain contains only structural units represented by general formula (A1) or general formula (A2) can be rigid and difficult to handle. The inclusion of a structural unit represented by general formula (A3) in the polynorbornene chain makes the electro-optic polymer flexible and easy to handle.

[0095] The polynorbornene chain preferably has a structural unit represented by the general formula (A1) and a structural unit represented by the general formula (A3). In this case, the ratio (molar ratio) of the structural unit represented by the general formula (A1) to the structural unit represented by the general formula (A3) is not particularly limited, but may be, for example, (A1):(A3)=1:1, 1:2, or 2:1.

[0096] Specific examples of when the polynorbornene chain has a structural unit represented by the above general formula (A1) and a structural unit represented by the above general formula (A3) include the following structures. The polymerized portion [ ]n of the structural unit represented by general formula (A1) A1 and the polymerized portion [ ]n of the structural unit represented by general formula (A3) A3 may be a block polymer or a random polymer. As the electro-optical molecule that forms the electro-optical structure, the molecule of formula (E3) or (E4) is used as an example.

[0097] The terminal of the binding site before binding to the electro-optical structure is an NCO group or an NHCOOR group. 1 An example in which the molecule of formula (E3) is used as an electro-optical molecule forming an electro-optical structure is shown below: The bonding site is a urethane bond. [ka]

[0098] The end of the binding site before binding to the electro-optical structure is COOR 1An example in which the molecule of formula (E4) is used as an electro-optical molecule forming an electro-optical structure is shown below: The bonding site is an amide bond. [ka]

[0099] The polynorbornene chain preferably has a structural unit represented by the general formula (A2) and a structural unit represented by the general formula (A3). In this case, the ratio (molar ratio) of the structural unit represented by the general formula (A2) to the structural unit represented by the general formula (A3) is not particularly limited, but may be, for example, (A2):(A3)=1:1, 1:2, or 2:1. Preferably, (A2):(A3)=1:1.

[0100] Specific examples of electro-optical polymers in which the polynorbornene chain has a constitutional unit represented by the above general formula (A2) and a constitutional unit represented by the above general formula (A3) include the following structures. The polymerized portion [ ]n of the structural unit represented by general formula (A2) A2 and the polymerized portion [ ]n of the structural unit represented by general formula (A3) A3 may be a block polymer or a random polymer. As the electro-optical molecule that forms the electro-optical structure, the molecule of formula (E3) or (E4) is used as an example.

[0101] The terminal of the binding site before binding to the electro-optical structure is an NCO group or an NHCOOR group. 1 An example of the case where the molecule of formula (E3) is used as an electro-optical molecule forming an electro-optical structure is shown below. The bonding site is a urethane bond. X 2 is an example of -O- rather than a binding site. [ka]

[0102] The end of the binding site before binding to the electro-optical structure is COOR 1An example of the case where the molecule of formula (E4) is used as the electro-optical molecule forming the electro-optical structure is shown below. The bonding site is an amide bond. X 2 is an example of -O- rather than a binding site. [ka]

[0103] The polynorbornene chain preferably has a structural unit represented by the general formula (A1), a structural unit represented by the general formula (A2), and a structural unit represented by the general formula (A3). In this case, the ratio (molar ratio) of the structural unit represented by the general formula (A1), the structural unit represented by the general formula (A2), and the structural unit represented by the general formula (A3) is not particularly limited, and may be, for example, (A1):(A2):(A3)=1:1:1.

[0104] Specific examples of when the polynorbornene chain has a structural unit represented by the above general formula (A1), a structural unit represented by the above general formula (A2), and a structural unit represented by the above general formula (A3) include the following structures. The polymerized portion [ ]n of the structural unit represented by general formula (A1) A1 , the polymerized portion [ ]n of the structural unit represented by general formula (A2) A2 and the polymerized portion [ ]n of the structural unit represented by general formula (A3) A3 may be a block polymer or a random polymer. As the electro-optical molecule that forms the electro-optical structure, the molecule of formula (E3) or (E4) is used as an example.

[0105] The terminal of the binding site before binding to the electro-optical structure is an NCO group or an NHCOOR group. 1 An example of the case where the molecule of formula (E3) is used as an electro-optical molecule forming an electro-optical structure is shown below. The bonding site is a urethane bond. X 2 is an example of -O- rather than a binding site. [ka]

[0106] The end of the binding site before binding to the electro-optical structure is COOR 1 An example of the case where the molecule of formula (E4) is used as the electro-optical molecule forming the electro-optical structure is shown below. The bonding site is an amide bond. X 2 is an example of -O- rather than a binding site. [ka]

[0107] The electro-optical polymer according to the first aspect preferably has a glass transition temperature (hereinafter also referred to as Tg) of 210° C. or higher, more preferably 230° C. or higher, and even more preferably 250° C. or higher. When Tg is 210° C. or higher, it can be said that the electro-optical polymer has sufficiently high heat resistance.

[0108] In this specification, the Tg of the electro-optical polymer can be determined by using a differential scanning calorimeter (Rigaku Thermo plus DSC 8230, manufactured by Rigaku Corporation) to measure a 10 mg measurement sample and an empty Al container as a reference sample under conditions of a nitrogen atmosphere and a heating rate of 10°C / min.

[0109] The electro-optical polymer according to the first embodiment can be produced by the following procedure. (1) Preparation of norbornene monomers having binding sites (2) Preparation of polynorbornene chains (3) Introduction of electro-optical structures

[0110] (1) Substituent X serving as a binding site 1 Preparation of norbornene monomer having Substituent X 1 The ethylene derivative having the formula ' is subjected to a Diels-Alder reaction with cyclopentadiene to produce a norbornene monomer by the following reaction. Substituent X 1 ´ is the X before bonding with the electro-optical structure 1 The structure is as follows. [ka]

[0111] (2) Preparation of polynorbornene chains The norbornene monomer obtained in (1) is polymerized to obtain a polynorbornene chain. In this case, the monomer that will become the structural unit represented by general formula (A1), the monomer that will become the structural unit represented by general formula (A2), and the monomer that will become the structural unit represented by general formula (A3) are appropriately mixed and polymerized. The following shows an example of polymerizing a monomer that becomes a structural unit represented by general formula (A1) and a monomer that becomes a structural unit represented by general formula (A3). [ka]

[0112] (3) Introduction of electro-optical structures For example, the polynorbornene chain obtained in (2) is reacted with an electro-optical molecule that forms an electro-optical structure in the presence of a solvent. The reaction may be carried out under heating (for example, at an internal temperature of 50 to 100°C). The reaction may also be carried out in the presence of a catalyst. By the above procedure, an electro-optical polymer having an electro-optical structure in a side chain of the main chain, which is a polynorbornene chain, can be obtained.

[0113] [Structure of the main chain of the second embodiment of the electro-optic polymer] A second aspect of the electro-optical polymer of the present invention has an electro-optical structure in a side chain of a main chain that is a (meth)acrylic chain having a constituent unit represented by the following general formula (B1), and further has a constituent unit represented by the following general formula (B2) that becomes a crosslinking site when copolymerized with a monomer that becomes the constituent unit represented by the general formula (B1). [ka] [In general formula (B1), 3 is the bonding site between the (meth)acrylic chain and the electro-optical structure. 2is a hydrogen atom or a methyl group. B1 is an integer greater than or equal to 1.] [ka] [In general formula (B2), R 3 and R 4 is a hydrogen atom or a methyl group. B2 is an integer greater than or equal to 1.]

[0114] In this specification, the term "(meth)acrylic chain" refers to an acrylic chain or a methacrylic chain, and the term "(meth)acrylate" refers to an acrylate (acrylic acid ester) or a methacrylate (methacrylic acid ester).

[0115] The main chain of the second embodiment of the electro-optic polymer has a structure represented by general formula (B2), in which (meth)acrylic chains are crosslinked at crosslinking sites. The presence of crosslinking sites results in a molecular structure with high heat resistance. Therefore, an electro-optic polymer with high heat resistance can be obtained.

[0116] It is preferable that the main chain, which is a (meth)acrylic chain, and the electro-optical structure are bonded by at least one bonding moiety selected from the group consisting of a (thio)ester bond, a (thio)urethane bond, a (thio)urea bond, and a (thio)amide bond.

[0117] X 3 is preferably a residue of a substituent that, together with a substituent located at a bonding site of the electro-optical structure, generates a bonding site consisting of at least one bond selected from the group consisting of a (thio)ester bond, a (thio)urethane bond, a (thio)urea bond, and a (thio)amide bond.

[0118] X 3 is, for example, a hydrogen atom, -R-NCO, -R-NHCOOR 1 , -R-COOR 1 , -COOR 1 , -R-COOH or COOH is preferably a residue whose end is bonded to the bonding site of the electro-optical structure. R is an alkylene group which may have a substituent. Examples of the substituent include a halogen, an alkyl group, and an aryl group. The number of carbon atoms in the alkylene group is not limited, but is preferably 2 to 8, more preferably 2 or 3, and even more preferably 2.

[0119] R 1 is an alkyl group which may have a substituent. The number of carbon atoms in the alkyl group is preferably 1 to 10. The alkyl group may be linear or branched, and examples of the substituent include halogen, aryl groups, etc. R 1 The alkyl group preferably has 1 or more and 12 or less carbon atoms, and more preferably has 1 or more and 4 or less carbon atoms. Specific examples include a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, an i-butyl group, a t-butyl group, an n-pentyl group, an n-hexyl group, an n-heptyl group, an n-octyl group, and a 2-ethylhexyl group. 1 is preferably a methyl group.

[0120] That is, R is an ethylene group, R 1 is preferably a methyl group, and X 3 is preferably a residue in which the end of -C2H4-NCO, -C2H4-NHCOOCH3, -C2H4-COOCH3, or -C2H4-COOH is bonded to the bonding site of the electro-optical structure.

[0121] R in general formula (B1) 2 is a hydrogen atom or a methyl group, and is preferably a methyl group.

[0122] An example of a monomer that can be used as a constituent unit represented by general formula (B1) is 2-isocyanatoethyl (meth)acrylate (trade name: Karenz (registered trademark) MOI or AOI (manufactured by Resonac Co., Ltd.)) represented by the following general formula (B1-a): [ka]

[0123] R in general formula (B2) 3 and R 4 is a hydrogen atom or a methyl group, and is preferably a methyl group.

[0124] An example of a monomer that becomes the structural unit represented by general formula (B2) is isosorbide (meth)acrylate. [ka]

[0125] The main chain has a structural unit represented by general formula (B1) and a structural unit represented by general formula (B2). The ratio (molar ratio) of the structural unit represented by general formula (B1) to the structural unit represented by general formula (B2) is not particularly limited, but may be, for example, (B1):(B2)=1:1, 1:2, or 2:1.

[0126] Specific examples of electro-optical polymers having a structural unit represented by general formula (B1) and a structural unit represented by general formula (B2) include the following structures. The polymerized portion [ ]n of the structural unit represented by general formula (B1) B1 and the polymerized portion [ ]n of the structural unit represented by general formula (B2) B2 may be a block polymer or a random polymer. The terminal of the binding site before binding to the electro-optical structure is an NCO group or an NHCOOR group. 1 An example in which the molecule of formula (E3) is used as an electro-optical molecule forming an electro-optical structure is shown below: The bonding site is a urethane bond.

