Classifications

• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F8/00—Chemical modification by after-treatment
  • C08F8/34—Introducing sulfur atoms or sulfur-containing groups
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
  • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
  • C08F220/10—Esters
  • C08F220/12—Esters of monohydric alcohols or phenols
  • C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
  • C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
  • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
  • C08F220/10—Esters
  • C08F220/26—Esters containing oxygen in addition to the carboxy oxygen
  • C08F220/28—Esters containing oxygen in addition to the carboxy oxygen containing no aromatic rings in the alcohol moiety
  • C08F220/281—Esters containing oxygen in addition to the carboxy oxygen containing no aromatic rings in the alcohol moiety and containing only one oxygen, e.g. furfuryl (meth)acrylate or 2-methoxyethyl (meth)acrylate
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
  • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
  • C08F220/10—Esters
  • C08F220/34—Esters containing nitrogen, e.g. N,N-dimethylaminoethyl (meth)acrylate
  • C08F220/36—Esters containing nitrogen, e.g. N,N-dimethylaminoethyl (meth)acrylate containing oxygen in addition to the carboxy oxygen, e.g. 2-N-morpholinoethyl (meth)acrylate or 2-isocyanatoethyl (meth)acrylate
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F8/00—Chemical modification by after-treatment
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F8/00—Chemical modification by after-treatment
  • C08F8/30—Introducing nitrogen atoms or nitrogen-containing groups
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
  • C08L33/04—Homopolymers or copolymers of esters
  • C08L33/14—Homopolymers or copolymers of esters of esters containing halogen, nitrogen, sulfur, or oxygen atoms in addition to the carboxy oxygen
• • G—PHYSICS
  • G02—OPTICS
  • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
  • G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
  • G02B1/04—Optical elements characterised by the material of which they are made; Optical coatings for optical elements made of organic materials, e.g. plastics

Definitions

• the present invention relates to a copolymer having a nonlinear optically active portion.
• nonlinear optical materials are materials that exhibit a polarization response that is proportional to the square, cube, or higher order terms of the magnitude of the electric field of light, and those that produce a first-order electro-optic effect (Pockels effect), which is a second-order nonlinear optical effect, are being considered for use in optical switches, optical modulation, and the like.
• lithium niobate and potassium dihydrogen phosphate have been put to practical use as inorganic nonlinear optical materials and are widely used.
• organic nonlinear optical materials which have advantages over these inorganic nonlinear optical materials, such as high nonlinear optical performance, low material costs, and high mass productivity, and active research and development is being conducted toward practical use.
• Known methods for fabricating devices using organic nonlinear optical materials include, for example, a method using a single crystal of a compound with nonlinear optical properties (nonlinear optical compound), a vapor deposition method, and an LB film method.
• Other methods include introducing a structure with nonlinear optical properties into the main chain or side chain of a polymer compound, or dispersing a nonlinear optical compound in a polymer matrix.
• polymer systems have the advantage of being easy to process, since films can be formed by casting, dipping, spin coating, and other methods.
• Patent Document 1 proposes a nonlinear optically active copolymer that contains at least a repeating unit A of a specific structure having an adamantyl group and a repeating unit B of a specific structure having a nonlinear optically active site in the same molecule. It also describes that the nonlinear optically active copolymer has sufficient orientation properties and can suppress orientation relaxation of the nonlinear optical material due to heat.
• a thick film formed from a nonlinear optical material is preferable because it allows for more accurate evaluation of absorption loss in wavelength bands with low absorption than a thin film.
• cracks are more likely to occur in the film, and when cracks occur in the film, scattering losses occur, making it impossible to accurately evaluate absorption loss.
• films formed using nonlinear optical materials are required to be thick and crack-free.
• films are often formed not only on flat surface structures, but also on various uneven surface structures, and the stress (distortion) caused by the uneven surface structures makes cracks more likely to occur. For this reason, there is a demand for the development of nonlinear optical materials that are less susceptible to cracking.
• the present invention has been made in consideration of the above problems, and aims to provide a copolymer having a nonlinear optically active site capable of forming a crack-free film, and a nonlinear optical material and an electro-optical element that contain the copolymer.
• the inventors conducted extensive research to solve the above problems and discovered that by introducing repeating structural units containing an adamantyl group having an alkoxy group with 1 to 10 carbon atoms into a polymer having a nonlinear optically active site and forming a film using the polymer, it is possible to form a film without cracks even when the film is thick.
• the present invention was completed based on this knowledge and through further research.
• R 1 represents a hydrogen atom or a methyl group
• W 1 represents -O-, -S- or -NH-
• L 2 represents a divalent hydrocarbon group having 1 to 30 carbon atoms which may contain an ether bond and/or an ester bond;
• Ad represents an adamantyl group which may be substituted with an alkyl group having 1 to 5 carbon atoms;
• R 2 represents an alkoxy group having 1 to 10 carbon atoms bonded to any of the carbon atoms constituting the a
• R 3 represents a hydrogen atom or a methyl group
• W 2 represents -O-, -S- or -NH-
• L 3 represents a divalent hydrocarbon group having 1 to 30 carbon atoms which may contain an ether bond and/or an ester bond
• L 4 represents a divalent hydrocarbon group having 1 to 30 carbon atoms which may contain an ether bond and/or an ester bond
• Z represents an atomic group exhibiting nonlinear optical activity.
• Item 4 The copolymer according to Item 3, further comprising a repeating structural unit (C) having a structure different from the repeating structural unit (A) and the repeating structural unit (B), and the content of the repeating structural unit (C) is 90 mol % or less.
• Item 5 A composition comprising the copolymer according to any one of items 1 to 4 and a solvent.
• Item 6. A nonlinear optical material comprising the copolymer according to any one of items 1 to 4.
• a nonlinear optical material comprising the copolymer according to item 1 and/or a polymer containing a repeating structural unit (A) having an adamantyl group represented by the following formula (1) and not containing a repeating structural unit (B) having a nonlinear optically active site, and a nonlinear optically active compound.
• R 1 represents a hydrogen atom or a methyl group
• W 1 represents -O-, -S- or -NH-
• L 2 represents a divalent hydrocarbon group having 1 to 30 carbon atoms which may contain an ether bond and/or an ester bond;
• Ad represents an adamantyl group which may be substituted with an alkyl group having 1 to 5 carbon atoms;
• R 2 represents an alkoxy group having 1 to 10 carbon atoms bonded to any of the carbon atoms constituting the adamantyl group; and
• n represents an integer from 1 to 15.
