Classifications

• • G—PHYSICS
  • G02—OPTICS
  • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
  • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
  • G02F1/35—Non-linear optics
  • G02F1/355—Non-linear optics characterised by the materials used
  • G02F1/361—Organic materials
• • 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
  • C08F222/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical and containing at least one other carboxyl radical in the molecule; Salts, anhydrides, esters, amides, imides, or nitriles thereof
  • C08F222/36—Amides or imides
  • C08F222/40—Imides, e.g. cyclic imides
  • C08F222/402—Alkyl substituted imides
• • 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
  • 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
• • G—PHYSICS
  • G02—OPTICS
  • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
  • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
  • G02F1/35—Non-linear optics
  • G02F1/355—Non-linear optics characterised by the materials used
  • G02F1/361—Organic materials
  • G02F1/3615—Organic materials containing polymers

Definitions

• the present invention relates to a nonlinear optically active copolymer having an organic nonlinear optically active site that is used for optical switches, optical information processing such as optical modulation, optical communication, and the like. It relates to an optically active copolymer and an organic nonlinear optical material using the copolymer.
• nonlinear optical materials In recent years, various electronic devices using nonlinear optical materials have been developed in fields such as optical information processing and optical communication. Among these nonlinear optical materials, materials that produce a first-order electro-optic effect (Pockels effect) due to a second-order nonlinear optical effect are expected to be applied to optical switches and optical modulation. Among nonlinear optical materials having the Pockels effect, inorganic nonlinear optical materials such as lithium niobate have already been put to practical use and are widely used. With the recent development of the information society, more advanced information processing is required.Instead of inorganic materials, organic nonlinear optical materials with excellent performance such as higher nonlinear optical properties and high-speed response are being developed. Development is desired.
• organic nonlinear optical materials polymeric materials can be easily formed into films by casting, dipping, spin coating, etc., and are attracting attention for their ease of processing in fabricating devices. ing.
• examples of such polymeric organic nonlinear optical materials include those in which an organic dye compound exhibiting a nonlinear optical effect is dispersed in a polymer matrix, and those in which an organic dye monomer is introduced into the main chain or side chain of a polymer compound. are being considered.
• polymer materials with organic dye monomers introduced into the main chain or side chain exhibit uniform optical properties throughout the film if it is possible to form a film with the organic dye sites dispersed uniformly at a high concentration. Therefore, it can be said that such a material can be an excellent material from the viewpoint of practical use of devices.
• the polymeric organic nonlinear optical material has a high glass transition temperature (Tg) and a large amount of the organic dye monomer (organic dye moiety) introduced.
• Tg glass transition temperature
• organic dye monomer organic dye moiety
• Non-Patent Document 1 discloses that the nonlinear optical effect increases when the concentration in the polymer of the organic dye portion exhibiting the nonlinear optical effect is high. In polymer materials in which organic dye monomers are introduced into side chains, it is important to increase the amount of the organic dye monomers introduced.
• An object of the present invention is to provide a nonlinear optically active copolymer that achieves both a high glass transition temperature (Tg) and a densified nonlinear optical dye, and to provide a nonlinear optical material obtained using the copolymer. do.
• the present inventors have made intensive studies to achieve the above object, and found that by incorporating a monomer unit derived from an N-substituted maleimide monomer, both a high Tg and a high introduction amount of the organic dye site can be achieved. perfected the invention.
• the present invention relates to a nonlinear optically active copolymer containing at least a repeating unit A represented by formula [1] and a repeating unit B represented by formula [2] having a nonlinear optically active site in the same molecule.
• R 1 is an alkyl group having 1 to 6 carbon atoms, an aralkyl group having 7 to 12 carbon atoms, a cycloalkyl group having 4 to 8 carbon atoms, an aliphatic bridged ring group having 6 to 14 carbon atoms, or represents an aryl group having 6 to 14 carbon atoms
• R 2 represents a hydrogen atom or a methyl group
• L 1 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 that exhibits nonlinear optical activity.
• the nonlinear optically active copolymer according to the first aspect which contains 20 to 80 mol % of the repeating unit A represented by the formula [1] in the same molecule.
• R 1 is an alkyl group having 1 to 3 carbon atoms, an aralkyl group having 7 to 10 carbon atoms, a cycloalkyl group having 6 to 8 carbon atoms, or an aliphatic bridge having 8 to 12 carbon atoms.
• the nonlinear optically active copolymer according to any one of the first to third aspects which is a cyclic group or an aryl group having 6 to 10 carbon atoms.
• it relates to the nonlinear optically active copolymer according to any one of the first to fourth aspects, wherein Z is an atomic group having a furan ring group represented by formula [3].
• Z has a structure represented by formula [4] or formula [5] (in which one hydrogen atom is removed in any of R 4 to R 9 in these chemical formulas). It relates to the nonlinear optically active copolymer according to the fifth aspect, which is an atomic group.
• R 4 and R 5 are each independently a hydrogen atom, an optionally substituted alkyl group having 1 to 10 carbon atoms, or an optionally substituted carbon atom number representing 6 to 10 aryl groups
• R 6 to R 9 each independently represents 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, an alkyl group having 1 to 6 carbon atoms and/or a silyloxy group having a phenyl group, or a halogen atom;
• R 10 and R 11 each independently represent the same meaning as above
• Ar represents a divalent aromatic group represented by formula [6] or formula [7].