[0127] [ka]

[0128] The main chain preferably further contains a structural unit represented by the following general formula (B3). [ka] [In general formula (B3), R 5 is a hydrogen atom or a methyl group, and R 6 represents a hydrogen atom, an alkyl group which may have a substituent, -COOR 7 group, or -COO-R 8 -NHCOOR 9 It is a group. R 7 and R 9 R is an alkyl group which may have a substituent. 8 is an alkylene group which may have a substituent. B3 is an integer greater than or equal to 1.]

[0129] R in general formula (B3) 5 is a hydrogen atom or a methyl group, and is preferably a methyl group. R in general formula (B3) 6 represents a hydrogen atom, an alkyl group which may have a substituent, -COOR 7 group, or -COO-R 8 -NHCOOR 9 It is the base. R 6 When is an alkyl group which may have a substituent, the alkyl group may be linear or branched, and examples of the substituent include halogen, aryl group, etc. Note that it is preferable not to have a substituent having active hydrogen which can be a bonding site (OH group, NH group, NCO group, COOH group, SH group, etc.) since these do not become a bonding site with the electro-optical structure. R 6 The alkyl group preferably has 1 or more and 12 or less carbon atoms, and more preferably has 1 or more and 4 or less carbon atoms. Specific examples include a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, an i-butyl group, a t-butyl group, an n-pentyl group, an n-hexyl group, an n-heptyl group, an n-octyl group, and a 2-ethylhexyl group. 6 is an alkyl group which may have a substituent; 6 is preferably a methyl group.

[0130] R8 is an alkylene group which may have a substituent. Examples of the substituent include halogen, an alkyl group, and an aryl group. The number of carbon atoms in the alkylene group is not limited, but is preferably 2 or more and 8 or less, more preferably 2 or 3, and even more preferably 2.

[0131] R 7 and R 9 are each independently an alkyl group which may have a substituent. The alkyl group may be straight-chain or branched, and examples of the substituent include halogen, aryl groups, etc. Note that it is preferable that the alkyl group does not have a substituent having active hydrogen which can serve as a bonding site (such as an OH group, an NH group, an NCO group, a COOH group, or an SH group) because these do not serve as a bonding site with the electro-optical structure. R 7 and R 9 The alkyl group preferably has 1 or more and 12 or less carbon atoms, and more preferably has 1 or more and 4 or less carbon atoms. Specific examples include a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, an i-butyl group, a t-butyl group, an n-pentyl group, an n-hexyl group, an n-heptyl group, an n-octyl group, and a 2-ethylhexyl group. 7 and R 9 is preferably a methyl group.

[0132] R 6 Ga-COO-R 8 -NHCOOR 9 R when it is a group 6 is preferably —COO—C2H4—NHCOOCH3.

[0133] The inclusion of a structural unit represented by general formula (B3) allows for the adjustment of the physical properties of the electro-optic polymer. Electro-optic polymers containing only structural units represented by general formula (B1) or (B2) can be rigid and difficult to handle. By incorporating a structural unit represented by general formula (B3), the electro-optic polymer becomes flexible and easy to handle.

[0134] Examples of the monomer that becomes the structural unit represented by general formula (B3) include alkyl carbamates of 2-isocyanatoethyl (meth)acrylate, as shown in the following general formula (B3-a). [ka] [In general formula (B3-a), R 5 is a hydrogen atom or a methyl group, and R 8 is an alkylene group which may have a substituent, and R 9 represents an alkyl group which may have a substituent.

[0135] The main chain preferably has a structural unit represented by general formula (B1), a structural unit represented by general formula (B2), and a structural unit represented by general formula (B3). In this case, the ratio (molar ratio) of the structural unit represented by general formula (B1), the structural unit represented by general formula (B2), and the structural unit represented by general formula (B3) is not particularly limited, but may be, for example, (B1):(B2):(B3)=1:1:1 or (B1):(B2):(B3)=1:2:1.

[0136] Specific examples of electro-optical polymers having a structural unit represented by general formula (B1), a structural unit represented by general formula (B2), and a structural unit represented by general formula (B3) include the following structures. The polymerized portion [ ]n of the structural unit represented by general formula (B1) B1、 The polymerized portion [ ]n of the structural unit represented by general formula (B2) B2 and the polymerized portion [ ]n of the structural unit represented by general formula (B3) B3 may be a block polymer or a random polymer. The terminal of the binding site before binding to the electro-optical structure is an NCO group or an NHCOOR group. 1 An example in which the molecule of formula (E3) is used as an electro-optical molecule forming an electro-optical structure is shown below: The bonding site is a urethane bond.

[0137] [ka]

[0138] The electro-optical polymer according to the second embodiment preferably has a glass transition temperature (hereinafter also referred to as Tg) of 230° C. or higher, more preferably 250° C. or higher. When Tg is 230° C. or higher, it can be said that the electro-optical polymer has sufficiently high heat resistance. The electro-optical polymer according to the second embodiment can be produced by the following procedure. (1) Preparation of materials to be used as copolymers (2) Copolymer production (3) Introduction of electro-optical structures

[0139] (1) Preparation of monomers to be copolymerized A monomer that will become the structural unit represented by general formula (B1) and a monomer that will become the structural unit represented by general formula (B2) are prepared. If necessary, a monomer that will become the structural unit represented by general formula (B3) is prepared.

[0140] (2) Copolymer production A copolymer having a (meth)acrylic chain is produced. The method for producing the copolymer is not particularly limited as long as it is a method for polymerizing a (meth)acrylic material, and may be any conventionally known production method.

[0141] (3) Introduction of electro-optical structures For example, the copolymer obtained in (2) is reacted with electro-optical molecules that form the electro-optical structure in the presence of a solvent. The reaction may be carried out under heating (for example, at an internal temperature of 50 to 100°C). The reaction may also be carried out in the presence of a catalyst. By the above procedure, an electro-optical polymer having an electro-optical structure in the side chain of the main chain, which is a (meth)acrylic chain, and having a crosslinking site can be obtained.

[0142] [Structure of the main chain of the third embodiment of the electro-optic polymer] A third embodiment of the electro-optic polymer of the present invention has an electro-optic structure in a side chain of the main chain, which is a polyimide chain.

[0143] The polyimide chain has a molecular structure with high heat resistance (high Tg), so by using a polyimide chain as the main chain of an electro-optic polymer, it is possible to obtain an electro-optic polymer with high heat resistance.

[0144] The polyimide constituting the polyimide chain is preferably a transparent polyimide, which does not absorb visible light and can therefore be suitably used as an electro-optical polymer. As an index of transparency, a total light transmittance of 85% or more is preferable, 88% or more is more preferable, and 90% or more is even more preferable.

[0145] The polyimide chain may be an aromatic polyimide or an aliphatic polyimide, but from the viewpoint of obtaining a transparent polyimide, an aliphatic polyimide is preferred.

[0146] The polyimide chain preferably has a constitutional unit represented by the following general formula (C1). [ka] [In general formula (C1), G is a tetravalent organic group, and A is a divalent organic group. G and / or A has a bonding site with the electro-optical structure. n c1 is an integer greater than or equal to 1.]

[0147] Furthermore, the polyimide chain preferably has a constitutional unit represented by the following general formula (C2). [ka] [In general formula (C2), G 1 is a tetravalent organic group, and A 1 is a divalent organic group. T is a bonding site for the electro-optical structure. n c2 is an integer greater than or equal to 1.]

[0148] The polyimide chain may further contain one or more repeating units represented by general formula (C3), general formula (C4) and general formula (C5) within the range that does not impair the various physical properties of the resulting electro-optical polymer.

[0149] [ka] [n in general formula (C3)] c3 , n in general formula (C4) c4 , n in general formula (C5) c5 is an integer greater than or equal to 1.]

[0150] In the general formula (C1), the general formula (C2) and the general formula (C3), G and G 1 represents a tetravalent organic group, preferably an organic group which may be substituted with a hydrocarbon group or a fluorine-substituted hydrocarbon group. 1 Examples of the aryl group include groups represented by formula (C6), formula (C7), formula (C8), formula (C9), formula (C10), formula (C11), general formula (C12), formula (C13), formula (C14) and formula (C15), and tetravalent chain hydrocarbon groups having 6 or less carbon atoms. * in formulas (C6) to (C15) represents a bond, and G in general formula (C12) represents a bond. 4 represents a single bond, -O-, -CH2-, -CH2-CH2-, -CH(CH3)-, -C(CH3)2-, -C(CF3)2-, -Ar-, -SO2-, -CO-, -O-Ar-O-, -Ar-O-Ar-, -Ar-CH2-Ar-, -Ar-C(CH3)2-Ar-, or -Ar-SO2-Ar-. Ar represents an arylene group having 6 to 20 carbon atoms (more specifically, a phenylene group, etc.) which may be substituted with a fluorine atom. From the viewpoint of suppressing the yellowness of the resulting polymer, G and G 1 preferably represents a group represented by formula (C6) to formula (C13). In particular, G in general formula (C12) 4 is preferably —C(CF 3 ) 2 —.

[0151] [ka]

[0152] In general formula (C4), G 2 represents a trivalent organic group, preferably an organic group which may be substituted with a hydrocarbon group or a fluorine-substituted hydrocarbon group. 2 Examples of the trivalent organic group represented by formula (C6), formula (C7), formula (C8), formula (C9), formula (C10), formula (C11), general formula (C12), formula (C13), formula (C14), and formula (C15) include groups in which one of the bonds is replaced with a hydrogen atom, and trivalent chain hydrocarbon groups having 6 or less carbon atoms.

[0153] In general formula (C5), G 3 represents a divalent organic group, preferably an organic group which may be substituted with a hydrocarbon group or a fluorine-substituted hydrocarbon group. 3 Examples of the divalent organic group represented by formula (C6), formula (C7), formula (C8), formula (C9), formula (C10), formula (C11), general formula (C12), formula (C13), formula (C14), and formula (C15) include groups in which two non-adjacent bonds are replaced with hydrogen atoms, and divalent chain hydrocarbon groups having 6 or less carbon atoms.

[0154] In general formula (C1) to general formula (C5), A, A 1 , A 2 and A 3 Each of A and A represents a divalent organic group, and preferably represents an organic group which may be substituted with a hydrocarbon group or a fluorine-substituted hydrocarbon group. 1 , A 2 , and A 3 Examples of the alkyl group include groups represented by formula (C16), formula (C17), formula (C18), formula (C19), general formula (C20), general formula (C21), general formula (C22), formula (C23), and formula (C24); groups in which these groups are substituted with a methyl group, a fluoro group, a chloro group, or a trifluoromethyl group; and chain hydrocarbon groups having 6 or less carbon atoms. * in formulas (C16) to (C24) represents a bond, and A in general formulas (C20) to (C22) represents a bond. 4, A 5 and A 6 each independently represents a single bond, -O-, -CH2-, -CH2-CH2-, -CH(CH3)-, -C(CH3)2-, -C(CF3)2-, -SO2- or -CO-. 4 and A 6 is -O- and A 5 represents -CH2-, -C(CH3)2-, -C(CF3)2- or -SO2-. 4 and A 5 , and A 5 and A 6 are each preferably in the meta or para position relative to the respective ring. Among these, in the general formula (C20), A 4 is -CH2- and the bond to the aromatic ring is in the para position.