• Item 8 An electro-optical element comprising the copolymer according to any one of items 1 to 4, or the nonlinear optical material according to item
• the copolymer of the present invention can form a crack-free film whether the film is thin or thick because the repeating structural unit (A) contains an adamantyl group having an alkoxy group having 1 to 10 carbon atoms.
• a thick, crack-free film formed using a copolymer having a nonlinear optically active site is highly preferable because it allows accurate evaluation of absorption losses at the wavelength used in a device containing the film.
• the copolymer of the present invention which can form a crack-free film, can expand the range of applications to devices using nonlinear optical materials.
• the copolymer of the present invention has the advantage that it is highly soluble in common membrane-forming solvents, making it possible to obtain a highly concentrated membrane-forming solution, which makes it easy to form thick membranes.
• the copolymer of the present invention has a large electro-optic coefficient (r) and exhibits superior electro-optic effects compared to conventional copolymers that have nonlinear optically active sites.
• the copolymer of the present invention has the above characteristics and is therefore suitable for use as a material for electro-optical elements such as optical switches, optical modulators, phase shifters, and terahertz wave generating and detecting elements.
• electro-optical elements such as optical switches, optical modulators, phase shifters, and terahertz wave generating and detecting elements.
• electro-optical elements such as optical switches, optical modulators, phase shifters, and terahertz wave generating and detecting elements.
• films are often formed not only on flat surface structures but also on various uneven surface structures. Films on uneven surface structures are more susceptible to cracking due to stress (distortion) caused by the structure, and therefore the copolymer of the present invention can broaden the scope of application to the electro-optical elements.
• (meth)acrylate means acrylate and/or methacrylate
• (meth)acrylic means acrylic and/or methacrylic
• (meth)acryloyl means acryloyl and/or methacryloyl
• (meth)acrylic acid means acrylic acid and/or methacrylic acid.
• copolymer of the present invention is characterized by comprising a repeating structural unit (A) having an adamantyl group represented by the following formula (1), and a repeating structural unit (B) having a nonlinear optically active site.
• R 1 represents a hydrogen atom or a methyl group
• W 1 represents -O-, -S- or -NH-
• L 2 represents a divalent hydrocarbon group having 1 to 30 carbon atoms which may contain an ether bond and/or an ester bond;
• Ad represents an adamantyl group which may be substituted with an alkyl group having 1 to 5 carbon atoms;
• R 2 represents an alkoxy group having 1 to 10 carbon atoms bonded to any of the carbon atoms constituting the adamantyl group; and
• n represents an integer from 1 to 15.
• the copolymer of the present invention may be a random copolymer or a block copolymer.
• the copolymer of the present invention contains a repeating structural unit (A) having an adamantyl group represented by the above formula (1).
• the repeating structural unit (A) may contain one type or two or more types.
• R 1 in formula (1) is a hydrogen atom or a methyl group, and is preferably a methyl group.
• W 1 in formula (1) is —O—, —S— or —NH—, and is preferably —O—.
• L 1 is a divalent hydrocarbon group having 1 to 30 carbon atoms which may contain a single bond, an ether bond and/or an ester bond, or *-L 2 -NHC( ⁇ O)O-.
• the "*" means a bond end with W 1.
• the L 2 is a divalent hydrocarbon group having 1 to 30 carbon atoms which may contain an ether bond and/or an ester bond.
• the divalent hydrocarbon group having 1 to 30 carbon atoms is not particularly limited and may be any of an aliphatic hydrocarbon group, an aromatic hydrocarbon group, or a combination thereof.
• the aliphatic hydrocarbon group may be linear, branched, or cyclic. Of these, an aliphatic hydrocarbon group is preferred, and an alkylene group having 1 to 6 carbon atoms is more preferred.
• divalent hydrocarbon group having 1 to 30 carbon atoms examples include linear aliphatic hydrocarbon groups such as methylene, ethylene, trimethylene, tetramethylene, pentamethylene, hexamethylene, octane-1,8-diyl, decane-1,10-diyl, icosane-1,20-diyl, and triacontane-1,30-diyl; branched aliphatic hydrocarbon groups such as methylethylene, 1-methyltrimethylene, and 2,2-dimethyltrimethylene; cyclic aliphatic hydrocarbon groups such as cyclopentane-1,3-diyl, cyclohexane-1,4-diyl, tricyclo[5.2.1.0 2,6 ]decanediyl, adamantanediyl, norbornanediyl, and norbornenediyl; and aromatic hydrocarbon groups such as phenylene, toluenediyl, and
• L 1 in formula (1) is preferably a single bond.
• Ad is an adamantyl group that may be substituted with an alkyl group having 1 to 5 carbon atoms.
• the alkyl group having 1 to 5 carbon atoms is not particularly limited and may be linear, branched, or cyclic, and examples thereof include methyl, ethyl, n-propyl, isopropyl, cyclopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, cyclobutyl, n-pentyl, neopentyl, and cyclopentyl groups.
• the Ad may have one alkyl group having 1 to 5 carbon atoms, or two or more alkyl groups having 1 to 5 carbon atoms.
• Ad is preferably an adamantyl group that is not substituted with an alkyl group having 1 to 5 carbon atoms.
• R 2 in formula (1) is an alkoxy group having 1 to 10 carbon atoms bonded to any of the carbon atoms constituting the adamantyl group.
• n in formula (1) is an integer of 1 to 15.
• the number of carbon atoms of the alkoxy group is preferably 1 to 5, more preferably 1 to 3, and even more preferably 1 or 2, from the viewpoint of increasing the glass transition temperature (Tg).
• Tg glass transition temperature
• n is preferably an integer of 1 to 10, more preferably an integer of 1 to 5, even more preferably an integer of 1 to 3, and particularly preferably 1.
• the number of carbon atoms of each alkoxy group may be the same or different.
• the copolymer of the present invention contains a repeating structural unit (B) having a nonlinear optically active site.
• the repeating structural unit (B) may contain one type or two or more types.
• the repeating structural unit (B) is not particularly limited as long as it has a nonlinear optically active site.
• the nonlinear optically active site means an atomic group that exhibits nonlinear optical activity.
• the atomic group that exhibits nonlinear optical activity means an atomic group derived from an organic nonlinear optical compound.
• the organic nonlinear optical compound is not particularly limited, and includes known compounds such as ⁇ -conjugated compounds having an electron-donating group at one end of a ⁇ -conjugated chain and an electron-withdrawing group at the other end, and is preferably one having a large molecular hyperpolarizability ⁇ . Examples of electron-donating groups include dialkylamino groups, and examples of electron-withdrawing groups include cyano groups, nitro groups, and fluoroalkyl groups.