• Z has a structure represented by formula [4] or formula [5] (in which one hydrogen atom is removed in either R 4 or R 5 ) It relates to the nonlinear optically active copolymer according to the sixth aspect, which is an atomic group. As an eighth aspect, it relates to an organic nonlinear optical material comprising the nonlinear optically active copolymer according to any one of the first to seventh aspects as a part of the material.
• a ninth aspect relates to an electro-optical device comprising the nonlinear optically active copolymer according to any one of the first to seventh aspects.
• a tenth aspect relates to an optical switching element comprising the nonlinear optically active copolymer according to any one of the first to seventh aspects.
• it relates to a varnish containing the nonlinear optically active copolymer according to any one of the first to seventh aspects.
• a step of applying the varnish according to the eleventh aspect on the surface of the substrate or on the outermost surface of a single layer or multiple layers laminated on the substrate to obtain a coating film
• the present invention relates to a method for producing an organic nonlinear optical material, comprising a step of applying an electric field under heating to orient atomic groups exhibiting nonlinear optical activity in a coating film.
• the present invention by combining a repeating unit having a nonlinear optically active site and a repeating unit derived from an N-substituted maleimide monomer, a high glass transition temperature (160° C. or higher) is realized and the nonlinear optical It is possible to provide a nonlinear optically active copolymer in which the amount of active sites introduced is increased compared to conventional ones.
• the nonlinear-optically active copolymer of the present invention having the above structure can be used as an organic nonlinear optical material that can suppress orientation relaxation of nonlinear optical sites and have excellent nonlinear optical properties.
• the nonlinear optically active copolymer of the present invention can be dissolved in a solvent to form a varnish and can be easily molded, so that it can be suitably used as an optical material with high handling properties in the field of optoelectronic materials. is obtained.
• the organic nonlinear optical material of the present invention has a large nonlinear optical constant and can be easily molded into an optical device.
• a polymeric material having an organic dye monomer (organic dye site) introduced into its main chain or side chain, including the nonlinear optically active copolymer of the present invention does not exhibit a nonlinear optical effect simply by forming a film. This is because the organic dye sites exhibiting nonlinear optical effects in the film are completely randomly oriented.
• the temperature of the element containing the film-formed polymer is raised to near the Tg of the polymer, and then poling treatment is performed by applying a voltage from one direction to orient the organic dye sites. After that, the substrate is cooled to Tg or lower, and the molecular motion is suppressed while the organic dye portion is oriented.
• Patent Document 2 discloses the effect of orientation relaxation due to elapsed time, and in the same document, a copolymer having a Tg of 172.5 ° C. having nonlinear optical activity was subjected to a high temperature condition of 85 ° C. for 1000 hours or more. The results show that the orientation relaxation is difficult to occur even if the The inventors of the present invention conducted further studies and came to the conclusion that if the Tg of the polymer having nonlinear optical activity is 160° C. or higher, the orientation relaxation can be suppressed even after 1000 hours at the temperature of 85° C. described above. .
• the condition of 1000 hours at a temperature of 85° C. is the condition of an accelerated life test of 5 years, which is generally the trial period of a device. That is, when the Tg of the nonlinear optically active polymer is 160° C. or more, the orientation relaxation is suppressed, and it can be judged that the polymer is useful as a nonlinear organic polymer material that can withstand practical use.
• the abundance ratio of adamantyl methacrylate-derived units for increasing Tg is set to 74 mol% or more, so that Tg finally increases.
• a high Tg is achieved, such as exceeding 160° C., it has been difficult to increase the concentration of the organic dye sites in the polymer.
• the material In addition to the performance required for nonlinear optical materials such as high Tg and high concentration of organic dye sites, from the viewpoint of polymer materials, the material must have good processability as described above. is desirable. For example, in order to obtain good film-forming properties, it is desirable that the polymeric material formed into a film be in a non-crystalline amorphous state. A phenomenon called so-called cracking, in which the film is uniform or the film is partially broken, tends to occur. In the technical field of optical materials to which the present invention is directed, optical signals are interrupted at cracks. Therefore, being able to form a uniform film without cracks is an important aspect for the practical use of optical devices.
• adamantyl methacrylate and other cycloalkane-based monomers described above generally tend to reduce the film-forming properties when introduced at a high concentration.
• Patent Document 2 in addition to a monomer unit having an adamantyl group and a monomer unit having a nonlinear optically active site, a varnish containing a copolymer containing other monomer units is prepared, and the varnish is formed into a film by spin coating to guide light. The points used as the core of the wave path are indicated.
• introduction of other monomer units may lead to further difficulty in increasing the concentration of organic dye moieties.
• the present inventors realized a nonlinear optically active copolymer that has a high glass transition temperature (Tg) by incorporating a monomer unit derived from an N-substituted maleimide monomer and that can be bound with a nonlinear optical dye at a high concentration. Furthermore, the inventors have also found that the copolymer is excellent in film-forming properties, and have completed the present invention.
• Tg glass transition temperature
• the nonlinear optically active copolymer of the present invention comprises, in the same molecule, at least a repeating unit A represented by the formula [1] and a repeating unit B represented by the formula [2] having a nonlinear optically active site. It is an active copolymer.
• R 1 is an alkyl group having 1 to 6 carbon atoms, an aralkyl group having 7 to 12 carbon atoms, a cycloalkyl group having 4 to 8 carbon atoms, or an aliphatic group having 6 to 14 carbon atoms. represents a bridged ring group or an aryl group having 6 to 14 carbon atoms;
• the alkyl group having 1 to 6 carbon atoms may have a branched structure, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group and sec-butyl group.