[0155] [ka]

[0156] The repeating units represented by general formula (C1), general formula (C2), and general formula (C3) are usually derived from a diamine and a tetracarboxylic acid compound. The repeating unit represented by general formula (C4) is usually derived from a diamine and a tricarboxylic acid compound. The repeating unit represented by general formula (C5) is usually derived from a diamine and a dicarboxylic acid compound. These carboxylic acid compounds (tetracarboxylic acid compounds, tricarboxylic acid compounds, and dicarboxylic acid compounds) may be carboxylic acid compound analogs (more specifically, carboxylic acid anhydrides, alkanoyl halides, etc.).

[0157] From the viewpoint of further improving the transparency of the electro-optical polymer, the tetracarboxylic acid compound is preferably an alicyclic tetracarboxylic acid dianhydride or a non-condensed polycyclic aromatic tetracarboxylic acid dianhydride, and more preferably 3,3',4,4'-biphenyltetracarboxylic acid dianhydride, 2,2',3,3'-biphenyltetracarboxylic acid dianhydride, 2,2-bis(3,4-dicarboxyphenyl)propane dianhydride, or 4,4'-(hexafluoroisopropylidene)diphthalic dianhydride (6FDA). These suitable tetracarboxylic acid compounds may be used alone or in combination of two or more.

[0158] Examples of tricarboxylic acid compounds include aromatic tricarboxylic acids, aliphatic tricarboxylic acids, and their related acid chloride compounds and acid anhydrides. These tricarboxylic acid compounds may be used alone or in combination of two or more. Examples of tricarboxylic acid compounds include 1,2,4-benzenetricarboxylic acid anhydride; 2,3,6-naphthalenetricarboxylic acid-2,3-anhydride; and compounds in which phthalic anhydride and benzoic acid are linked via a single bond, -CH-, -C(CH)-, -C(CF)-, -SO-, or a phenylene group.

[0159] Examples of dicarboxylic acid compounds include aromatic dicarboxylic acids, aliphatic dicarboxylic acids, and their analogous acid chloride compounds and acid anhydrides. These dicarboxylic acid compounds may be used alone or in combination of two or more. Examples of dicarboxylic acid compounds include terephthalic acid, isophthalic acid, naphthalenedicarboxylic acid, 4,4'-biphenyldicarboxylic acid, 3,3'-biphenyldicarboxylic acid, dicarboxylic acid compounds of chain hydrocarbons having 8 or less carbon atoms, and compounds in which two benzoic acids are linked by -CH-, -C(CH)-, -C(CF)-, -SO-, or a phenylene group.

[0160] Examples of diamines include aliphatic diamines, aromatic diamines, and mixtures thereof. In this specification, the term "aromatic diamine" refers to a diamine in which an amino group is directly bonded to an aromatic ring, and may contain an aliphatic group or other substituent as part of its structure. The aromatic ring may be a single ring or a condensed ring. Examples of aromatic rings include, but are not limited to, a benzene ring, a naphthalene ring, an anthracene ring, and a fluorene ring. Of the aromatic rings, a benzene ring is preferred. In this specification, the term "aliphatic diamine" refers to a diamine in which an amino group is directly bonded to an aliphatic group, and may contain an aromatic ring or other substituent as part of its structure.

[0161] Among the above diamines, from the viewpoint of high transparency and low coloration, it is preferable to use one or more selected from the group consisting of aromatic diamines having a biphenyl structure, and it is more preferable to use one or more selected from the group consisting of 2,2'-dimethylbenzidine, 2,2'-bis(trifluoromethyl)benzidine (TFMB) derivatives, and 4,4'-bis(4-aminophenoxy)biphenyl. The diamine is preferably a diamine having a biphenyl structure and a fluorine-based substituent, such as a 2,2'-bis(trifluoromethyl)benzidine (TFMB) derivative.

[0162] Also, a diphenylmethanediamine derivative is preferred, and a derivative having a substituent in diphenylmethanediamine that serves as a bonding site with the electro-optical structure is preferred. An example of the derivative is 5,5'-methylenebis(2-aminobenzoic acid) (MBAA) having a COOH group on each of the two aromatic rings of diphenylmethanediamine.

[0163] In the polyimide chain, the following forms can be mentioned depending on the position of the bonding site with the electro-optical structure in general formula (C1) or general formula (C2). (Form A) A form in which the organic group G in the structure represented by general formula (C1) or general formula (C2) has a bonding site with the electro-optical structure (Form B) A form in which the organic group A in the structure represented by general formula (C1) or (C2) has a bonding site with the electro-optical structure (Form C) A form in which the binding site T in the structure represented by general formula (C2) is a binding site to the electro-optical structure

[0164] The structure shown in general formula (C2) is a structure in which the COOH group terminal of the polyamic acid, which is a precursor of the imide structure, serves as a bonding site with the electro-optical structure, and in this specification, a main chain having such a site is also included in the polyimide chain. In the case of a main chain having the structure shown in general formula (C2), imide rings are formed by an imidization reaction at locations where the COOH group terminals of the polyamic acid are not bonded to the electro-optical structure, and therefore the main chain as a whole can be regarded as a polyimide chain.

[0165] The bonding sites in the polyimide chain with the electro-optical structure will be described below. In the case of polyimide chains (form A) G and G as tetravalent organic groups shown in the above formulas (C6) to (C15) 1 In the above, the site that is not a bond is a bonding site with the electro-optical structure. The structure of the binding site may be the same as that of the general formula (A1) of the first embodiment of the electro-optical polymer. 1 The same structure as (hereinafter, X 4 ) can be used. That is, the bonding site is preferably a residue of a substituent that generates at least one bonding site selected from the group consisting of a (thio)ester bond, a (thio)urethane bond, a (thio)urea bond, and a (thio)amide bond. G and G as tetravalent organic groups 1 may have one or more binding sites.

[0166] X 4For example, -COO-R-NCO, -COO-R-NHCOOR 1 , -R-COOR 1 , -COOR 1 , -R-COOH or COOH is a residue bound to the binding site of the electro-optical structure.

[0167] R is an alkylene group which may have a substituent. Examples of the substituent include a halogen, an alkyl group, and an aryl group. The number of carbon atoms in the alkylene group is not limited, but is preferably 2 to 8, more preferably 2 or 3, and even more preferably 2.

[0168] R 1 is an alkyl group which may have a substituent. The number of carbon atoms in the alkyl group is preferably 1 to 10. The alkyl group may be linear or branched, and examples of the substituent include halogen, aryl groups, etc. R 1 The alkyl group preferably has 1 or more and 12 or less carbon atoms, and more preferably has 1 or more and 4 or less carbon atoms. Specific examples include a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, an i-butyl group, a t-butyl group, an n-pentyl group, an n-hexyl group, an n-heptyl group, an n-octyl group, and a 2-ethylhexyl group. 1 is preferably a methyl group.

[0169] That is, R is an ethylene group, R 1 is preferably a methyl group, and X 4 is preferably a residue in which the end of -COO-C2H4-NCO, -COO-C2H4-NHCOOCH3, -C2H4-COOCH3 or -C2H4-COOH is bonded to the bonding site of the electro-optical structure. 4 HA-COOR 1 The terminal or -COOH terminal is preferably a residue that is bonded to the binding site of the electro-optical structure.

[0170] X before bonding with the electro-optic structure 4The structure is -COO-R-NCO or -COO-R-NHCOOR 1 If the terminal is NCO or NHCOOR 1 The end reacts with the OH group of the bonding site of the electro-optical structure to form a (thio)urethane bond. 4 is a residue that reacted with the OH group of the bonding site of the electro-optical structure to form a (thio)urethane bond. X 4 GA-R-COOR 1 , -COOR 1 If -R is a residue of -COOH or -COOR 1 The terminal or COOH terminal is a bonding site with the electro-optical structure, and X 4 may be a residue that reacts with the OH group of the bonding site of the electro-optical structure to form a (thio)ester bond. 4 GA-R-COOR 1 , -COOR 1 , where X is a residue of -R-COOH or -COOH 4 may be a residue that reacts with the NH2 group of the binding site of the electro-optical structure to form a (thio)amide bond.

[0171] Examples of polyimide chains of (Form A) include the following structures: The following shows a tetravalent organic group G of formula (C12), 4 The structure of the tetracarboxylic acid anhydride, which is the precursor to -C(CF3)2-, is shown below. In the structure shown below, each of the benzene rings that make up the tetravalent organic group G has a substituent X. 4 '. Substituent X 4 ´ is the X before bonding with the electro-optical structure 4 The structure is as follows. [ka]

[0172] The following structure is an example of a structure in which electro-optical molecules that form an electro-optical structure are bonded to this structure and reacted with diamine to form a polyimide. The end of the binding site before binding to the electro-optical structure is COOR 1 An example in which the molecule of formula (E3) is used as the electro-optical molecule forming the electro-optical structure is shown below: The bonding site is an ester bond. [ka]

[0173] In the case of polyimide chains (form B) A and A shown in the above formulas (C16) to (C24) 1 In the above, the site that is not a bond is a bonding site with the electro-optical structure. The structure of the binding site is X described in (Form A). 4 The same structure can be used.

[0174] Examples of polyimide chains of (form B) include the following structures: The following shows a compound in which the divalent organic group A is represented by the general formula (C20), 4 The structure of the precursor diamine is shown below, where each of the benzene rings that make up the divalent organic group A has a substituent X. 4 '. Substituent X 4 ´ is the X before bonding with the electro-optical structure 4 The structure is as follows. [ka]

[0175] The following structure is an example of a structure in which electro-optical molecules that form an electro-optical structure are bonded to this structure and reacted with tetracarboxylic acid to form a polyimide. The end of the binding site before binding to the electro-optical structure is COOR 1 An example in which the molecule of formula (E3) is used as the electro-optical molecule forming the electro-optical structure is shown below: The bonding site is an ester bond. [ka]

[0176] In the case of polyimide chains (form C) Examples of such a structure include an electro-optical molecule that forms an electro-optical structure and is bonded to the binding site T shown in the general formula (C2) above.

[0177] Examples of polyimide chains of (Form C) include the following structures: This shows an example in which the molecule of formula (E3) is used as the electro-optical molecule that forms the electro-optical structure. [ka]

[0178] In one polyimide chain constituting the electro-optical polymer, the bonding site with the electro-optical structure may be any one, any two, or any three of (Form A), (Form B), and (Form C). The ratio of the structures of (Form A), (Form B), and (Form C) is not particularly limited.

[0179] The electro-optical polymer according to the third embodiment preferably has a glass transition temperature (hereinafter also referred to as Tg) of 230° C. or higher, more preferably 250° C. or higher. When Tg is 230° C. or higher, it can be said that the electro-optical polymer has sufficiently high heat resistance.