• the repeating structural unit (B) having a nonlinear optically active site preferably contains a repeating structural unit (B1) represented by the following formula (2-1) and/or a repeating structural unit (B2) represented by the following formula (2-2):
• R 3 represents a hydrogen atom or a methyl group
• W 2 represents -O-, -S- or -NH-
• L 3 represents a divalent hydrocarbon group having 1 to 30 carbon atoms which may contain an ether bond and/or an ester bond
• L 4 represents a divalent hydrocarbon group having 1 to 30 carbon atoms which may contain an ether bond and/or an ester bond
• Z represents an atomic group exhibiting nonlinear optical activity.
• R 3 in formulas (2-1) and (2-2) is a hydrogen atom or a methyl group, and is preferably a methyl group.
• W 2 in formulae (2-1) and (2-2) is —O—, —S— or —NH—, and is preferably —O—.
• L 3 is a divalent hydrocarbon group having 1 to 30 carbon atoms which may contain an ether bond and/or an ester bond, or *-L 4 -NHC( ⁇ O)O-.
• the "*" indicates the bond end with W 2.
• L 4 is a divalent hydrocarbon group having 1 to 30 carbon atoms which may contain an ether bond and/or an ester bond.
• the divalent hydrocarbon group having 1 to 30 carbon atoms is not particularly limited and may be any of an aliphatic hydrocarbon group, an aromatic hydrocarbon group, or a combination thereof.
• the aliphatic hydrocarbon group may be linear, branched, or cyclic.
• divalent hydrocarbon group having 1 to 30 carbon atoms examples include linear aliphatic hydrocarbon groups such as methylene, ethylene, trimethylene, tetramethylene, pentamethylene, hexamethylene, octane-1,8-diyl, decane-1,10-diyl, icosane-1,20-diyl, and triacontane-1,30-diyl; branched aliphatic hydrocarbon groups such as methylethylene, 1-methyltrimethylene, and 2,2-dimethyltrimethylene; cyclic aliphatic hydrocarbon groups such as cyclopentane-1,3-diyl, cyclohexane-1,4-diyl, tricyclo[5.2.1.0 2,6 ]decanediyl, adamantanediyl, norbornanediyl, and norbornenediyl; and aromatic hydrocarbon groups such as phenylene, toluenediyl, and
• L3 in formulas (2-1) and (2-2) is preferably an aliphatic hydrocarbon group having 1 to 30 carbon atoms, more preferably an alkylene group having 1 to 6 carbon atoms, even more preferably an alkylene group having 1 to 4 carbon atoms, and particularly preferably an alkylene group having 2 to 4 carbon atoms.
• Z in formulas (2-1) and (2-2) is an atomic group that exhibits nonlinear optical activity.
• the atomic group is an atomic group derived from an organic nonlinear optical compound, and the organic nonlinear optical compound is not particularly limited and may be any known compound, such as a ⁇ -conjugated compound having an electron-donating group at one end of a ⁇ -conjugated chain and an electron-withdrawing group at the other end.
• the electron-donating group include a dialkylamino group
• examples of the electron-withdrawing group include a cyano group, a nitro group, and a fluoroalkyl group.
• Z in the formulas (2-1) and (2-2) is preferably an atomic group represented by the following formula (3-1) or (3-2).
• R 4 represents -O- or -NR 5 -;
• R 5 represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms;
• R 6 and R 7 each independently represent a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, a halogenated alkyl group having 1 to 5 carbon atoms, or an aryl group having 6 to 10 carbon atoms; and the symbol * represents a bond to the remaining structure constituting the atomic group Z that exhibits nonlinear optical activity.
• Z in formulas (2-1) and (2-2) is preferably an atomic group having a functional group derived from a compound represented by the following formula (4-1) or (4-2), i.e., an atomic group obtained by removing one or two hydrogen atoms from any of R 8 to R 20 in a compound represented by the following formula (4-1) or (4-2).
• R 4 represents -O- or -NR 5 -;
• R 5 represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms;
• R 6 and R 7 each independently represent a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, a halogenated alkyl group having 1 to 5 carbon atoms, or an aryl group having 6 to 10 carbon atoms;
• R 8 and R 9 each independently represent a hydrogen atom, an alkyl group having 1 to 10 carbon atoms which may have a substituent, or an aryl group having 6 to 10 carbon atoms which may have a substituent;
• R 10 to R Each of 13 independently represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, a hydroxyl group, an alkoxy group having 1 to 10 carbon atoms, an alkylcarbonyloxy group having 2 to 11 carbon atoms, an aryloxy group having 4 to 10 carbon atoms, an arylcarbony
• R to R each independently represent a hydrogen atom, an alkyl group having 1 to 10 carbon atoms which may have a substituent, or an aryl group having 6 to 10 carbon atoms which may have a substituent, the substituent may be a group capable of reacting with an isocyanate group, and the symbol * represents a bond.
• R 4 is -O- or -NR 5 -, and R 5 is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms.
• R 4 is preferably -O-.
• R 6 and R 7 in formulas (3-1) and (4-1) are each independently a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, a halogenated alkyl group having 1 to 5 carbon atoms, or an aryl group having 6 to 10 carbon atoms.
• the alkyl group having 1 to 5 carbon atoms may have a branched structure or a cyclic structure, and examples thereof include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, a cyclopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, a cyclobutyl group, an n-pentyl group, a neopentyl group, and a cyclopentyl group.
• the halogenated alkyl group having 1 to 5 carbon atoms may have a branched structure or a cyclic structure, and examples thereof include a fluoromethyl group, a trifluoromethyl group, a bromodifluoromethyl group, a 2-chloroethyl group, a 2-bromoethyl group, a 1,1-difluoroethyl group, a 2,2,2-trifluoroethyl group, a 1,1,2,2-tetrafluoroethyl group, a 2-chloro-1,1,2-trifluoroethyl group, a pentafluoroethyl group, a 3-bromopropyl group, a 2,2,3,3-tetrafluoropropyl group, a 1,1,2,3,3,3-hexafluoropropyl group, a 1,1,1,3,3,3-hexafluoropropan-2-yl group, a 3-bromo-2-methylprop
• R 6 and R 7 each independently represent preferably a halogenated alkyl group having 1 to 5 carbon atoms or an aryl group having 6 to 10 carbon atoms, more preferably a trifluoromethyl group or a phenyl group.