• Aralkyl groups having 7 to 12 carbon atoms include phenylmethyl group (benzyl group), 2-phenylethyl group, 3-phenyl-n-propyl group, 4-phenyl-n-butyl group, 5-phenyl-n- Examples include, but are not limited to, pentyl group, 6-phenyl-n-hexyl group, and the like.
• Cycloalkyl groups having 4 to 8 carbon atoms include cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl and cyclooctyl groups.
• the aliphatic bridged ring group having 6 to 14 carbon atoms may have an unsaturated double bond, and examples thereof include an isobornyl group, a dicyclopentanyl group, a dicyclopentenyl group, and an adamantyl group. or a group in which these bridged ring groups are bonded to an alkyl group having 1 to 4 carbon atoms.
• Examples of the aryl group having 6 to 14 carbon atoms include phenyl group, tolyl group, xylyl group, naphthyl group, anthryl group and phenanthryl group.
• R 1 is an alkyl group having 1 to 3 carbon atoms, an aralkyl group having 7 to 10 carbon atoms, a cycloalkyl group having 6 to 8 carbon atoms, and an aliphatic bridged ring group having 8 to 12 carbon atoms. , or an aryl group having 6 to 10 carbon atoms, preferably an ethyl group, a phenylmethyl group (benzyl group), a cyclohexyl group, an adamantyl group, or a phenyl group, especially when R 1 is a cyclohexyl group Preferably.
• R 2 represents a hydrogen atom or a methyl group.
• L 1 represents 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 may be either an aliphatic group or an aromatic group. It can be anything. Among them, an aliphatic group is preferable, and an alkylene group having 1 to 6 carbon atoms is more preferable.
• Examples of such divalent hydrocarbon groups having 1 to 30 carbon atoms include methylene group, ethylene group, trimethylene group, tetramethylene group, pentamethylene group, hexamethylene group and octane-1,8-diyl group.
• Z represents an atomic group that exhibits nonlinear optical activity.
• An atomic group that exhibits nonlinear optical activity refers to an atomic group derived from an organic nonlinear optical compound.
• the organic nonlinear optical compound is preferably a ⁇ -conjugated compound having an electron-donating group at one end of a ⁇ -conjugated chain and an electron-withdrawing group at the other end, and having a large molecular hyperpolarizability ⁇ .
• electron-donating groups include dialkylamino groups
• examples of electron-withdrawing groups include cyano groups, nitro groups, and fluoroalkyl groups.
• preferred atomic groups that exhibit nonlinear optical activity in the present invention include atomic groups having a furan ring group represented by the following formula [3].
• R 10 and R 11 each independently represent a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, a haloalkyl group having 1 to 5 carbon atoms, or an aryl group having 6 to 10 carbon atoms.
• a black dot ( ⁇ ) represents a bond with the remaining structure constituting the atomic group Z that exhibits nonlinear optical activity.
• the preferred atomic group (Z) that exhibits the nonlinear optical activity specifically, an atomic group having a functional group derived from the structure represented by the following formula [4], or an atomic group represented by the following formula [5]
• An atomic group having a functional group derived from the structure can be mentioned. That is, the atomic group (Z) is an atom of a structure represented by formula [4] or formula [5] (in which one hydrogen atom is removed from any of R 4 to R 9 ) Groups are preferred.
• R 4 and R 5 each independently represent a hydrogen atom, an optionally substituted alkyl group having 1 to 10 carbon atoms, or a substituent represents an aryl group having 6 to 10 carbon atoms which may be present;
• the alkyl group having 1 to 10 carbon atoms may have a branched structure, a cyclic structure, or an arylalkyl group.
• the aryl group having 6 to 10 carbon atoms includes phenyl group, tolyl group, xylyl group, naphthyl group and the like.
• substituents include amino group; hydroxy group; carboxy group; epoxy group; alkoxycarbonyl group such as methoxycarbonyl group and tert-butoxycarbonyl group; silyloxy groups such as an oxy group and a triphenylsilyloxy group; and halogen atoms such as a fluoro group, a chloro group, a bromo group and an iodo group.
• the bond of the atomic group (Z) is preferably a bond obtained by removing one hydrogen atom from R 4 or R 5 .
• R 6 to R 9 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, an alkyl group having 1 to 6 carbon atoms and/or a phenyl group; represents a silyloxy group or a halogen atom.
• Examples of the alkyl group having 1 to 10 carbon atoms include the groups exemplified for R 4 and R 5 above.
• the alkoxy group having 1 to 10 carbon atoms includes, for example, a group in which the above alkyl group having 1 to 10 carbon atoms is bonded through an oxygen atom.
• alkylcarbonyloxy groups having 2 to 11 carbon atoms include groups in which the above alkyl groups having 1 to 10 carbon atoms are bonded via a carbonyloxy group.
• the aryloxy group having 4 to 10 carbon atoms includes phenoxy group, naphthalene-2-yloxy group, furan-3-yloxy group, thiophen-2-yloxy group and the like.
• the arylcarbonyloxy group having 5 to 11 carbon atoms includes benzoyloxy group, 1-naphthoyloxy group, furan-2-carbonyloxy group, thiophene-3-carbonyloxy group and the like.