[0180] The electro-optical polymer according to the third embodiment can be produced by the following procedure in the case of (Form A) or (Form B). (1) Preparation of polyimide precursor material (2) Introduction of electro-optical structures (3) Copolymer production

[0181] (1) Preparation of polyimide precursor material Diamine and tetracarboxylic acid compounds are prepared as polyimide precursor materials. If necessary, dicarboxylic acid compounds and tricarboxylic acid compounds may be used in combination. In the case of (Configuration A), a substituent that serves as a bonding site with the electro-optical structure is introduced into the tetracarboxylic acid compound. In the case of (Configuration B), a substituent that serves as a bonding site with the electro-optical structure is introduced into the diamine.

[0182] (2) Introduction of electro-optical structures For example, the diamine or tetracarboxylic acid compound prepared in (1) may be reacted with electro-optical molecules that form the electro-optical structure in the presence of a solvent. The reaction may be carried out under heating (for example, at an internal temperature of 50 to 100°C). The reaction may also be carried out in the presence of a catalyst. In the case of (Configuration C), the electro-optical structure is not introduced at this stage.

[0183] (3) Copolymer production The polyimide precursor material is polymerized in a solvent to form the precursor of the polyimide chain, followed by an imidization process to form the imide ring and obtain the polyimide chain.

[0184] The electro-optical polymer according to the third embodiment (form C) can be produced by the following procedure. (1) Preparation of polyimide precursor material (2) Formation of polyimide chain precursors (3) Introduction of electro-optical structures (4) Imidization process

[0185] (1) Preparation of polyimide precursor material Diamine and tetracarboxylic acid compounds are prepared as polyimide precursor materials. If necessary, dicarboxylic acid compounds and tricarboxylic acid compounds may be used in combination.

[0186] (2) Formation of polyimide chain precursors The polyimide precursor material is polymerized in a solvent to form a polyamic acid, which is the precursor of the polyimide chain.

[0187] (3) Introduction of electro-optical structures The electro-optical structure is introduced by reacting some of the COOH groups of the polyamic acid with electro-optical molecules, using them as bonding sites for the electro-optical structure.

[0188] (4) Imidization process The imidization step is carried out on the COOH groups that are not bonded to the electro-optical structure, and the COOH groups of the polyamic acid that are bonded to the electro-optical structure are not ring-closed.

[0189] The formation of the copolymer precursor and the imidization step may be carried out in accordance with a conventionally known production method. By the above procedure, an electro-optical polymer having electro-optical structures in the side chains of the main chain, which is a polyimide chain, can be obtained.

[0190] Below are examples of the synthesis of electro-optic polymers in (Form A), (Form B) and (Form C) according to the above process. Example of (Form A) Steps (1) and (2) Substituent X shown below 4 A tetracarboxylic acid compound having a COOH group as a ' is prepared. [ka]

[0191] An electro-optical structure is introduced by reacting an electro-optical molecule with the COOH group of the tetracarboxylic acid compound. The example below shows the case where the molecule of formula (E3) is used as the electro-optical molecule that forms the electro-optical structure. The bonding site is an ester bond. [ka]

[0192] Process (3) The tetracarboxylic acid compound prepared in step (2) is reacted with a diamine and polymerized in a solvent to form a polyimide chain precursor. The subsequent imidization step forms imide rings, yielding a polyimide chain with the following structure: [ka]

[0193] Example of (Form B) Steps (1) and (2) Substituent X shown below 4 A diamine having a COOH group as a diamine is prepared. [ka]

[0194] An electro-optical structure is introduced by reacting an electro-optical molecule with the COOH group of the diamine. The example below shows the case where the molecule of formula (E3) is used as the electro-optical molecule that forms the electro-optical structure. The bonding site is an ester bond. [ka]

[0195] Process (3) The diamine and tetracarboxylic acid compound prepared in step (2) are reacted and polymerized in a solvent to form a polyimide chain precursor. The imidization step is then carried out to form imide rings, yielding a polyimide chain with the following structure: [ka]

[0196] Example of (Form C) Steps (1) and (2) The diamine and the tetracarboxylic acid compound are reacted to obtain the polyamic acid shown below, which is a precursor of the polyimide chain. [ka]

[0197] Process (3) An electro-optical structure is introduced by reacting an electro-optical molecule with the COOH group of the polyamic acid prepared in step (2). The example below shows the case where the molecule of formula (E3) is used as the electro-optical molecule that forms the electro-optical structure. The bonding site is an ester bond. [ka]

[0198] Process (4) The imidization step is carried out on the COOH groups that are not bonded to the electro-optical structure, and the COOH groups of the polyamic acid that are bonded to the electro-optical structure are not ring-closed. [ka]

[0199] [Structure of the main chain of the fourth embodiment of the electro-optic polymer] A fourth embodiment of the electro-optical polymer of the present invention has an electro-optical structure in a side chain of a main chain having a triazine ring.

[0200] A main chain having a triazine ring has a molecular structure with high heat resistance (high Tg), so by using a main chain having a triazine ring as the main chain of an electro-optic polymer, it is possible to obtain an electro-optic polymer with high heat resistance.

[0201] It is preferred that the main chain having a triazine ring has a structure in which the triazine ring is formed by polymerizing constitutional units represented by the following general formula (D1), and that some OCN terminals are bonding sites with the electro-optical structure. [ka] In general formula (D1), Ar2 represents a phenylene group, a naphthylene group, or a biphenylene group. When Ar2 is a phenylene group, Ar1 represents a naphthylene group or a biphenylene group, and when Ar2 is a naphthylene group or a biphenylene group, Ar1 represents a phenylene group, a naphthylene group, or a biphenylene group. R x is Ar1 Placement of is a substitution group, and each R x may be the same or different groups, and each represents a hydrogen atom, an alkyl group, or an aryl group. y is Ar2 Placement of is a substitution group, and each R y may be the same or different groups, and each Basic, represents an alkyl group or an aryl group. D1 is an integer greater than or equal to 1.]

[0202] The OCN terminal of the structure represented by general formula (D1) is the bonding site with the electro-optical structure, and reacts with the OH group at the bonding site of the electro-optical structure to form a cyanate ester bond.

[0203] The main chain having a triazine ring preferably further has a structural unit having an epoxy group.

[0204] The structural unit having an epoxy group may be a part of the epoxy resins exemplified below: Examples include bisphenol A type epoxy resins, bisphenol F type epoxy resins, biphenyl type epoxy resins, phenol novolac type epoxy resins, cresol novolac type epoxy resins, xylene novolac type epoxy resins, triglycidyl isocyanurate, alicyclic epoxy resins, dicyclopentadiene novolac type epoxy resins, biphenyl novolac type epoxy resins, phenol aralkyl novolac type epoxy resins, and naphthol aralkyl novolac type epoxy resins.

[0205] When introducing a structural unit having an epoxy group into the main chain having a triazine ring, an epoxy resin curing agent can be used.As the epoxy resin curing agent, generally known ones can be used, for example, imidazole derivatives such as 2-methylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 1-cyanoethyl-2-phenylimidazole, 1-cyanoethyl-2-ethyl-4-methylimidazole, 2-phenyl-4,5-dihydroxymethylimidazole, 2-phenyl-4-methyl-5-hydroxymethylimidazole, etc., amine compounds such as dicyandiamide, benzyldimethylamine, 4-methyl-N,N-dimethylbenzylamine, etc., and phosphine-based or phosphonium-based phosphorus compounds can be mentioned.

[0206] Specific examples of electro-optical polymers having a structural unit represented by general formula (D1) include the following structures. The * mark in the following structure indicates a bond, and may be a site to which an electro-optical structure is bonded, as in the structure on the lower right, or may be a site to which an electro-optical structure is not bonded.

[0207] [ka]

[0208] The electro-optical polymer according to the fourth aspect preferably has a glass transition temperature (hereinafter also referred to as Tg) of 230° C. or higher, more preferably 250° C. or higher. When Tg is 230° C. or higher, it can be said that the electro-optical polymer has sufficiently high heat resistance.

[0209] The electro-optical polymer according to the fourth embodiment can be produced by the following procedure. (1) Preparation of cyanate monomer (2) Introduction of electro-optical structures (3) Preparation of cyanate ester resin having a triazine ring

[0210] (1) Preparation of cyanate monomer A cyanate monomer having an OCN group at its terminal is prepared. For example, a monomer manufactured by Mitsubishi Gas Chemical Company, Inc. (CYTESTER (registered trademark)) can be used.

[0211] (2) Introduction of electro-optical structures The cyanate monomer and the electro-optical molecule that will form the electro-optical structure are reacted in the presence of a solvent. The reaction may be carried out under heating (for example, at an internal temperature of 50 to 100°C). The reaction may also be carried out in the presence of a catalyst. By adjusting the number of moles of the OCN group in the cyanate monomer and the number of moles of the binding site in the electro-optical molecule, the electro-optical structure can be introduced into some of the OCN groups in the cyanate monomer.

[0212] (3) Preparation of cyanate ester resin having a triazine ring The cyanate monomer partially incorporating the electro-optical structure prepared in (2) is mixed with a curing catalyst to prepare a curable resin composition. If necessary, other resins such as epoxy resins may be added to the curable resin composition. Examples of the curing catalyst include metal salts such as zinc octoate, zinc naphthenate, cobalt naphthenate, copper naphthenate, and iron acetylacetonate, and compounds having an active hydroxyl group such as phenols, alcohols, and amines. The electro-optic polymer can be obtained by thermally curing the curable resin composition. If the curing temperature is too low, the curing will not proceed, and if it is too high, the cured product will deteriorate. Therefore, the curing temperature is preferably in the range of 150°C to 300°C.

[0213] The present specification discloses the following:

[0214] The present disclosure (1) is an electro-optical polymer having an electro-optical structure in a side chain of a main chain that is a polynorbornene chain.

[0215] The present disclosure (2) is the electro-optical polymer according to the present disclosure (1), in which the main chain, which is a polynorbornene chain, and the electro-optical structure are bonded by at least one bonding moiety selected from the group consisting of a (thio)ester bond, a (thio)urethane bond, a (thio)urea bond, and a (thio)amide bond.

[0216] The present disclosure (3) is an electro-optical polymer according to the present disclosure (1) or (2) having a constitutional unit represented by the following general formula (A2). [ka] [In general formula (A2), X 1 and X 2 At least one of X is a bonding site between the polynorbornene chain and the electro-optical structure. 1 is the binding site, X 2 is not a bonding site and may be -O- or -NH-. 2 is the binding site, X 1 may be a hydrogen atom or an alkyl group which may have a substituent. A2 is an integer greater than or equal to 1.]

[0217] The present disclosure (4) is an electro-optical polymer according to any one of the present disclosures (1) to (3) having a constitutional unit represented by the following general formula (A3). [ka] [In the general formula (A3), Z represents a hydrogen atom or an alkyl group which may have a substituent. A3 is an integer greater than or equal to 1.]