• R 8 and R 9 in formulas (4-1) and (4-2) are each independently a hydrogen atom, an alkyl group having 1 to 10 carbon atoms which may have a substituent, or an aryl group having 6 to 10 carbon atoms which may have a substituent.
• the alkyl group having 1 to 10 carbon atoms may have a branched structure or a cyclic structure, or may be an arylalkyl group, such as a methyl group, an ethyl group, an n-propyl group, an isopropyl group, a cyclopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, an n-pentyl group, a neopentyl group, a cyclopentyl group, an n-hexyl group, a cyclohexyl group, an n-octyl group, an n-decyl group, a 1-adamantyl group, a benzyl group, or a phenethyl group.
• arylalkyl group such as a methyl group, an ethyl group, an n-propy
• Examples of the aryl group having 6 to 10 carbon atoms include a phenyl group, a tolyl group, a xylyl group, and a naphthyl group.
• Examples of the substituent include an amino group, a hydroxy group, a carboxy group, an epoxy group, an alkoxycarbonyl group such as a methoxycarbonyl group or a tert-butoxycarbonyl group, a silyloxy group such as a trimethylsilyloxy group, a tert-butyldimethylsilyloxy group, a tert-butyldiphenylsilyloxy group or a triphenylsilyloxy group, and a halogen atom such as a fluoro group, a chloro group, a bromo group or an iodo group.
• the bond of the atomic group (Z) is preferably a bond derived from a group capable of reacting with an isocyanate group contained in
• R 8 and R 9 are each preferably an alkyl group having 1 to 10 carbon atoms which may have a substituent, more preferably an alkyl group having 1 to 5 carbon atoms which may have a substituent, and even more preferably an alkyl group having 1 to 3 carbon atoms which may have a substituent.
• the substituent is preferably a hydroxy group.
• R 10 to R 13 in formulas (4-1) and (4-2) are each independently a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, a hydroxy group, an alkoxy group having 1 to 10 carbon atoms, an alkylcarbonyloxy group having 2 to 11 carbon atoms, an aryloxy group having 4 to 10 carbon atoms, an arylcarbonyloxy group having 5 to 11 carbon atoms, a silyloxy group having an alkyl group having 1 to 6 carbon atoms and/or a phenyl group, or a halogen atom.
• Examples of the alkyl group having 1 to 10 carbon atoms include the groups exemplified in R 8 and R 9.
• Examples of the alkoxy group having 1 to 10 carbon atoms include a group in which the alkyl group having 1 to 10 carbon atoms is bonded via an oxygen atom.
• Examples of the alkylcarbonyloxy group having 2 to 11 carbon atoms include a group in which the alkyl group having 1 to 10 carbon atoms is bonded via a carbonyloxy group.
• Examples of the aryloxy group having 4 to 10 carbon atoms include a phenoxy group, a benzyloxy group, a naphthalene-2-yloxy group, a furan-3-yloxy group, and a thiophene-2-yloxy group.
• Examples of the arylcarbonyloxy group having 5 to 11 carbon atoms include a benzoyloxy group, a 1-naphthoyloxy group, a furan-2-carbonyloxy group, and a thiophene-3-carbonyloxy group.
• Examples of the silyloxy group having an alkyl group and/or a phenyl group having 1 to 6 carbon atoms include a trimethylsilyloxy group, a tert-butyldimethylsilyloxy group, a tert-butyldiphenylsilyloxy group, and a triphenylsilyloxy group.
• Examples of the halogen atom include a fluoro group, a chloro group, a bromo group, and an iodo group.
• R 10 to R 13 are each preferably independently a hydrogen atom or an aryloxy group having 4 to 10 carbon atoms, and more preferably a hydrogen atom or a benzyloxy group.
• R to R in formulas ( 5 ) to (7) each independently represent a hydrogen atom, an alkyl group having 1 to 10 carbon atoms which may have a substituent, or an aryl group having 6 to 10 carbon atoms which may have a substituent, and the substituent may be a group capable of reacting with an isocyanate group.
• the alkyl group having 1 to 10 carbon atoms, the aryl group having 6 to 10 carbon atoms, and the substituent include the groups exemplified above for R 8 and R 9 .
• Ar in formulas (4-1) and (4-2) is a divalent organic group represented by formula (5), (6) or (7), preferably a divalent organic group represented by formula (6), and R 18 and R 19 in formula (6) are preferably hydrogen atoms.
• the copolymer of the present invention may contain a repeating structural unit (C) having a structure different from the repeating structural units (A) and (B) in order to adjust the content of the nonlinear optically active moiety and Tg, improve the solvent resistance and suppress the orientation relaxation in a molded article (e.g., a cured film) obtained using the copolymer of the present invention, or to enable the formation of a molded article by thermal curing.
• the repeating structural unit (C) may contain one type or two or more types.
• the copolymer of the present invention as an optically active material, for example, as a core of an optical waveguide, it is desirable to select the repeating structural unit (C) such that it does not adversely affect the transparency or moldability of the copolymer.
• repeating structural unit (C) examples include structural units derived from monomers such as alkyl (meth)acrylates, alkoxy group-containing (meth)acrylates, alicyclic group-containing (meth)acrylates, aryl group-containing (meth)acrylates, hydroxy group-containing (meth)acrylates, epoxy group-containing (meth)acrylates, carboxy group-containing (meth)acrylates, and isocyanate group-containing (meth)acrylates.
• alkyl (meth)acrylates examples include methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, isopropyl (meth)acrylate, n-butyl (meth)acrylate, isobutyl (meth)acrylate, tert-butyl (meth)acrylate, sec-butyl (meth)acrylate, n-pentyl (meth)acrylate, n-hexyl (meth)acrylate, n-octyl (meth)acrylate, isooctyl (meth)acrylate, and n-octyl (meth)acrylate.
• acrylates examples include ethylhexyl (meth)acrylate, isononyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, decyl (meth)acrylate, dodecyl (meth)acrylate, tridecyl (meth)acrylate, tetradecyl (meth)acrylate, hexadecyl (meth)acrylate, octadecyl (meth)acrylate, isostearyl (meth)acrylate, eicosyl (meth)acrylate, behenyl (meth)acrylate, and tetrahydrofurfuryl (meth)acrylate.
• alkoxy group-containing (meth)acrylates examples include 2-methoxyethyl (meth)acrylate, methoxyethylene glycol (meth)acrylate, 2-ethoxyethyl (meth)acrylate, and ethyl carbitol (meth)acrylate.