• Examples of the silyloxy group having an alkyl group having 1 to 6 carbon atoms and/or a phenyl group include a trimethylsilyloxy group, a tert-butyldimethylsilyloxy group, a tert-butyldiphenylsilyloxy group, a triphenylsilyloxy group, and the like.
• Halogen atoms include a fluoro group, a chloro group, a bromo group, an iodo group and the like.
• R 10 and R 11 each independently represent the same meaning as R 10 and R 11 in formula [3] above, that is, each independently represents a hydrogen atom, represents an alkyl group having 1 to 5 carbon atoms, a haloalkyl 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, methyl group, ethyl group, n-propyl group, isopropyl group, cyclopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, cyclobutyl group, n-pentyl group, neopentyl group, cyclopentyl group and the like.
• the haloalkyl group having 1 to 5 carbon atoms may have a branched structure or a cyclic structure, and includes fluoromethyl, trifluoromethyl, bromodifluoromethyl, 2-chloroethyl, 2-bromoethyl, 1 ,1-difluoroethyl group, 2,2,2-trifluoroethyl group, 1,1,2,2-tetrafluoroethyl group, 2-chloro-1,1,2-trifluoroethyl group, pentafluoroethyl group , 3-bromopropyl group, 2,2,3,3-tetrafluoropropyl group, 1,1,2,3,3,3-hexafluoropropyl group, 1,1,1,3,3,3-hexa fluoropropan-2-yl group, 3-bromo-2-methylpropyl group, 2,2,3,3-tetrafluorocyclopropyl group, 4-bromobutyl group, perfluoropen
• Ar represents a divalent aromatic group represented by Formula [6] or Formula [7] below.
• R 12 to R 17 each independently represent a hydrogen atom, an optionally substituted alkyl group having 1 to 10 carbon atoms, or a substituent. represents an aryl group having 6 to 10 carbon atoms which may be present;
• examples of 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 for R 4 and R 5 above.
• nonlinear optically active copolymer of the present invention includes repeating units other than the repeating unit A represented by the above formula [1] and the repeating unit B represented by the formula [2] having a nonlinear optically active site (other repeating units unit).
• repeating units forming a polymer matrix can be introduced into the nonlinear optically active copolymer in order to adjust the content of nonlinear optically active sites.
• thermosetting A repeating unit having a structure capable of (crosslinking) can be introduced into the nonlinear optically active copolymer.
• a repeating unit containing a cycloalkane such as an adamantyl ring may be introduced into the nonlinear optically active copolymer for adjusting the glass transition temperature.
• nonlinear optically active copolymer of the present invention is used as an optically active material, such as the core of an optical waveguide, such other repeating units have a structure that does not significantly affect the transparency and moldability of the copolymer. It is desirable to choose one.
• the polymer matrix in the repeating unit forming the polymer matrix examples include resins such as polymethyl methacrylate, polycarbonate, polystyrene, silicone-based resins, epoxy-based resins, polysulfone, polyethersulfone, and polyimide.
• the nonlinear-optically active polymer of the present invention has a repeating unit A represented by the above formula [1], a formula having a nonlinear-optically active site A mode in which the repeating unit B represented by [2] and the repeating unit of the polymer matrix are, so to speak, copolymerized can be employed.
• thermosetting (crosslinkable) structure a preferred example of the thermosetting (crosslinkable) structure is an isocyanate group protected with a blocking agent.
• the blocking agent is not particularly limited as long as it can be dissociated (deblocked) by heating to regenerate active isocyanate groups.
• Examples include phenol, o-nitrophenol, p-chlorophenol, o-, m- or Phenols such as p-cresol; Alcohols such as methanol, ethanol, isopropanol, n-butanol, 2-ethoxyhexanol, 2-N,N-dimethylaminoethanol, 2-ethoxyethanol and cyclohexanol; Dimethyl malonate, malon Active methylene group-containing compounds such as diethyl acid and methyl acetoacetate; pyrazoles such as 5-dimethylpyrazole and 3-methylpyrazole; thiols such as dodecanethiol and benzenethiol; Examples of the repeating unit having a thermosetting (crosslinkable) structure include repeating units represented by the following formula [8].
• R 18 represents a hydrogen atom or a methyl group
• L 3 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 for L 3 include the same groups as those exemplified for L 1 above.
• the cycloalkane is not particularly limited, and includes monocyclic rings, condensed rings, and the like, and these rings may be bridged.
• Condensed rings include, for example, bicyclo rings and tricyclo rings.
• bridged rings include dicyclopentane and adamantyl.
• the average molecular weight of the nonlinear optically active copolymer containing at least the repeating unit A represented by the formula [1] and the repeating unit B represented by the formula [2] of the present invention is not particularly limited, but the weight average molecular weight is preferably 10,000 to 1,000,000.
• the weight average molecular weight in the present invention is a value measured by gel permeation chromatography (converted to polystyrene).
• the ratio of the repeating unit A represented by the formula [1] in the same molecule is not particularly limited, but the ratio is, for example, 1 to 99 mol%, or, for example, 20 to 80 mol%. can do.
• the mixing ratio of the repeating unit A represented by formula [1] and the repeating unit B represented by formula [2] is not particularly limited.
• B 99: 1 to 1: 99, or 90: 10 to 10: 90, or 80: 20 to 20: 80, or 70: 30 to 50: 50, or 60: 40 to 50: 50, Alternatively, it can be 90:10 to 60:40.
• a high Tg can be achieved by increasing the blending ratio of the repeating unit A represented by the formula [1], and an increase in the introduction amount of the organic dye moiety (the repeating unit B represented by the formula [2]) is considered.