[0218] The present disclosure (5) provides a polymerizable composition comprising a (meth)acrylic chain having an electro-optical structure in a side chain of a main chain that is a structural unit represented by the following general formula (B1): Furthermore, the electro-optical polymer has a structural unit represented by the following general formula (B2) which becomes a crosslinking site when copolymerized with a monomer that becomes the structural unit represented by the general formula (B1). [ka] [In general formula (B1), 3 is the bonding site between the (meth)acrylic chain and the electro-optical structure. 2 is a hydrogen atom or a methyl group. B1 is an integer greater than or equal to 1.] [ka] [In general formula (B2), R 3 and R 4 is a hydrogen atom or a methyl group. B2 is an integer greater than or equal to 1.]

[0219] The present disclosure (6) is an electro-optical polymer having an electro-optical structure in a side chain of a main chain that is a polyimide chain.

[0220] The present disclosure (7) is the electro-optical polymer according to the present disclosure (6), in which the polyimide chain has a constitutional unit represented by the following general formula (C1): [ka] [In general formula (C1), G is a tetravalent organic group, and A is a divalent organic group. G and / or A has a bonding site with the electro-optical structure. n c1 is an integer greater than or equal to 1.]

[0221] The present disclosure (8) is an electro-optical polymer having an electro-optical structure in a side chain of a main chain having a triazine ring.

[0222] The present disclosure (9) is an electro-optical polymer according to the present disclosure (8), in which the main chain having the triazine ring has a structure in which a constitutional unit represented by the following general formula (D1) is polymerized to form a triazine ring, and some OCN terminals are bonding sites with an electro-optical structure. [ka] In general formula (D1), Ar2 represents a phenylene group, a naphthylene group, or a biphenylene group. When Ar2 is a phenylene group, Ar1 represents a naphthylene group or a biphenylene group, and when Ar2 is a naphthylene group or a biphenylene group, Ar1 represents a phenylene group, a naphthylene group, or a biphenylene group. R x R are all substituents of Ar1, and each may independently be the same or different groups. x represents hydrogen, an alkyl group, or an aryl group. y R are all substituents of Ar2, and each may independently be the same or different groups. y represents a hydrogen atom, an alkyl group, or an aryl group. D1 is an integer greater than or equal to 1.]

[0223] The present disclosure (10) is the electro-optical polymer according to any one of the present disclosures (1) to (9), wherein the electro-optical structure is a structure represented by a donor structure portion-a bridge structure portion-an acceptor structure portion.

[0224] The present disclosure (11) is the electro-optical polymer according to any one of the present disclosures (1) to (10), in which the electro-optical structure is a structure represented by the following formula (Ea): [ka] [In general formula (Ea), R D 1a , R D 2a and R D 3a are each independently a hydrogen atom, an alkyl group, an alkoxy group, an aryloxy group, an aralkyloxy group, a silyloxy group, an alkenyloxy group, an alkynyloxy group, a hydroxy group, -Rd 1 -OH(wherein, Rd 1 is a hydrocarbon group), -ORd 2 -OH(wherein, Rd 2 is a hydrocarbon group), -OC(=O)Rd 3 (In the formula, Rd 3 is a hydrocarbon group), amino group, -Rd 4-NH2(wherein, Rd 4 is a hydrocarbon group), a thiol group, -Rd 5 -SH (wherein Rd 5 is a hydrocarbon group), -NCO or -Rd 6 -NCO(in the formula, Rd 6 indicates a hydrocarbon group). R D 4a and R D 5a At least one of the groups is a structure containing a bonding site with the main chain, and is an acyloxyalkyl group, a silyloxyalkyl group, -Rd 1 -OH(wherein, Rd 1 is a hydrocarbon group), -Rd 4 -NH2(wherein, Rd 4 is a hydrocarbon group), -Rd 5 -SH (wherein Rd 5 is a hydrocarbon group) or -Rd 6 -NCO(in the formula, Rd 6 indicates a residue in which a hydrocarbon group is bonded to the main chain binding site. R D 4a and R D 5a The structures that are not bonded to the main chain are alkyl groups, haloalkyl groups, acyloxyalkyl groups, silyloxyalkyl groups, -Rd 1 -OH(wherein, Rd 1 is a hydrocarbon group), -Rd 4 -NH2(wherein, Rd 4 is a hydrocarbon group), an aryl group, -Rd 5 -SH (wherein Rd 5 is a hydrocarbon group) or -Rd 6 -NCO(in the formula, Rd 6 indicates a hydrocarbon group). B represents a linking group, and R A 1a and R A 2a are each independently a hydrogen atom, an alkyl group, an alkenyl group, a cycloalkyl group, a cycloalkenyl group, an alkoxy group, a halogenated hydrocarbon group, an aryl group, a hydroxy group, -Ra 1 -OH(in the formula, Ra 1is a hydrocarbon group), -ORa 2 -OH(in the formula, Ra 2 is a hydrocarbon group), amino group, -Ra 4 -NH2(wherein, Ra 4 is a hydrocarbon group), thiol group, -Ra 5 -SH(in the formula, Ra 5 represents a hydrocarbon group), -NCO or -Ra 6 -NCO(in the formula, Ra 6 represents a hydrocarbon group). [Example]

[0225] The present invention will be specifically described below with reference to examples, but the present invention is not limited to these examples as long as they do not deviate from the gist of the present invention.

[0226] [Tg measurement] The Tg of the electro-optical polymer synthesized in each example was measured using a differential scanning calorimeter (Rigaku Thermo plus DSC 8230, manufactured by Rigaku Corporation) under conditions of a 10 mg measurement sample, an empty Al container as a reference sample, a nitrogen atmosphere, and a heating rate of 10°C / min.

[0227] (Example of the first aspect of the electro-optic polymer) (Examples 1-1 to 1-8) An electro-optical polymer having a polynorbornene chain composed of a structural unit represented by general formula (A1) and a structural unit represented by general formula (A3) was synthesized. The composition of the electro-optical polymer is shown in Table 1.

[0228] (Examples 1-9 to 1-10) An electro-optical polymer having a polynorbornene chain composed of a structural unit represented by general formula (A2) and a structural unit represented by general formula (A3) was synthesized. The composition of the electro-optical polymer is shown in Table 1.

[0229] The substituents in Table 1 have the following meanings. SC-1: residue of -COO-C2H4-NHCOOCH3 SC-2: -C2H4-COOH residue SC-3: 2-ethylhexyl group SC-4: n-butyl group SC-5: Hydrogen atom

[0230] Substituent X having a binding site 1 is SC-1, the electro-optical structure is a structure using a molecule of formula (E3) as the electro-optical molecule. 1 is SC-2, the electro-optical structure is a structure using the molecule of formula (E4) as the electro-optical molecule.

[0231] The ratio of each structural unit in Table 1 is a molar ratio. (A1):(A3)=33:67 is the molar ratio (A1):(A3)=1:2 (A1):(A3)=50:50 is the molar ratio (A1):(A3)=1:1 (A1):(A3)=67:33 is the molar ratio (A1):(A3)=2:1 (A2):(A3)=50:50 is the molar ratio (A2):(A3)=1:1 Each of these is intended to be:

[0232] [Table 1]

[0233] All of the electro-optical polymers synthesized in each example had a high Tg. In Examples 1-1 to 1-6, the lower the proportion of the structural unit (A3), the higher the Tg. A higher proportion of the structural unit (A3) results in a material that is easier to handle, so the proportion of the structural unit (A3) can be determined by taking into account the balance between the required Tg and ease of handling.

[0234] (Example of the second aspect of the electro-optic polymer) (Examples 2-1 to 2-3) An electro-optical polymer was synthesized having a structural unit represented by general formula (B1) and a structural unit represented by general formula (B2) as the main chain (meth)acrylic chain. In Examples 2-2 and 2-3, a structural unit represented by general formula (B3) was also used. The electro-optical structure was a structure using a molecule of formula (E3) as the electro-optical molecule. The composition of the electro-optical polymer is shown in Table 2.

[0235] X in general formula (B1) 3 is -C2H4-NCO, and R 2 is a methyl group. R in general formula (B2) 3 and R 4 is a methyl group. R in general formula (B3) 6 is -COO-C2H4-NHCOOCH3, and R 5 is a methyl group.

[0236] The ratio of each structural unit in Table 2 is a molar ratio. (B1):(B2)=33:67 is the molar ratio (B1):(B2)=1:2 (B1):(B2):(B3)=25:50:25 is the molar ratio (B1):(B2):(B3)=1:2:1 (B1):(B2):(B3)=33:33:33 is the molar ratio (B1):(B2):(B3)=1:1:1 Each of these is intended to be:

[0237] [Table 2]

[0238] All of the electro-optical polymers synthesized in the examples had high Tg. The lower the proportion of the structural unit (B3), the higher the Tg. A higher proportion of the structural unit (B3) results in a material that is easier to handle, so the proportion of the structural unit (B3) can be determined by taking into account the balance between the required Tg and ease of handling.

[0239] (Example of the third aspect of the electro-optic polymer) Example 3-1 This example is an example of a method for producing an electro-optic polymer according to the example of (Form B). As a tetracarboxylic acid compound, 4,4'-(hexafluoroisopropylidene)diphthalic dianhydride (6FDA) was prepared. 5,5'-methylenebis(2-aminobenzoic acid) (MBAA) was prepared as a diamine.

[0240] The COOH group in the side chain of MBAA was reacted with the electro-optical molecule of formula (E3) which has an electro-optical structure, to obtain MBAA with an electro-optical structure introduced in the side chain.

[0241] The copolymer precursor was prepared by reacting 6FDA with MBAA containing electro-optical structures, and then the imidization process was carried out to form imide rings, resulting in the polyimide chains. The polyimide chain synthesis reaction was carried out according to the conditions described in JP 2019-174801 A.

[0242] [Table 3]

[0243] The electro-optical polymer synthesized in Example 3-1 had a high Tg.

[0244] (Example of the fourth aspect of the electro-optic polymer) (Examples 4-1 to 4-4, Comparative Example 4-1) In Examples 4-1 to 4-4, an electro-optical structure was introduced into a cyanate monomer having an OCN group at its terminal, and the resulting monomer was polymerized to synthesize a main chain having a triazine ring. In Examples 4-3 and 4-4, an epoxy resin was further added. As the electro-optical structure, a structure using an electro-optical molecule of formula (E3) was used. In Comparative Example 4-1, a main chain having a triazine ring was synthesized by polymerization without introducing an electro-optical structure into a cyanate monomer. The composition of the electro-optic polymer is shown in Table 4.

[0245] As the cyanate monomer, bisphenol-type cyanate (CYTESTER TA manufactured by Mitsubishi Gas Chemical Company, Inc.) was used. As the epoxy resin, a biphenyl aralkyl type epoxy resin (NC-3000H manufactured by Nippon Kayaku Co., Ltd.) was used.