• alicyclic group-containing (meth)acrylates examples include cyclohexyl (meth)acrylate, tert-butylcyclohexyl (meth)acrylate, isobornyl (meth)acrylate, dicyclopentanyl (meth)acrylate, dicyclopentenyl (meth)acrylate, and adamantyl (meth)acrylate.
• aryl group-containing (meth)acrylates include aryl group-containing (meth)acrylates having 6 to 15 carbon atoms, such as phenyl (meth)acrylate, benzyl (meth)acrylate, and phenoxyethyl (meth)acrylate.
• hydroxy group-containing (meth)acrylates examples include 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, 6-hydroxyhexyl (meth)acrylate, 8-hydroxyoctyl (meth)acrylate, 10-hydroxydecyl (meth)acrylate, and 12-hydroxylauryl (meth)acrylate.
• epoxy group-containing (meth)acrylates examples include glycidyl (meth)acrylate and epoxycyclohexyl (meth)acrylate.
• carboxy group-containing (meth)acrylates include acrylic acid, methacrylic acid, carboxyethyl (meth)acrylate, carboxybutyl (meth)acrylate, and carboxypentyl (meth)acrylate.
• isocyanate group-containing (meth)acrylates examples include (meth)acryloyloxyethyl isocyanate.
• repeating structural unit (C) examples include structural units derived from monomers such as 2-(meth)acryloyloxyethylsuccinic acid, maleic acid, itaconic acid, maleic anhydride, itaconic anhydride, vinyl acetate, vinyl propionate, styrene, ⁇ -methylstyrene, N-vinylcaprolactam, cyclohexylmaleimide, phenylmaleimide, cyclohexylmaleimide, phenylmaleimide, methylmaleimide, ethylmaleimide, n-butylmaleimide, laurylmaleimide, and silicone-containing monomers.
• monomers such as 2-(meth)acryloyloxyethylsuccinic acid, maleic acid, itaconic acid, maleic anhydride, itaconic anhydride, vinyl acetate, vinyl propionate, styrene, ⁇ -methylstyrene, N
• the repeating structural unit (C) may be, for example, a structural unit derived from a resin such as poly(meth)acrylate, polycarbonate, polystyrene, silicone-based resin, epoxy-based resin, polysulfone, polyethersulfone, or polyimide.
• a resin such as poly(meth)acrylate, polycarbonate, polystyrene, silicone-based resin, epoxy-based resin, polysulfone, polyethersulfone, or polyimide.
• a repeating structural unit (C) having a structure that can be thermoset (crosslinked) may be introduced into the copolymer of the present invention.
• An example of the structure that can be thermoset (crosslinked) is an isocyanate group protected with a blocking agent.
• the blocking agent is not particularly limited as long as it can dissociate (deblock) by heating to regenerate an active isocyanate group, and examples thereof include phenols such as phenol, o-nitrophenol, p-chlorophenol, o-, m-, or p-cresol; alcohols such as methanol, ethanol, isopropanol, n-butanol, 2-ethoxyhexanol, 2-N,N-dimethylaminoethanol, 2-ethoxyethanol, and cyclohexanol; active methylene group-containing compounds such as dimethyl malonate, diethyl malonate, and methyl acetoacetate; oximes such as acetone oxime, methyl ethyl ketone oxime, methyl isobutyl ketone oxime, cyclohexanone oxime, acetophenone oxime, and benzophenone oxime; lactams such as ⁇ -caprolactam;
• the repeating unit having a structure capable of being thermally cured (crosslinked) may, for example, be a repeating structural unit represented by the following formula (8).
• R21 represents a hydrogen atom or a methyl group
• L4 represents a divalent hydrocarbon group having 1 to 30 carbon atoms which may contain an ether bond and/or an ester bond
• Y represents an isocyanate group protected with a blocking agent.
• examples of the divalent hydrocarbon group having 1 to 30 carbon atoms include the same groups as those exemplified above for L 2 and L 3 .
• the contents of the repeating structural units (A) and (B) in the copolymer of the present invention are not particularly limited.
• the content of the repeating structural unit (A) is preferably 5 to 95 mol %, and the content of the repeating structural unit (B) is preferably 5 to 95 mol %, more preferably the content of the repeating structural unit (A) is 20 to 90 mol %, the content of the repeating structural unit (B) is 10 to 50 mol %, and even more preferably the content of the repeating structural unit (A) is 35 to 85 mol %, and the content of the repeating structural unit (B) is 15 to 20 mol %.
• the content of the repeating structural unit (C) in the copolymer of the present invention (out of 100 mol % of all repeating structural units) is preferably 90 mol % or less, more preferably 1 to 50 mol %, even more preferably 2 to 10 mol %, and particularly preferably 3 to 5 mol %.
• Examples of the form of the copolymer of the present invention include linear, crosslinked, and network-like.
• the copolymer of the present invention contains the repeating structural unit (B2) represented by the formula (2-2), for example, it is crosslinked or network-like.
• B2 repeating structural unit represented by the formula (2-2)
• the crosslinked or network-like copolymer of the present invention it is possible to more effectively prevent cracks from occurring in the film when the film is formed.
• by forming the copolymer of the present invention into a crosslinked or network-like form it is possible to increase the glass transition temperature, thereby preventing the orientation relaxation of the nonlinear optical active site due to heat, and thus preventing the decrease in the electro-optic effect due to heat.
• the weight average molecular weight of the copolymer of the present invention is not particularly limited, but is, for example, 10,000 to 200,000, and from the viewpoint of solubility, is preferably 10,000 to 150,000, and more preferably 10,000 to 100,000.
• the weight average molecular weight in the present invention is a value measured by gel permeation chromatography (polystyrene equivalent).
• the glass transition temperature (Tg) of the copolymer of the present invention is not particularly limited, but the midpoint of Tg is preferably 130 to 200° C., more preferably 150 to 200° C., from the viewpoint of suppressing the occurrence of cracks in the film even if the film is thick, and from the viewpoint of heat resistance.
• the viscosity of the copolymer of the present invention is not particularly limited, but for example, in a 20% by weight cyclohexanone solution (25° C.), it is usually about 20 to 400 cP, and from the viewpoint of coatability, it is preferably 20 to 300 cP, more preferably 20 to 200 cP.
• the method for producing the copolymer of the present invention is not particularly limited, and any known production method may be used.
• the copolymer can be obtained by copolymerizing a (meth)acrylic acid derivative and/or a (meth)acrylamide derivative having an alkoxyadamantyl group with a (meth)acrylic acid derivative having a functional group for introducing a nonlinear optical active site, and then reacting the functional group with a compound having a nonlinear optical active site.