• the molar ratio A:B can be, for example, 80:20-20:80, 90:10-60:40, or 60:40-40:60.
• the mixing ratio of the repeating unit A represented by formula [1] and the other repeating unit is not particularly limited.
• Other repeating units 99:1 to 10:90, or 80:20 to 10:90, or 75:25 to 10:90, or 60:40 to 10:90, or 95:5 to 30 :70.
• the ratio of the total number of moles of repeating unit A represented by formula [1] and other repeating units to the number of moles of repeating unit B represented by formula [2] can be the above ratio. .
• the nonlinear optically active copolymer containing at least the repeating unit A represented by the formula [1] and the repeating unit B represented by the formula [2] of the present invention can introduce, for example, an N-substituted maleimide and a nonlinear optically active site. It can be obtained by copolymerizing a (meth)acrylic acid derivative having a functional group and then reacting the functional group with a compound having a nonlinear optically active site.
• the functional group for introducing the target site include isocyanate group, hydroxy group, carboxyl group, epoxy group, amino group, halogenated allyl group, halogenated acyl group and the like.
• a nonlinear optically active site is introduced to obtain a repeating unit B represented by formula [2].
• a compound having a functional group capable of reacting with an isocyanate group and a nonlinear optically active site in the same molecule allows the production of the nonlinear optically active copolymers of the present invention.
• the functional group capable of reacting with the isocyanate group is not particularly limited, but examples thereof include groups having active hydrogen such as hydroxy group, amino group and carboxy group, and epoxy groups capable of generating active hydrogen.
• nonlinear optically active site examples include sites derived from the organic nonlinear optical compound mentioned in the description of Z (atomic group exhibiting nonlinear optical activity) in formula [2].
• a site having a furan ring group represented by the above formula [3] is preferable.
• the compound having a functional group capable of reacting with an isocyanate group and a nonlinear optically active site in the same molecule includes the compound represented by the above formula [4] and the compound represented by formula [5].
• the repeating unit B represented by the above formula [2] can be obtained by reacting the hydroxy group or the like present in the present compound with the isocyanate group.
• the nonlinear optically active copolymer of the present invention is used as a nonlinear optical material, it is generally used in the form of a thin film.
• the nonlinear optically active copolymer of the present invention is dissolved in a suitable organic solvent to form a varnish, and the varnish is applied to a suitable substrate (for example, silicon/silicon dioxide coated substrate, silicon nitride substrate, Substrates such as metals (e.g., aluminum, molybdenum, chromium, etc.
• coated substrates glass substrates, quartz substrates, ITO substrates, etc.
• films e.g., triacetylcellulose films, polyester films, resin films such as acrylic films
• a wet coating method in which a film is formed by coating by spin coating, flow coating, roll coating, slit coating, spin coating followed by a slit, inkjet coating, printing, or the like is preferred.
• the above varnishes are also subject of the present invention.
• the solvent used for varnish preparation dissolves the nonlinear optically active copolymer containing at least the repeating unit A represented by the formula [1] and the repeating unit B represented by the formula [2], and is optionally added.
• the type and structure of the solvent are not particularly limited as long as the solvent has such dissolving ability.
• Examples of preferred organic solvents 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, propylene glycol monomethyl ether and the like. These solvents can be used singly or in combination of two or more.
• tetrahydrofuran, cyclopentanone, chloroform, etc. are highly soluble in copolymers containing at least repeating units A and B represented by formulas [1] and [2], and from the viewpoint of good coating properties. more preferred.
• the proportion of solids in the varnish is, for example, 0.5 to 30% by mass, and is, for example, 5 to 30% by mass.
• the solid content referred to herein means the mass of substances (nonlinear optically active copolymer and, if desired, additives described later) after removing the solvent from the varnish. Therefore, it is preferable to use the prepared varnish after filtering using a filter having a pore size of about 0.2 ⁇ m.
• the thin film (molded article) formed from the above varnish can be thermally cured (crosslinked).
• the blocking agent that protects the isocyanate group is dissociated (deblocked) by heating to regenerate the active isocyanate group, and the active isocyanate group reacts with each other or with another curing agent (crosslinking agent). and hardens (crosslinks).
• the curing (crosslinking) temperature is not particularly limited as long as it is a temperature at which the blocking agent protecting the isocyanate group dissociates. is within the range of
• the varnish may optionally contain an antioxidant such as hydroquinone, an ultraviolet absorber such as benzophenone, a rheology modifier such as silicone oil, a surfactant, and a silane coupling agent.
• an antioxidant such as hydroquinone
• an ultraviolet absorber such as benzophenone
• a rheology modifier such as silicone oil
• surfactant such as benzophenone
• silane coupling agent such as silicone oil
• Adhesion adjuvants such as agents, cross-linking agents for polymer matrices, compatibilizers, curing agents, pigments, storage stabilizers, antifoaming agents and the like can be contained.
• the nonlinear optically active copolymer of the present invention can be applied as a material for various conventionally proposed electro-optical elements.
• a typical electro-optical element is an optical switching element (optical communication element) such as a Mach-Zehnder optical modulator.
• a varnish containing the nonlinear optically active copolymer of the present invention is coated on a substrate such as glass or plastic, and then processed by lithography using light or electron beams, wet and dry etching, or nanoimprinting.
• a substrate such as glass or plastic
• an optical waveguide structure is formed by coating and laminating a material having a refractive index smaller than that of the varnish containing the nonlinear optically active copolymer. Active copolymers (varnishes) are applicable.