[0246] The ratio of each structural unit in Table 4 is a molar ratio. (Cyanate monomer):(Electro-optic molecule)=67:33 is the molar ratio (Cyanate monomer):(Electro-optic molecule)=2:1 (Cyanate monomer):(Electro-optic molecule)=50:50 is the molar ratio (Cyanate monomer):(Electro-optic molecule)=1:1 (Cyanate monomer):(Electro-optical molecule)(Epoxy resin)=33:33:33 is the molar ratio (Cyanate monomer):(Electro-optical molecule)(Epoxy resin)=1:1:1 (Cyanate monomer):(Electro-optical molecule)(Epoxy resin)=25:50:25 is the molar ratio (Cyanate monomer):(Electro-optical molecule)(Epoxy resin)=1:2:1 Each of these is intended to be:

[0247] [Table 4]

[0248] The polymer of Comparative Example 4-1, which did not have an electro-optical structure, had the highest Tg. Although Tg tends to decrease as the proportion of electro-optical molecules increases, the electro-optical polymers synthesized in each example still had sufficiently high Tg. [Explanation of symbols]

[0249] 1A Optical laminate 10 Support 20 Electro-optics section 21 Cladding layer 21a First cladding layer 21b Second cladding layer 21c Third cladding layer 21d Fourth cladding layer 22 Lower electrode 23 Upper electrode 23a 1st upper electrode 23b 2nd upper electrode 24 Electro-optic polymer layer 24a First electro-optic polymer layer 24aa First layer of the first electro-optic polymer layer 24ab Second layer of the first electro-optic polymer layer 24b Second electro-optic polymer layer 24ba First layer of the second electro-optic polymer layer

Claims

1. An electro-optical polymer having an electro-optical structure in a side chain of a main chain which is a polynorbornene chain, It has a structural unit represented by the following general formula (A2): 【Chemistry 1】 [In general formula (A2), X １ and X ２ At least one of X is a bonding site between the polynorbornene chain and the electro-optical structure. １ is the binding site, X ２ is a bonding site, —O— or —NH—. ２ is the binding site, X １ is a bonding site, a hydrogen atom, or an alkyl group which may have a substituent. Ａ２ is an integer of 1 or greater. The electro-optical polymer has an electro-optical structure represented by the following formula (Ea) or (Eb): 【Chemistry 2】 [In general formula (E-a), R D 1a , R D 2a and R D 3a each independently represent a hydrogen atom, an alkyl group, an alkoxy group, an aryloxy group, an aralkyloxy group, a silyloxy group, an alkenyloxy group, an alkynyloxy group, a hydroxy group, —Rd 1 —OH (in which Rd 1 is a hydrocarbon group), —ORd 2 —OH (in which Rd 2 is a hydrocarbon group), —OC(═O)Rd 3 (in which Rd 3 is a hydrocarbon group), an amino group, —Rd 4 —NH 2 (in which Rd 4 is a hydrocarbon group), a thiol group, —Rd 5 —SH (in which Rd 5 is a hydrocarbon group), —NCO or —Rd 6 —NCO (in which Rd 6 is a hydrocarbon group). At least one of R D 4a and R D 5a has a structure including a bonding site to the main chain, and represents a residue in which an acyloxyalkyl group, a silyloxyalkyl group, -Rd 1 -OH (wherein Rd 1 is a hydrocarbon group), -Rd 4 -NH 2 (wherein Rd 4 is a hydrocarbon group), -Rd 5 -SH (wherein Rd 5 is a hydrocarbon group), or -Rd 6 -NCO (wherein Rd 6 is a hydrocarbon group) is bonded to the bonding site of the main chain. Of R D 4a and R D 5a , the structure that is not a bonding site to the main chain represents an alkyl group, a haloalkyl group, an acyloxyalkyl group, a silyloxyalkyl group, -Rd 1 -OH (wherein Rd 1 is a hydrocarbon group), -Rd 4 -NH 2 (wherein Rd 4 is a hydrocarbon group), an aryl group, -Rd 5 -SH (wherein Rd 5 is a hydrocarbon group), or -Rd 6 -NCO (wherein Rd 6 is a hydrocarbon group). B represents a linking group, and R A 1a and R A 2a each independently represent a hydrogen atom, an alkyl group, an alkenyl group, a cycloalkyl group, a cycloalkenyl group, an alkoxy group, a halogenated hydrocarbon group, an aryl group, a hydroxy group, -Ra 1 -OH (wherein Ra 1 is a hydrocarbon group), -ORa 2 -OH (wherein Ra 2 is a hydrocarbon group), an amino group, -Ra 4 -NH 2 (wherein Ra 4 is a hydrocarbon group), a thiol group, -Ra 5 -SH (wherein Ra 5 is a hydrocarbon group), -NCO, or -Ra 6 -NCO (wherein Ra 6 is a hydrocarbon group). 【Transformation 3】 [In general formula (E-b), at least one of R D4b , R D5b , R 7a , R 7b , R 7c , R 7d , R 8a , R 8b , R 8c and R 8d has a structure including a bonding site to the main chain. The structures including the bonding site to the main chain each independently represent a residue in which a hydroxy group, -Rd 1 -OH (wherein Rd 1 is a hydrocarbon group), an amino group, -Rd 4 -NH 2 (wherein Rd 4 is a hydrocarbon group), a thiol group, -Rd 5 -SH (wherein Rd 5 is a hydrocarbon group), -NCO, or -Rd 6 -NCO (wherein Rd 6 is a hydrocarbon group) is bonded to the bonding site of the main chain. The structures that are not bonding sites to the main chain are each independently a hydrogen atom, a hydrocarbon group, a hydroxy group, -Rd 1 -OH (wherein Rd 1 is a hydrocarbon group), an amino group, -Rd 4 -NH 2 (wherein Rd 4 is a hydrocarbon group), a thiol group, -Rd 5 -SH (wherein Rd 5 is a hydrocarbon group), -NCO, or -Rd 6 -NCO (wherein Rd 6 is a hydrocarbon group).

2. 2. The electro-optical polymer according to claim 1, wherein the main chain, which is a polynorbornene chain, and the electro-optical structure are bonded together by at least one bonding moiety selected from the group consisting of a (thio)ester bond, a (thio)urethane bond, a (thio)urea bond, and a (thio)amide bond.

3. 2. The electro-optical polymer according to claim 1, which has a structural unit represented by the following general formula (A3): 【Chemistry 4】 In the general formula (A3), Z represents a hydrogen atom or an alkyl group which may have a substituent. Ａ３ is an integer of 1 or greater.

4. An electro-optical polymer having an electro-optical structure in a side chain of a main chain which is a polynorbornene chain, It has a structural unit represented by the following general formula (A3): 【Transformation 5】 In the general formula (A3), Z represents a hydrogen atom or an alkyl group which may have a substituent. Ａ３ is an integer of 1 or greater. The electro-optical polymer has an electro-optical structure represented by the following formula (Ea) or (Eb): 【Transformation 6】 [In general formula (E-a), R D 1a , R D 2a and R D 3a each independently represent a hydrogen atom, an alkyl group, an alkoxy group, an aryloxy group, an aralkyloxy group, a silyloxy group, an alkenyloxy group, an alkynyloxy group, a hydroxy group, —Rd 1 —OH (in which Rd 1 is a hydrocarbon group), —ORd 2 —OH (in which Rd 2 is a hydrocarbon group), —OC(═O)Rd 3 (in which Rd 3 is a hydrocarbon group), an amino group, —Rd 4 —NH 2 (in which Rd 4 is a hydrocarbon group), a thiol group, —Rd 5 —SH (in which Rd 5 is a hydrocarbon group), —NCO or —Rd 6 —NCO (in which Rd 6 is a hydrocarbon group). At least one of R D 4a and R D 5a has a structure including a bonding site to the main chain, and represents a residue in which an acyloxyalkyl group, a silyloxyalkyl group, -Rd 1 -OH (wherein Rd 1 is a hydrocarbon group), -Rd 4 -NH 2 (wherein Rd 4 is a hydrocarbon group), -Rd 5 -SH (wherein Rd 5 is a hydrocarbon group), or -Rd 6 -NCO (wherein Rd 6 is a hydrocarbon group) is bonded to the bonding site of the main chain. Of R D 4a and R D 5a , the structure that is not a bonding site to the main chain represents an alkyl group, a haloalkyl group, an acyloxyalkyl group, a silyloxyalkyl group, -Rd 1 -OH (wherein Rd 1 is a hydrocarbon group), -Rd 4 -NH 2 (wherein Rd 4 is a hydrocarbon group), an aryl group, -Rd 5 -SH (wherein Rd 5 is a hydrocarbon group), or -Rd 6 -NCO (wherein Rd 6 is a hydrocarbon group). B represents a linking group, and R A 1a and R A 2a each independently represent a hydrogen atom, an alkyl group, an alkenyl group, a cycloalkyl group, a cycloalkenyl group, an alkoxy group, a halogenated hydrocarbon group, an aryl group, a hydroxy group, -Ra 1 -OH (wherein Ra 1 is a hydrocarbon group), -ORa 2 -OH (wherein Ra 2 is a hydrocarbon group), an amino group, -Ra 4 -NH 2 (wherein Ra 4 is a hydrocarbon group), a thiol group, -Ra 5 -SH (wherein Ra 5 is a hydrocarbon group), -NCO, or -Ra 6 -NCO (wherein Ra 6 is a hydrocarbon group). 【Transformation 7】 [In general formula (E-b), at least one of R D4b , R D5b , R 7a , R 7b , R 7c , R 7d , R 8a , R 8b , R 8c and R 8d has a structure including a bonding site to the main chain. The structures including the bonding site to the main chain each independently represent a residue in which a hydroxy group, -Rd 1 -OH (wherein Rd 1 is a hydrocarbon group), an amino group, -Rd 4 -NH 2 (wherein Rd 4 is a hydrocarbon group), a thiol group, -Rd 5 -SH (wherein Rd 5 is a hydrocarbon group), -NCO, or -Rd 6 -NCO (wherein Rd 6 is a hydrocarbon group) is bonded to the bonding site of the main chain. The structures that are not bonding sites to the main chain are each independently a hydrogen atom, a hydrocarbon group, a hydroxy group, -Rd 1 -OH (wherein Rd 1 is a hydrocarbon group), an amino group, -Rd 4 -NH 2 (wherein Rd 4 is a hydrocarbon group), a thiol group, -Rd 5 -SH (wherein Rd 5 is a hydrocarbon group), -NCO, or -Rd 6 -NCO (wherein Rd 6 is a hydrocarbon group).

5. 5. The electro-optical polymer according to claim 4, wherein the main chain, which is a polynorbornene chain, and the electro-optical structure are bonded together by at least one bonding moiety selected from the group consisting of a (thio)ester bond, a (thio)urethane bond, a (thio)urea bond, and a (thio)amide bond.