• the functional group for introducing a nonlinear optical active site examples include an isocyanate group, a hydroxy group, a carboxy group, an epoxy group, an amino group, a halogenated allyl group, and a halogenated acyl group.
• the copolymer of the present invention can be obtained by reacting a (meth)acrylic acid derivative and/or a (meth)acrylamide derivative having an alkoxyadamantyl group with a (meth)acrylic acid derivative having an isocyanate group, and then reacting the compound having a functional group capable of reacting with an isocyanate group and a nonlinear optical active site in the same molecule.
• the functional group capable of reacting with an isocyanate group is not particularly limited, and examples thereof include a group having active hydrogen such as a hydroxy group, an amino group, and a carboxy group, and an epoxy group capable of generating active hydrogen.
• the nonlinear optically active moiety may be a moiety derived from an organic nonlinear optical compound as described in the description of Z (atomic group exhibiting nonlinear optical activity) in the formulas (2-1) and (2-2), and is preferably the atomic group represented by the formula (3).
• Examples of compounds having a functional group capable of reacting with an isocyanate group and a nonlinear optically active moiety in the same molecule include compounds represented by the formulas (4-1) and (4-2), and a hydroxy group or an amino group present in the compound may react with an isocyanate group to obtain the repeating structural unit (B1) represented by the formula (2-1) or the repeating structural unit (B2) represented by the formula (2-2).
• the copolymer of the present invention is suitable for use as a material for electro-optical elements such as optical switches, optical modulators, and phase shifters, etc.
• the copolymer of the present invention can also be used for applications such as electric field sensors that detect changes in an electric field as changes in the refractive index.
• composition of the present invention comprises the copolymer of the present invention and a solvent.
• the solvent is not particularly limited as long as it can dissolve or disperse the copolymer of the present invention, and examples thereof include tetrahydrofuran, methyltetrahydrofuran, 1,4-dioxane, diethylene glycol dimethyl ether, acetone, methyl ethyl ketone, cyclopentanone, cyclohexanone, ethyl acetate, cyclohexanol, 1,2-dichloroethane, chloroform, toluene, chlorobenzene, xylene, N,N-dimethylformamide, N,N-dimethylacetamide, dimethylsulfoxide, chlorobenzene, and propylene glycol methyl ether.
• solvents can be used alone or in combination of two or more.
• these solvents from the viewpoint of high solubility of the copolymer of the present invention and good coatability, at least one selected from the group consisting of tetrahydrofuran, cyclopentanone, and chloroform is preferred.
• the content of the copolymer of the present invention in the composition is not particularly limited, and is usually about 3 to 30% by weight. From the viewpoint of coatability and facilitating the formation of a thick film by using a high-concentration composition, it is preferably 3 to 25% by weight, and more preferably 3 to 20% by weight. It is preferable to filter the prepared composition using a filter with a pore size of about 200 nm to remove insoluble matter before use.
• composition of the present invention may contain additives such as antioxidants such as hydroquinone, ultraviolet absorbers such as benzophenone, rheology modifiers such as silicone oil and surfactants, adhesion aids such as silane coupling agents, crosslinking agents, compatibilizers, curing agents, pigments, storage stabilizers, and defoamers, as necessary, so long as the effects of the present invention are not impaired.
• additives such as antioxidants such as hydroquinone, ultraviolet absorbers such as benzophenone, rheology modifiers such as silicone oil and surfactants, adhesion aids such as silane coupling agents, crosslinking agents, compatibilizers, curing agents, pigments, storage stabilizers, and defoamers, as necessary, so long as the effects of the present invention are not impaired.
• Nonlinear optical materials ⁇ Nonlinear optical material A> contains the copolymer of the present invention.
• the content of the copolymer of the present invention is not particularly limited, but is usually 85% by weight or more, preferably 90 to 100% by weight, more preferably 95 to 100% by weight, and even more preferably 99 to 100% by weight.
• the nonlinear optical material A of the present invention may further contain a nonlinear optically active compound.
• a nonlinear optically active compound known inorganic nonlinear optically active compounds and/or organic nonlinear optically active compounds can be used without particular limitation, and organic nonlinear optically active compounds are preferred.
• inorganic nonlinear optically active compounds include lithium niobate, potassium dihydrogen phosphate, and zinc telluride. These may be contained alone or in combination of two or more.
• the organic nonlinear optically active compound may, for example, be the compound represented by the formula (4-1) or (4-2), the compounds described in U.S. Patent No. 6,067,186, JP2004-501159A, WO2011/024774A, WO2023/021921A, "Organic Materials for Nonlinear Optics” (Edited by the Chemical Society of Japan, Quarterly Chemistry Review No. 15 (1992)), "Organic Nonlinear Optical Materials ... Examples of the compounds that exhibit second-order nonlinear optical effects include those described in "Reals” (Ch. Bosshard, et.
• the organic nonlinear optically active compound is not particularly limited as long as it is a compound that exhibits a second-order nonlinear optical effect, but is preferably a compound that has a conjugated chemical structure and further has an electron-donating group and an electron-withdrawing group in the molecule.
• conjugated chemical structures 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 chemical structures in which these compounds are bonded together via carbon-carbon unsaturated bonds or nitrogen-nitrogen unsaturated bonds.
• 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
• electron-donating groups include amino groups which may be substituted with alkyl groups, aryl groups, or acyl groups, alkoxy groups, allyloxy groups, and thioether groups.
• electron-withdrawing groups include nitro groups, cyano groups, dicyanovinyl groups, tricyanovinyl groups, halogen atoms, carbonyl groups, sulfone groups, perfluoroalkyl groups, tricyanovinylfuran, and tricyanofuran.
• the organic nonlinear optically active compound is preferably a compound represented by formula (4-1) and/or (4-2).
• the content of the nonlinear optically active compound may be appropriately adjusted depending on the application of the nonlinear optical material A, etc.
• the nonlinear optical material A of the present invention may further include a polymer (hereinafter also referred to as "polymer X") that contains a repeating structural unit (A) having an adamantyl group represented by formula (1) above, but does not contain a repeating structural unit (B) having a nonlinear optically active site.
• polymer X a polymer that contains a repeating structural unit (A) having an adamantyl group represented by formula (1) above, but does not contain a repeating structural unit (B) having a nonlinear optically active site.
• the polymer X may be a homopolymer consisting of the repeating structural unit (A), or may be a copolymer containing the repeating structural unit (A) and the repeating structural unit (C). When the polymer X is a copolymer, the polymer X may be a random copolymer or a block copolymer.