• a Mach-Zehnder optical modulator which is a typical optical switching device, a high-frequency voltage is applied to both or one of the branched optical waveguide structures to develop electro-optical characteristics and change the refractive index to change the propagating light. produces a phase change of High-speed modulation of light becomes possible by changing the light intensity after branching and multiplexing by this phase change.
• the electro-optical element referred to here is not limited to phase and intensity modulation, and can be used as, for example, a polarization conversion element, a demultiplexing/multiplexing element, and the like.
• the nonlinear optically active copolymer of the present invention can be used for applications other than communication devices, such as electric field sensors that detect changes in electric field as changes in refractive index.
• An optical waveguide using a varnish containing the nonlinear optically active copolymer of the present invention as a core material can be produced, for example, by the method disclosed in WO2016/035823.
• a poling treatment is required in order to develop the secondary nonlinear optical properties of the material (for example, thin film) produced using the varnish containing the nonlinear optically active copolymer.
• the poling process involves heating the material to a temperature above the glass transition temperature and below the melting point of the material, applying a predetermined electric field, and cooling the material while maintaining the electric field. This is an operation to orient optically active sites (atomic groups exhibiting nonlinear optical activity). This manipulation allows the material to develop macroscopic nonlinear optical properties.
• the orientation of the nonlinear optically active sites is random when the nonlinear optically active copolymer is simply formed into a thin film in the form of a varnish. 15° C., preferably 10° C. lower than the glass transition temperature of (approximately 120° C. or higher if the nonlinear optically active copolymer does not exhibit a glass transition temperature) to a temperature below the melting point and poling. , to develop nonlinear optical properties.
• Tg glass transition point
• the nonlinear optical compound used in the present invention is not particularly limited, but is selected, for example, from organic dye compounds exhibiting second-order nonlinear optical properties.
• Reference Example 1 Production of nonlinear optical compound (1) The following compound [EO-1] was used as the nonlinear optical compound (1) to be introduced into the side chain of the polymer. The following compounds are X.I. Zhang et al., Tetrahedron Lett. , 51, p5823 (2010).
• Nonlinear optical compound (2) The following compound [EO-2] was used as the nonlinear optical compound (2) to be introduced into the side chain of the polymer.
• the following compounds were produced by the following methods. After dissolving N-methyl-N-(2-hydroxyethyl)-4-aminobenzaldehyde (manufactured by Combi-Blocks, CAS No. 1201-91-8) in ethanol, impurities were filtered and re-treated with toluene. Purified by precipitation. 8.96 g (50 mmol) of purified N-methyl-N-(2-hydroxyethyl)-4-aminobenzaldehyde was dissolved in 50 mL of ethanol.
• the reaction solution was cooled to room temperature and dried hexane was used to precipitate the polymer. This precipitate was collected with a filter and dried under reduced pressure to obtain a precursor polymer of a nonlinear optically active copolymer (13.3 g, yield 89%).
• the isocyanate groups of the precursor polymer and the hydroxy groups of the nonlinear optical compound (1) were condensed under stirring at room temperature in an inert atmosphere.
• methanol was added to eliminate the unreacted isocyanate groups.
• THF was concentrated, and a large amount of methanol was added to precipitate the polymer.
• the precipitate was collected with a filter, dried sufficiently, and the target nonlinear optically active copolymer having a repeating unit represented by the following formula: EOP-P-50 (Example 1) and EOP-P-60 (Example 1) Example 2) were each obtained with a yield of about 90%.
• the numerical values and symbols (50, m, 50-m, etc. in the case of Example 1) attached to the repeating units represent the molar ratio of each repeating unit (total 100).
• m represents the molar ratio of repeating units in which the isocyanate groups of the precursor polymer and the nonlinear optical compound have reacted.
• the molar ratio of the repeating units in which the unreacted isocyanate groups were reacted with methanol to eliminate the unreacted isocyanate groups was determined by subtracting m from the molar ratio of repeating units having isocyanate groups in the precursor polymer (50 in the case of Example 1). It is represented by the subtracted value.
• This precipitate was collected by a filter and dried under reduced pressure to obtain a precursor polymer of a nonlinear optically active copolymer (3.8 g, yield 90%).
• Nonlinear Optically Active Copolymer 2.0 g of the nonlinear optical compound (1) [EO-1] is added to 2.0 g of the resulting precursor polymer (with isocyanate groups of about 5.3 mmol) (precursor polymer and the nonlinear optical compound (1) in an amount of 50% by mass, 3.4 mmol), 100 g of dry THF was added, and the mixture was uniformly dissolved by stirring. 0.1 g of DBTDL (5 mass % with respect to the precursor polymer) was added here. The isocyanate groups of the precursor polymer and the hydroxy groups of the nonlinear optical compound (1) were condensed under stirring at room temperature in an inert atmosphere.
• This precipitate was collected by a filter and dried under reduced pressure to obtain a precursor polymer (3.75 g, yield 88%) of a nonlinear optically active copolymer.
• Nonlinear Optically Active Copolymer 0.86 g of nonlinear optical compound (1) [EO-1] (precursor polymer and the nonlinear optical compound (1) in an amount of 30% by mass, 1.5 mmol), 100 g of dry THF was added, and the mixture was uniformly dissolved by stirring. 0.1 g of DBTDL (5 mass % with respect to the precursor polymer) was added here. The isocyanate groups of the precursor polymer and the hydroxy groups of the nonlinear optical compound (1) were condensed under stirring at room temperature in an inert atmosphere. When the GPC peak of the unreacted nonlinear optical compound (1) disappeared or was no longer observed to decrease, methanol was added to quench the unreacted isocyanate group.