6. The polymerizable compound has an electro-optical structure in a side chain of a main chain that is a (meth)acrylic chain having a structural unit represented by the following general formula (B1), Furthermore, the copolymer further has a structural unit represented by the following general formula (B2) that becomes a crosslinking site upon copolymerization with a monomer that becomes the structural unit represented by the general formula (B1): 【Transformation 8】 [In general formula (B1), X ３ is the bonding site between the (meth)acrylic chain and the electro-optical structure. ２ is a hydrogen atom or a methyl group. Ｂ１ is an integer of 1 or greater. 【Chemistry 9】 [In general formula (B2), R ３ and R ４ is a hydrogen atom or a methyl group. Ｂ２ is an integer of 1 or greater. The electro-optical polymer has an electro-optical structure represented by the following formula (Ea) or (Eb): 【Chemistry 10】 [In general formula (E-a), R D 1a , R D 2a and R D 3a each independently represent a hydrogen atom, an alkyl group, an alkoxy group, an aryloxy group, an aralkyloxy group, a silyloxy group, an alkenyloxy group, an alkynyloxy group, a hydroxy group, —Rd 1 —OH (in which Rd 1 is a hydrocarbon group), —ORd 2 —OH (in which Rd 2 is a hydrocarbon group), —OC(═O)Rd 3 (in which Rd 3 is a hydrocarbon group), an amino group, —Rd 4 —NH 2 (in which Rd 4 is a hydrocarbon group), a thiol group, —Rd 5 —SH (in which Rd 5 is a hydrocarbon group), —NCO or —Rd 6 —NCO (in which Rd 6 is a hydrocarbon group). At least one of R D 4a and R D 5a has a structure including a bonding site to the main chain, and represents a residue in which an acyloxyalkyl group, a silyloxyalkyl group, -Rd 1 -OH (wherein Rd 1 is a hydrocarbon group), -Rd 4 -NH 2 (wherein Rd 4 is a hydrocarbon group), -Rd 5 -SH (wherein Rd 5 is a hydrocarbon group), or -Rd 6 -NCO (wherein Rd 6 is a hydrocarbon group) is bonded to the bonding site of the main chain. Of R D 4a and R D 5a , the structure that is not a bonding site to the main chain represents an alkyl group, a haloalkyl group, an acyloxyalkyl group, a silyloxyalkyl group, -Rd 1 -OH (wherein Rd 1 is a hydrocarbon group), -Rd 4 -NH 2 (wherein Rd 4 is a hydrocarbon group), an aryl group, -Rd 5 -SH (wherein Rd 5 is a hydrocarbon group), or -Rd 6 -NCO (wherein Rd 6 is a hydrocarbon group). B represents a linking group, and R A 1a and R A 2a each independently represent a hydrogen atom, an alkyl group, an alkenyl group, a cycloalkyl group, a cycloalkenyl group, an alkoxy group, a halogenated hydrocarbon group, an aryl group, a hydroxy group, -Ra 1 -OH (wherein Ra 1 is a hydrocarbon group), -ORa 2 -OH (wherein Ra 2 is a hydrocarbon group), an amino group, -Ra 4 -NH 2 (wherein Ra 4 is a hydrocarbon group), a thiol group, -Ra 5 -SH (wherein Ra 5 is a hydrocarbon group), -NCO, or -Ra 6 -NCO (wherein Ra 6 is a hydrocarbon group). 【Chemistry 11】 [In general formula (E-b), at least one of R D4b , R D5b , R 7a , R 7b , R 7c , R 7d , R 8a , R 8b , R 8c and R 8d has a structure including a bonding site to the main chain. The structures including the bonding site to the main chain each independently represent a residue in which a hydroxy group, -Rd 1 -OH (wherein Rd 1 is a hydrocarbon group), an amino group, -Rd 4 -NH 2 (wherein Rd 4 is a hydrocarbon group), a thiol group, -Rd 5 -SH (wherein Rd 5 is a hydrocarbon group), -NCO, or -Rd 6 -NCO (wherein Rd 6 is a hydrocarbon group) is bonded to the bonding site of the main chain. The structures that are not bonding sites to the main chain are each independently a hydrogen atom, a hydrocarbon group, a hydroxy group, -Rd 1 -OH (wherein Rd 1 is a hydrocarbon group), an amino group, -Rd 4 -NH 2 (wherein Rd 4 is a hydrocarbon group), a thiol group, -Rd 5 -SH (wherein Rd 5 is a hydrocarbon group), -NCO, or -Rd 6 -NCO (wherein Rd 6 is a hydrocarbon group).

7. An electro-optical polymer having an electro-optical structure in a side chain of a main chain having a triazine ring, the main chain having a triazine ring has a structure in which a triazine ring is formed by polymerization of a structural unit represented by the following general formula (D1), and a part of the OCN terminals is a bonding site with the electro-optical structure, 【Chemistry 12】 [In general formula (D1), Ar ２ represents a phenylene group, a naphthylene group, or a biphenylene group. ２ is a phenylene group, Ar １ represents a naphthylene group or a biphenylene group, Ar ２ is a naphthylene group or a biphenylene group, Ar １ represents a phenylene group, a naphthylene group or a biphenylene group. R ｘ is Ar １ and each R ｘ may be the same or different groups, and each represents hydrogen, an alkyl group, or an aryl group. ｙ is Ar ２ and each R ｙ may be the same or different groups, and each represents hydrogen, an alkyl group, or an aryl group. Ｄ１ is an integer of 1 or greater. The electro-optical polymer has an electro-optical structure represented by the following formula (Ea) or (Eb): 【Chemistry 13】 [In general formula (E-a), R D 1a , R D 2a and R D 3a each independently represent a hydrogen atom, an alkyl group, an alkoxy group, an aryloxy group, an aralkyloxy group, a silyloxy group, an alkenyloxy group, an alkynyloxy group, a hydroxy group, —Rd 1 —OH (in which Rd 1 is a hydrocarbon group), —ORd 2 —OH (in which Rd 2 is a hydrocarbon group), —OC(═O)Rd 3 (in which Rd 3 is a hydrocarbon group), an amino group, —Rd 4 —NH 2 (in which Rd 4 is a hydrocarbon group), a thiol group, —Rd 5 —SH (in which Rd 5 is a hydrocarbon group), —NCO or —Rd 6 —NCO (in which Rd 6 is a hydrocarbon group). At least one of R D 4a and R D 5a has a structure including a bonding site to the main chain, and represents a residue in which an acyloxyalkyl group, a silyloxyalkyl group, -Rd 1 -OH (wherein Rd 1 is a hydrocarbon group), -Rd 4 -NH 2 (wherein Rd 4 is a hydrocarbon group), -Rd 5 -SH (wherein Rd 5 is a hydrocarbon group), or -Rd 6 -NCO (wherein Rd 6 is a hydrocarbon group) is bonded to the bonding site of the main chain. Of R D 4a and R D 5a , the structure that is not a bonding site to the main chain represents an alkyl group, a haloalkyl group, an acyloxyalkyl group, a silyloxyalkyl group, -Rd 1 -OH (wherein Rd 1 is a hydrocarbon group), -Rd 4 -NH 2 (wherein Rd 4 is a hydrocarbon group), an aryl group, -Rd 5 -SH (wherein Rd 5 is a hydrocarbon group), or -Rd 6 -NCO (wherein Rd 6 is a hydrocarbon group). B represents a linking group, and R A 1a and R A 2a each independently represent a hydrogen atom, an alkyl group, an alkenyl group, a cycloalkyl group, a cycloalkenyl group, an alkoxy group, a halogenated hydrocarbon group, an aryl group, a hydroxy group, -Ra 1 -OH (wherein Ra 1 is a hydrocarbon group), -ORa 2 -OH (wherein Ra 2 is a hydrocarbon group), an amino group, -Ra 4 -NH 2 (wherein Ra 4 is a hydrocarbon group), a thiol group, -Ra 5 -SH (wherein Ra 5 is a hydrocarbon group), -NCO, or -Ra 6 -NCO (wherein Ra 6 is a hydrocarbon group). 【Chemistry 14】 [In general formula (E-b), at least one of R D4b , R D5b , R 7a , R 7b , R 7c , R 7d , R 8a , R 8b , R 8c and R 8d has a structure including a bonding site to the main chain. The structures including the bonding site to the main chain each independently represent a residue in which a hydroxy group, -Rd 1 -OH (wherein Rd 1 is a hydrocarbon group), an amino group, -Rd 4 -NH 2 (wherein Rd 4 is a hydrocarbon group), a thiol group, -Rd 5 -SH (wherein Rd 5 is a hydrocarbon group), -NCO, or -Rd 6 -NCO (wherein Rd 6 is a hydrocarbon group) is bonded to the bonding site of the main chain. The structures that are not bonding sites to the main chain are each independently a hydrogen atom, a hydrocarbon group, a hydroxy group, -Rd 1 -OH (wherein Rd 1 is a hydrocarbon group), an amino group, -Rd 4 -NH 2 (wherein Rd 4 is a hydrocarbon group), a thiol group, -Rd 5 -SH (wherein Rd 5 is a hydrocarbon group), -NCO, or -Rd 6 -NCO (wherein Rd 6 is a hydrocarbon group).

8. An electro-optical polymer having an electro-optical structure in a side chain of a main chain which is a polynorbornene chain, It has a structural unit represented by the following general formula (A2): 【Chemistry 15】 [In general formula (A2), X １ and X ２ At least one of X is a bonding site between the polynorbornene chain and the electro-optical structure. １ is the binding site, X ２ is a bonding site, —O— or —NH—. ２ is the binding site, X １ is a bonding site, a hydrogen atom, or an alkyl group which may have a substituent. Ａ２ is an integer of 1 or greater. The electro-optical polymer has an electro-optical structure represented by the following formula (Ea): 【Chemistry 16】 [In general formula (E-a), R Ｄ １ａ , R Ｄ ２ａ and R Ｄ ３ａ are each independently a hydrogen atom, an alkyl group, an alkoxy group, an aryloxy group, an aralkyloxy group, a silyloxy group, an alkenyloxy group, an alkynyloxy group, a hydroxy group, -Rd １ -OH (wherein, Rd １ represents a hydrocarbon group), -ORd ２ -OH (wherein, Rd ２ represents a hydrocarbon group), —OC(═O)Rd ３ (In the formula, Rd ３ is a hydrocarbon group), an amino group, -Rd ４ -NH ２ (In the formula, Rd ４ is a hydrocarbon group), a thiol group, -Rd ５ -SH (wherein Rd ５ is a hydrocarbon group), —NCO or —Rd ６ -NCO (wherein, Rd ６ represents a hydrocarbon group). R Ｄ ４ａ and R Ｄ ５ａ At least one of the groups is a structure containing a bonding site with the main chain, and is an acyloxyalkyl group, a silyloxyalkyl group, -Rd １ -OH (wherein, Rd １ is a hydrocarbon group), -Rd ４ -NH ２ (In the formula, Rd ４ is a hydrocarbon group), -Rd ５ -SH (wherein Rd ５ is a hydrocarbon group) or -Rd ６ -NCO (wherein, Rd ６ indicates a residue in which a hydrocarbon group is bonded to the main chain bonding site. R Ｄ ４ａ and R Ｄ ５ａ Among these, the structures that are not bonded to the main chain are alkyl groups, haloalkyl groups, acyloxyalkyl groups, silyloxyalkyl groups, -Rd １ -OH (wherein, Rd １ is a hydrocarbon group), -Rd ４ -NH ２ (In the formula, Rd ４ is a hydrocarbon group), an aryl group, -Rd ５ -SH (wherein Rd ５ is a hydrocarbon group) or -Rd ６ -NCO (wherein, Rd ６ represents a hydrocarbon group). B represents a linking group, and R Ａ １ａ and R Ａ ２ａ are each independently a hydrogen atom, an alkyl group, an alkenyl group, a cycloalkyl group, a cycloalkenyl group, an alkoxy group, a halogenated hydrocarbon group, an aryl group, a hydroxy group, -Ra １ -OH (in the formula, Ra １ is a hydrocarbon group), -ORa ２ -OH (in the formula, Ra ２ is a hydrocarbon group), an amino group, -Ra ４ -NH ２ (In the formula, Ra ４ is a hydrocarbon group), a thiol group, -Ra ５ -SH (in the formula, Ra ５ is a hydrocarbon group), —NCO or —Ra ６ -NCO (in the formula, Ra ６ represents a hydrocarbon group).