• the content of the polymer X may be appropriately adjusted depending on the application of the nonlinear optical material A, etc.
• the nonlinear optical material A of the present invention may contain additives such as antioxidants such as hydroquinone, ultraviolet absorbers such as benzophenone, rheology modifiers such as silicone oil and surfactants, adhesion aids such as silane coupling agents, crosslinkers, compatibilizers, curing agents, pigments, storage stabilizers, and defoamers, as necessary.
• antioxidants such as hydroquinone
• ultraviolet absorbers such as benzophenone
• rheology modifiers such as silicone oil and surfactants
• adhesion aids such as silane coupling agents, crosslinkers, compatibilizers, curing agents, pigments, storage stabilizers, and defoamers, as necessary.
• the nonlinear optical material B contains the polymer X and the nonlinear optically active compound.
• the content of the polymer X and the nonlinear optically active compound may be appropriately adjusted depending on the application of the nonlinear optical material B.
• the nonlinear optical material B of the present invention may contain the above-mentioned additives as necessary.
• the form of the nonlinear optical material of the present invention is not particularly limited, but is usually in the form of a film.
• the method for producing the film is not particularly limited, and for example, the raw material of the nonlinear optical material of the present invention is dissolved or dispersed in the solvent to form a composition (preferably a solution), and the composition is applied to a suitable substrate (e.g., silicon/silicon dioxide-coated substrate, silicon nitride substrate, substrate coated with metal (e.g., aluminum, molybdenum, chromium, etc.), glass substrate, quartz substrate, ITO substrate, etc.) or a film (e.g., triacetyl cellulose film, polyester film, acrylic film, etc. resin film) or other substrate by spin coating, dip coating, spray coating, bar coating, flow coating, gravure coating, roll coating, etc. to form a film.
• a suitable substrate e.g., silicon/silicon dioxide-coated substrate, silicon nitride substrate, substrate coated with metal (e
• the formed film is subjected to a poling treatment in order to express second-order nonlinear optical properties.
• Poling is an operation in which the copolymer or nonlinear optically active compound of the present invention is heated to a temperature near the glass transition temperature, a specified electric field is applied in that state, and then the compound is cooled while maintaining the electric field, thereby orienting the nonlinear optically active sites (atomic groups that express nonlinear optical activity) contained therein. This operation allows the film (nonlinear optical material) to express macroscopic nonlinear optical properties.
• the nonlinear optical material of the present invention is in the form of a film
• its thickness is not particularly limited, but is usually about 0.1 to 10 ⁇ m, preferably 0.3 to 3.0 ⁇ m, and more preferably 0.5 to 2.0 ⁇ m. Since the nonlinear optical material of the present invention contains the copolymer of the present invention and/or the polymer X, cracks are unlikely to occur even when the film is thick.
• the refractive index (n) of the nonlinear optical material of the present invention is not particularly limited, but is usually about 1.5 to 1.7 at a wavelength of 1308 nm, and is usually about 1.5 to 1.7 at a wavelength of 1532 nm.
• the electro-optic coefficient (r) of the nonlinear optical material of the present invention is not particularly limited, but for example, at a wavelength of 1308 nm, it is usually about 85 to 105 pm/V, and at a wavelength of 1550 nm, it is usually about 50 to 75 pm/V.
• the figure of merit (n 3 r) of the nonlinear optical material of the present invention is not particularly limited, but is usually about 370 to 470 pm/V at a wavelength of 1308 nm, and is usually about 225 to 300 pm/V at a wavelength of 1550 nm.
• Electro-optical element contains the copolymer of the present invention or the nonlinear optical material of the present invention.
• the copolymer of the present invention is suitably used as a material for various electro-optical elements. Examples of electro-optical elements include optical switches, optical modulators, and phase shifters.
• an optical waveguide structure is formed by applying and laminating a composition (solution) containing the copolymer of the present invention to a material having a smaller refractive index than the composition (solution) containing the copolymer of the present invention, but the present invention is not limited to this structure, and the composition (solution) containing the copolymer of the present invention can also be applied to other optical waveguide structures.
• a high-frequency voltage is applied to either or both of the branched optical waveguide structures to produce electro-optical properties, changing the refractive index and causing a phase change in the propagating light.
• This phase change changes the light intensity after branching and combining, making it possible to perform high-speed modulation of light.
• the electro-optical element of the present invention is not limited to phase and intensity modulation, but can also be used, for example, as a polarization conversion element, or a splitting and multiplexing element.
• Optical waveguides using the copolymer of the present invention as a core material can be manufactured, for example, by the method disclosed in WO 2016/035823.
• AdOMe 3-methoxy-1-adamantyl methacrylate
• AdOEt 3-ethoxy-1-adamantyl methacrylate
• MOI 2-isocyanatoethyl methacrylate (manufactured by Showa Denko K.K., Karenz MOI (registered trademark))
• AdMA 1-adamantyl methacrylate (Osaka Organic Chemical Industry Co., Ltd., Adamantate M-104)
• DCPMA dicyclopentanyl methacrylate (Tokyo Chemical Industry Co., Ltd.) AIBN: 2,2'-azobis(isobutyronitrile) (Tokyo Chemical Industry Co., Ltd.)
• DBTDL dibutyltin dilaurate (Tokyo Chemical Industry Co., Ltd.)
• THF tetrahydrofuran
• the organic layer was washed with 2% hydrochloric acid (50 g) and then with water (50 g), and the solvent was concentrated to obtain a concentrated liquid.
• the resulting concentrated liquid was purified by distillation to obtain 17 g of AdOMe, a colorless, transparent liquid.
• Synthesis Example 2 [Synthesis of AdOEt] AdOEt was synthesized in the same manner as in Synthesis Example 1, except that ethanol was used instead of methanol in Synthesis Example 1 to react with 3-methanesulfonyloxy-1-adamantyl methacrylate.
• Example 1 (Preparation of Copolymer) (1) Preparation of intermediate Under an argon atmosphere, 8.863 g (35.4 mmol) of AdOMe, 1.350 g (8.70 mmol) of MOI, and 0.354 g (2.16 mmol) of AIBN were dissolved in 20 ml of dehydrated toluene. The resulting solution was dropped into 20 ml of dehydrated toluene heated to 70° C. over 20 minutes. The mixture was then stirred at 72 to 75° C. for 2 hours. After cooling to room temperature (approximately 23° C.), the resulting reaction mixture was dropped into 500 ml of dehydrated IPE (isopropyl ether) to precipitate a polymer.