• the reaction solution was cooled to room temperature and dried hexane was used to precipitate the polymer. This precipitate was collected with a filter and dried under reduced pressure to obtain a precursor polymer of a nonlinear optically active copolymer (18.5 g, yield 93%).
• Nonlinear Optically Active Copolymer 6.67 g of nonlinear optical compound (1) [EO-1] (precursor polymer and the nonlinear optical compound (1) in an amount of 40% by mass, 11.4 mmol), 250 g of dry THF was added, and the mixture was uniformly dissolved by stirring. 0.5 g of DBTDL (5 mass % with respect to the precursor polymer) was added here. The isocyanate groups of the precursor polymer and the hydroxy groups of the nonlinear optical compound (1) were condensed under stirring at room temperature in an inert atmosphere. When the GPC peak of the unreacted nonlinear optical compound (1) disappeared or was no longer observed to decrease, methanol was added to quench the unreacted isocyanate group.
• Example 7 Production of nonlinear optically active copolymer (EOP-CA-40) (1) Production of precursor polymer 8.96 g (50 mmol) of CM, 3.88 g (25 mmol) of NCO, 5.51 g of Ada are placed in a 300 mL round bottom flask. (25 mmol), 70.0 mg (0.4 mmol) of AIBN, 0.35 g (1.0 mmol) of CPTC, and 80 g of dry toluene were added, sufficiently bubbled with nitrogen, and then stirred to form a uniform reaction solution. Polymerization was allowed to occur overnight in an oil bath at 80°C.
• CM:Ada:NCO 50:25:25 mol %, which was the same as the ratio of the monomers, according to the proton ratio of 1 H NMR.
• Nonlinear Optically Active Copolymer 6.67 g of nonlinear optical compound (1) [EO-1] (precursor polymer and the nonlinear optical compound (1) in an amount of 40% by mass, 11.4 mmol), 250 g of dry THF was added, and the mixture was uniformly dissolved by stirring. 0.5 g of DBTDL (5 mass % with respect to the precursor polymer) was added here. The isocyanate groups of the precursor polymer and the hydroxy groups of the EO dye were condensed under stirring at room temperature in an inert atmosphere. When the GPC peak of the unreacted nonlinear optical compound (1) disappeared or was no longer observed to decrease, methanol was added to quench the unreacted isocyanate group.
• Example 8 Production of nonlinear optically active copolymer (EOP-C-50) (1) Production of precursor polymer 5.38 g (30 mmol) of CM, 4.65 g (30 mmol) of NCO, 39.4 mg of AIBN are placed in a 300 mL round bottom flask. (0.24 mmol), 20.7 mg (0.6 mmol) of CPTC, and 40 g of dry toluene were added, and after sufficient nitrogen bubbling, the mixture was stirred to form a uniform reaction solution.
• precursor polymer 5.38 g (30 mmol) of CM, 4.65 g (30 mmol) of NCO, 39.4 mg of AIBN are placed in a 300 mL round bottom flask. (0.24 mmol), 20.7 mg (0.6 mmol) of CPTC, and 40 g of dry toluene were added, and after sufficient nitrogen bubbling, the mixture was stirred to form a uniform reaction solution.
• the reaction solution was cooled to room temperature, and dried hexane was used to precipitate the polymer.This precipitate was collected by a filter and dried under reduced pressure to obtain a nonlinear optically active copolymer.
• a precursor polymer (10.2 g, yield 91%) of was obtained.
• Nonlinear Optically Active Copolymer 8.0 g of the nonlinear optical compound (2) [EO-2] was added to 8.0 g of the obtained precursor polymer (with isocyanate groups of about 23.4 mmol) (precursor polymer and the nonlinear optical compound (2) in an amount of 50% by mass, 16.8 mmol), 500 g of dry THF was added, and the mixture was uniformly dissolved by stirring. 0.4 g of DBTDL (5 mass % with respect to the precursor polymer) was added here. The isocyanate groups of the precursor polymer and the hydroxy groups of the nonlinear optical compound (2) were condensed under stirring at room temperature in an inert atmosphere.
• Example 9 Production of nonlinear optically active copolymer (EOP-CNe-50) (1) Production of precursor polymer 5.38 g (30 mmol) of CM, 5.97 g (30 mmol) of Neg, 39.4 mg of AIBN are placed in a 200 mL round bottom flask. (0.24 mmol), 20.7 mg (0.6 mmol) of CPTC, and 50 g of dry toluene were added, and after sufficient nitrogen bubbling, the mixture was stirred to obtain a uniform reaction solution. Polymerization was allowed to occur overnight in an oil bath at 80°C. After confirming the synthesis of the polymer by GPC, the reaction solution was cooled to room temperature and dried hexane was used to precipitate the polymer.