9. An electro-optical polymer having an electro-optical structure in a side chain of a main chain which is a polynorbornene chain, It has a structural unit represented by the following general formula (A3): 【Chemistry 17】 In the general formula (A3), Z represents a hydrogen atom or an alkyl group which may have a substituent. Ａ３ is an integer of 1 or greater. The electro-optical polymer has an electro-optical structure represented by the following formula (Ea): [Chemistry 18] [In general formula (E-a), R Ｄ １ａ , R Ｄ ２ａ and R Ｄ ３ａ are each independently a hydrogen atom, an alkyl group, an alkoxy group, an aryloxy group, an aralkyloxy group, a silyloxy group, an alkenyloxy group, an alkynyloxy group, a hydroxy group, -Rd １ -OH (wherein, Rd １ represents a hydrocarbon group), -ORd ２ -OH (wherein, Rd ２ represents a hydrocarbon group), —OC(═O)Rd ３ (In the formula, Rd ３ is a hydrocarbon group), an amino group, -Rd ４ -NH ２ (In the formula, Rd ４ is a hydrocarbon group), a thiol group, -Rd ５ -SH (wherein Rd ５ is a hydrocarbon group), —NCO or —Rd ６ -NCO (wherein, Rd ６ represents a hydrocarbon group). R Ｄ ４ａ and R Ｄ ５ａ At least one of the groups is a structure containing a bonding site with the main chain, and is an acyloxyalkyl group, a silyloxyalkyl group, -Rd １ -OH (wherein, Rd １ is a hydrocarbon group), -Rd ４ -NH ２ (In the formula, Rd ４ is a hydrocarbon group), -Rd ５ -SH (wherein Rd ５ is a hydrocarbon group) or -Rd ６ -NCO (wherein, Rd ６ indicates a residue in which a hydrocarbon group is bonded to the main chain bonding site. R Ｄ ４ａ and R Ｄ ５ａ Among these, the structures that are not bonded to the main chain are alkyl groups, haloalkyl groups, acyloxyalkyl groups, silyloxyalkyl groups, -Rd １ -OH (wherein, Rd １ is a hydrocarbon group), -Rd ４ -NH ２ (In the formula, Rd ４ is a hydrocarbon group), an aryl group, -Rd ５ -SH (wherein Rd ５ is a hydrocarbon group) or -Rd ６ -NCO (wherein, Rd ６ represents a hydrocarbon group). B represents a linking group, and R Ａ １ａ and R Ａ ２ａ are each independently a hydrogen atom, an alkyl group, an alkenyl group, a cycloalkyl group, a cycloalkenyl group, an alkoxy group, a halogenated hydrocarbon group, an aryl group, a hydroxy group, -Ra １ -OH (in the formula, Ra １ is a hydrocarbon group), -ORa ２ -OH (in the formula, Ra ２ is a hydrocarbon group), an amino group, -Ra ４ -NH ２ (In the formula, Ra ４ is a hydrocarbon group), a thiol group, -Ra ５ -SH (in the formula, Ra ５ is a hydrocarbon group), —NCO or —Ra ６ -NCO (in the formula, Ra ６ represents a hydrocarbon group).

10. The polymerizable compound has an electro-optical structure in a side chain of a main chain that is a (meth)acrylic chain having a structural unit represented by the following general formula (B1), Furthermore, the copolymer further has a structural unit represented by the following general formula (B2) that becomes a crosslinking site upon copolymerization with a monomer that becomes the structural unit represented by the general formula (B1): 【Chemistry 19】 [In general formula (B1), X ３ is the bonding site between the (meth)acrylic chain and the electro-optical structure. ２ is a hydrogen atom or a methyl group. Ｂ１ is an integer of 1 or greater. 【Chemistry 20】 [In general formula (B2), R ３ and R ４ is a hydrogen atom or a methyl group. Ｂ２ is an integer of 1 or greater. The electro-optical polymer has an electro-optical structure represented by the following formula (Ea): 【Chemistry 21】 [In general formula (E-a), R Ｄ １ａ , R Ｄ ２ａ and R Ｄ ３ａ are each independently a hydrogen atom, an alkyl group, an alkoxy group, an aryloxy group, an aralkyloxy group, a silyloxy group, an alkenyloxy group, an alkynyloxy group, a hydroxy group, -Rd １ -OH (wherein, Rd １ represents a hydrocarbon group), -ORd ２ -OH (wherein, Rd ２ represents a hydrocarbon group), —OC(═O)Rd ３ (In the formula, Rd ３ is a hydrocarbon group), an amino group, -Rd ４ -NH ２ (In the formula, Rd ４ is a hydrocarbon group), a thiol group, -Rd ５ -SH (wherein Rd ５ is a hydrocarbon group), —NCO or —Rd ６ -NCO (wherein, Rd ６ represents a hydrocarbon group). R Ｄ ４ａ and R Ｄ ５ａ At least one of the groups is a structure containing a bonding site with the main chain, and is an acyloxyalkyl group, a silyloxyalkyl group, -Rd １ -OH (wherein, Rd １ is a hydrocarbon group), -Rd ４ -NH ２ (In the formula, Rd ４ is a hydrocarbon group), -Rd ５ -SH (wherein Rd ５ is a hydrocarbon group) or -Rd ６ -NCO (wherein, Rd ６ indicates a residue in which a hydrocarbon group is bonded to the main chain bonding site. R Ｄ ４ａ and R Ｄ ５ａ Among these, the structures that are not bonded to the main chain are alkyl groups, haloalkyl groups, acyloxyalkyl groups, silyloxyalkyl groups, -Rd １ -OH (wherein, Rd １ is a hydrocarbon group), -Rd ４ -NH ２ (In the formula, Rd ４ is a hydrocarbon group), an aryl group, -Rd ５ -SH (wherein Rd ５ is a hydrocarbon group) or -Rd ６ -NCO (wherein, Rd ６ represents a hydrocarbon group). B represents a linking group, and R Ａ １ａ and R Ａ ２ａ are each independently a hydrogen atom, an alkyl group, an alkenyl group, a cycloalkyl group, a cycloalkenyl group, an alkoxy group, a halogenated hydrocarbon group, an aryl group, a hydroxy group, -Ra １ -OH (in the formula, Ra １ is a hydrocarbon group), -ORa ２ -OH (in the formula, Ra ２ is a hydrocarbon group), an amino group, -Ra ４ -NH ２ (In the formula, Ra ４ is a hydrocarbon group), a thiol group, -Ra ５ -SH (in the formula, Ra ５ is a hydrocarbon group), —NCO or —Ra ６ -NCO (in the formula, Ra ６ represents a hydrocarbon group).

11. An electro-optical polymer having an electro-optical structure in a side chain of a main chain having a triazine ring, the main chain having a triazine ring has a structure in which a triazine ring is formed by polymerization of a structural unit represented by the following general formula (D1), and a part of the OCN terminals is a bonding site with the electro-optical structure, 【Chemistry 22】 [In general formula (D1), Ar ２ represents a phenylene group, a naphthylene group, or a biphenylene group. ２ is a phenylene group, Ar １ represents a naphthylene group or a biphenylene group, Ar ２ is a naphthylene group or a biphenylene group, Ar １ represents a phenylene group, a naphthylene group or a biphenylene group. R ｘ is Ar １ and each R ｘ may be the same or different groups, and each represents hydrogen, an alkyl group, or an aryl group. ｙ is Ar ２ and each R ｙ may be the same or different groups, and each represents hydrogen, an alkyl group, or an aryl group. Ｄ１ is an integer of 1 or greater. The electro-optical polymer has an electro-optical structure represented by the following formula (Ea): 【Chemistry 23】 [In general formula (E-a), R Ｄ １ａ , R Ｄ ２ａ and R Ｄ ３ａ are each independently a hydrogen atom, an alkyl group, an alkoxy group, an aryloxy group, an aralkyloxy group, a silyloxy group, an alkenyloxy group, an alkynyloxy group, a hydroxy group, -Rd １ -OH (wherein, Rd １ represents a hydrocarbon group), -ORd ２ -OH (wherein, Rd ２ represents a hydrocarbon group), —OC(═O)Rd ３ (In the formula, Rd ３ is a hydrocarbon group), an amino group, -Rd ４ -NH ２ (In the formula, Rd ４ is a hydrocarbon group), a thiol group, -Rd ５ -SH (wherein Rd ５ is a hydrocarbon group), —NCO or —Rd ６ -NCO (wherein, Rd ６ represents a hydrocarbon group). R Ｄ ４ａ and R Ｄ ５ａ At least one of the groups is a structure containing a bonding site with the main chain, and is an acyloxyalkyl group, a silyloxyalkyl group, -Rd １ -OH (wherein, Rd １ is a hydrocarbon group), -Rd ４ -NH ２ (In the formula, Rd ４ is a hydrocarbon group), -Rd ５ -SH (wherein Rd ５ is a hydrocarbon group) or -Rd ６ -NCO (wherein, Rd ６ indicates a residue in which a hydrocarbon group is bonded to the main chain bonding site. R Ｄ ４ａ and R Ｄ ５ａ Among these, the structures that are not bonded to the main chain are alkyl groups, haloalkyl groups, acyloxyalkyl groups, silyloxyalkyl groups, -Rd １ -OH (wherein, Rd １ is a hydrocarbon group), -Rd ４ -NH ２ (In the formula, Rd ４ is a hydrocarbon group), an aryl group, -Rd ５ -SH (wherein Rd ５ is a hydrocarbon group) or -Rd ６ -NCO (wherein, Rd ６ represents a hydrocarbon group). B represents a linking group, and R Ａ １ａ and R Ａ ２ａ are each independently a hydrogen atom, an alkyl group, an alkenyl group, a cycloalkyl group, a cycloalkenyl group, an alkoxy group, a halogenated hydrocarbon group, an aryl group, a hydroxy group, -Ra １ -OH (in the formula, Ra １ is a hydrocarbon group), -ORa ２ -OH (in the formula, Ra ２ is a hydrocarbon group), an amino group, -Ra ４ -NH ２ (In the formula, Ra ４ is a hydrocarbon group), a thiol group, -Ra ５ -SH (in the formula, Ra ５ is a hydrocarbon group), —NCO or —Ra ６ -NCO (in the formula, Ra ６ represents a hydrocarbon group).

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