• IPE isopropyl ether
• Example 2 (Preparation of Copolymer) (1) Preparation of intermediate Under an argon atmosphere, 8.910 g (33.7 mmol) of AdOEt, 1.359 g (8.76 mmol) of MOI, and 0.355 g (2.16 mmol) of AIBN were dissolved in 20 ml of dehydrated toluene. The obtained solution was dropped into 20 ml of dehydrated toluene heated to 70° C. over 20 minutes. Then, the mixture was stirred at 72 to 75° C. for 2 hours. After cooling to room temperature (approximately 23° C.), the obtained reaction mixture was dropped into 500 ml of dehydrated IPE to precipitate a viscous polymer.
• Example 3 (Preparation of Copolymer) (1) Preparation of intermediate Under an argon atmosphere, 4.49 g (17.9 mmol) of AdOMe, 3.96 g (18.0 mmol) of AdMA, 1.29 g (8.31 mmol) of MOI, and 0.25 g (1.52 mmol) of AIBN were dissolved in 20 ml of dehydrated toluene. The obtained solution was added dropwise to 20 ml of dehydrated toluene heated to 70° C. over 20 minutes. Then, the mixture was stirred at 72 to 75° C. for 2 hours.
• reaction mixture After cooling to room temperature (approximately 23° C.), the obtained reaction mixture was added dropwise to 450 ml of dehydrated IPE to precipitate a polymer. The precipitate was filtered, washed with dehydrated IPE and dehydrated hexane in that order, and then dried under reduced pressure at 70° C. to obtain 7.06 g of a white powder intermediate having repeating structural units derived from AdOMe, AdMA, and MOI.
• Example 4 (Preparation of Copolymer) (1) Preparation of intermediate Under an argon atmosphere, 8.87 g (35.4 mmol) of AdOMe, 1.42 g (9.15 mmol) of MOI, and 0.354 g (2.16 mmol) of AIBN were dissolved in 18 ml of dehydrated toluene and stirred at 70° C. for 2 hours. After cooling to room temperature (approximately 23° C.), the resulting reaction mixture was added to 450 ml of dehydrated IPE to precipitate a polymer. The precipitate was filtered, washed with dehydrated IPE and dehydrated hexane in that order, and then dried under reduced pressure at 70° C.
• the resulting reaction mixture was precipitated with 450 ml of IPE, and the precipitate was filtered.
• the crude product was added to 50 ml of THF, heated and dissolved at 60°C, and dispersed in 500 ml of IPE for reprecipitation.
• the precipitate was filtered, washed, and then dried under reduced pressure at 70°C to obtain 1.28 g of a dark reddish brown powder copolymer having the following repeating structural units (A1), (B1), and (C1).
• the following formula shows, from the left, repeating structural units (A1), (B1), and (C1).
• Example 5 (Preparation of Copolymer) (1) Preparation of intermediate Under an argon atmosphere, 4.65 g (18.6 mmol) of AdOMe, 4.13 g (26.6 mmol) of MOI, and 0.222 g (1.35 mmol) of AIBN were dissolved in 14.5 ml of dehydrated toluene and stirred at 70° C. for 2 hours. After cooling to room temperature (approximately 23° C.), the reaction mixture was added to 370 ml of dehydrated IPE to precipitate a polymer. The precipitate was filtered, washed with dehydrated IPE, and dried under reduced pressure at 70° C. to obtain 7.05 g of a white powder intermediate having repeating structural units derived from AdOMe and MOI.
• the resulting reaction mixture was precipitated with 1050 ml of IPE, and the precipitate was filtered.
• the resulting precipitate was washed with IPE:THF (12:1), then with IPE, and finally with hexane, and then dried under reduced pressure at 70° C. to obtain 2.55 g of a copolymer having the following repeating structural units (A1), (B2), (C1), and (C4) as a dark brown powder.
• the following formula shows the repeating structural units (A1), (B2), (C1), and (C4) in that order from the left.
• Comparative Example 1 (Preparation of Copolymer) (1) Preparation of intermediate Under an argon atmosphere, 8.38 g (38.0 mmol) of AdMA, 1.258 g (8.11 mmol) of MOI, and 0.387 g (2.16 mmol) of AIBN were dissolved in 20 ml of dehydrated toluene. The resulting solution was dropped into 20 ml of dehydrated toluene heated to 70° C. over 20 minutes. The mixture was then stirred at 72-75° C. for 2 hours. After cooling to room temperature (approximately 23° C.), the resulting reaction mixture was dropped into 450 ml of dehydrated IPE to precipitate a polymer.
• Tg measuring device Photo-DSC 204 F1 Phoenix (registered trademark) manufactured by NETZSCH Measurement conditions: Nitrogen atmosphere Heating rate: 30°C/min (-50 to 250°C)
• Viscosity Measurement The viscosity of a solution prepared by dissolving the copolymer in cyclohexanone at a concentration of 20% by weight was measured using a viscometer (HVROC-L, manufactured by RHEOSENSE).
• the electro-optic coefficient of the prepared thin film was measured by the same method as that described in the reference paper ("Transmission ellipsometric method without an aperture for simple and reliable evaluation of electro-optic properties", Toshiki Yamada and Akira Otomo, Optics Express, vol. 21, pages 29240-48 (2013).
• the laser light source used was a DFB laser 81663A (wavelengths 1308 nm and 1550 nm) manufactured by Agilent Technologies.
• the copolymers (Examples 1 to 5) containing a repeating structural unit (A) having an alkoxyadamantyl group were capable of forming a film free of cracks whether the film thickness was thin or thick.
• the copolymers (Comparative Example 1) containing a repeating structural unit having an adamantyl group and the copolymers (Comparative Example 2) containing a repeating structural unit having an adamantyl group and a repeating structural unit having a dicyclopentanyl group caused cracks in the film whether the film thickness was thin or thick.
• the films formed using the copolymers obtained in Examples 1 to 5 had a higher figure of merit (n 3 r) and were superior in electro-optical effect compared to the films formed using the copolymers obtained in Comparative Examples 1 and 2.
• the copolymer of the present invention is suitable for use as a material for electro-optical elements such as optical switches, optical modulators, phase shifters, and terahertz wave generating and detecting elements.
• the copolymer of the present invention can also be used for applications such as electric field sensors that detect changes in the electric field as changes in the refractive index.
• films are often formed not only on flat surface structures, but also on various uneven surface structures, and films on uneven surface structures are more susceptible to cracking due to stress (distortion) caused by the structure, so the copolymer of the present invention can be used to expand the range of applications to electro-optical elements.

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