• precursor polymer 5.38 g (30 mmol) of CM, 5.97 g (30 mmol) of Neg, 39.4 mg of AIBN are placed in a 200 mL round bottom flask. (0.24 mmol), 20.7 mg (0.6 mmol)
• Nonlinear Optically Active Copolymer 8.0 g of the nonlinear optical compound (2) [EO-2] was added to 8.0 g of the obtained precursor polymer (with about 21.1 mmol of isocyanate group) (precursor polymer and the nonlinear optical compound (2) in an amount of 50% by mass, 16.8 mmol), 500 g of dry THF was added, and the mixture was uniformly dissolved by stirring. 0.4 g of DBTDL (5 mass % with respect to the precursor polymer) was added here. The isocyanate groups of the precursor polymer and the hydroxy groups of the nonlinear optical compound (2) were condensed under stirring at room temperature in an inert atmosphere.
• Example 10 Production of nonlinear optically active copolymer (EOP-CANe-50) (1) Production of precursor polymer 5.38 g (30 mmol) of CM, 3.59 g (18 mmol) of Neg, and 2.64 g of Ada are placed in a 200 mL round bottom flask. (12 mmol), 39.4 mg (0.24 mmol) of AIBN, and 20.7 mg (0.6 mmol) of CPTC were mixed with 50 g of dry toluene, sufficiently bubbled with nitrogen, and then stirred to form a uniform reaction solution. Polymerization was allowed to occur overnight in an oil bath at 80°C.
• the reaction solution was cooled to room temperature and dried hexane was used to precipitate the polymer. This precipitate was collected with a filter and dried under reduced pressure to obtain a precursor polymer (11.1 g, yield 90%) of a nonlinear optically active copolymer.
• Nonlinear Optically Active Copolymer 5.3 g of nonlinear optical compound (2) [EO-2] (precursor polymer and the nonlinear optical compound (2) in an amount of 40% by mass, 11.2 mmol), 500 g of dry THF was added, and the mixture was uniformly dissolved by stirring. 0.4 g of DBTDL (5 mass % with respect to the precursor polymer) was added thereto. The isocyanate groups of the precursor polymer and the hydroxy groups of the nonlinear optical compound (2) were condensed under stirring at room temperature in an inert atmosphere. When the GPC peak of the unreacted nonlinear optical compound (2) disappeared or no peak reduction was observed, methanol was added to quench the unreacted isocyanate group.
• Example 11 Production of nonlinear optically active polymer (EOP-P31-40) (1) Production of precursor polymer In a 200 mL round-bottomed flask, PM5.19 g (30 mmol), NCO1.55 g (10 mmol), polymerization initiator AIBN26.3 mg (0 .16 mmol), 0.138 g (0.4 mmol) of a chain transfer agent CPTC, and 30 g of CPN were added, and after sufficient nitrogen bubbling, the mixture was stirred to obtain a uniform reaction solution. Polymerization was allowed to occur overnight in an oil bath at 80°C. After confirming the synthesis of the polymer by GPC, the reaction solution was cooled to room temperature and dried hexane was used to precipitate the polymer.
• nonlinear optically active copolymer 1.33 g of nonlinear optical compound (1) [EO-1] was added to 2.0 g of the obtained precursor polymer (with about 3.0 mmol of isocyanate group). The amount charged to the total amount of the polymer and the nonlinear optical compound (1): 40% by mass, 2.3 mmol) was charged into the flask. Dry THF was added thereto so as to be 25 times the mass of the solid content, and was uniformly dissolved by stirring. 0.1 g of DBTDL (5% by mass relative to the precursor polymer) was further added here. The isocyanate groups of the precursor polymer and the hydroxy groups of the nonlinear optical compound (1) were condensed under stirring at room temperature in an inert atmosphere.
• Example 12 Production of nonlinear optically active polymer (EOP-P13-50) (1) Production of precursor polymer In a 200 mL round bottom flask, PM 1.73 g (10 mmol), NCO 4.65 g (30 mmol), polymerization initiator AIBN 26.3 mg (0 .16 mmol), 0.138 g (0.4 mmol) of a chain transfer agent CPTC, and 30 g of CPN were added, and after sufficient nitrogen bubbling, the mixture was stirred to obtain a uniform reaction solution. Polymerization was allowed to occur overnight in an oil bath at 80°C. After confirming the synthesis of the polymer by GPC, the reaction solution was cooled to room temperature and dried hexane was used to precipitate the polymer.
• Table 1 shows the types and molar ratios of the monomer components used in the preparation of the precursor polymers, the types of the nonlinear optical compounds, and the amounts of the nonlinear optical compounds charged, for the nonlinear optically active copolymers prepared in Examples and Comparative Examples. each shown.
• the charged amount of the nonlinear optical compound refers to the charged amount (% by mass) of the nonlinear optical compound with respect to the total amount (mass) of the precursor polymer and the nonlinear optical compound.
• the content of the structure derived from the nonlinear-optical compound in the copolymer obtained from the maximum absorption intensity is As the introduction rate [% by mass] of Table 1 also shows the reaction conversion rate of the nonlinear optical compound expressed as the ratio of the introduction rate [%] of the nonlinear optical compound in the nonlinear optically active copolymer to the charged amount [%] of the nonlinear optical compound. Table 1 also shows the glass transition point of each of the nonlinear optically active copolymers prepared.
• the nonlinear optically active copolymers obtained in Examples 1 to 12 were even when various N-substituted maleimides and NCO-containing (meth)acrylic acid derivatives were used as the monomer components of the precursor polymer. Also, even when other monomers were used, all of them had a high glass transition point (Tg) of 160° C. or higher. Among them, Examples 1 to 5, 8 to 9, and 12 achieved a high introduction ratio exceeding 40% and achieved a high glass transition point, regardless of the type of nonlinear optical compound.

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