JPWO2019069925A1 - Crosslinked polymer composition containing an organic nonlinear optical compound - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a polymer matrix capable of not only suppressing the relaxation of orientation of an organic nonlinear optical compound but also being able to orient the organic nonlinear optical compound to a higher degree and facilitating viscosity adjustment. To provide a composition containing an organic nonlinear optical compound and an optical material obtained by using the composition. A composition containing a norborneneimide copolymer having a structural unit represented by the formula [1] and a structural unit represented by the formula [2], and an organic nonlinear optical compound. (In the formula, R1 is an alkyl group having 1 to 12 carbon atoms which may have a substituent, or an aryl group having 6 to 10 carbon atoms which may have a substituent. Represented, L1 represents a divalent organic group having 1 to 30 carbon atoms.) [Selection diagram] None

Description

The present invention relates to a polymer composition containing an organic nonlinear optical compound used for optical switches, optical information processing such as optical modulation, optical communication, etc., and more specifically, a composition in which an organic nonlinear optical compound is dispersed in a crosslinked polymer matrix. It relates to an object and an optical material formed from the composition.

In recent years, in fields such as optical information processing and optical communication, development of various optoelectronic devices using materials containing fluorescent dyes and nonlinear optical materials has been promoted. Of these, the nonlinear optical material is a material that exhibits a polarization response proportional to the square, cube, or higher-order term of the electric field of light, and is the second harmonic generation (SHG) or the first order. For those that produce a second-order nonlinear optical effect such as the Pockels effect, which is the electro-optical effect of the above, applications such as a light source, an optical switch, and optical modulation are considered.

Conventionally, lithium niobate and potassium dihydrogen phosphate have been put into practical use and widely used as inorganic nonlinear optical materials. However, in recent years, organic nonlinear optical materials, which have advantages such as high nonlinear optical performance, low material cost, and high mass productivity, have attracted attention over these inorganic materials, and active research and development are being carried out for practical use. It has been.

As a method for manufacturing a device using an organic material, a method using a single crystal of a compound having a nonlinear optical property (organic nonlinear optical compound), a vapor deposition method, and an LB film method are known. Further, there is a method of introducing a structure having nonlinear optical characteristics into the main chain or side chain of the polymer compound, or a method of dispersing the nonlinear optical compound in the polymer matrix. In particular, in the case of a polymer system, the film can be formed by a casting method, a dip method, a spin coating method, or the like, so that processing is easy.

Among these, in the method of dispersing the organic nonlinear optical compound in the polymer matrix, it is required that the organic nonlinear optical compound is dispersed at a high concentration without agglomeration and becomes optically uniform.
As the organic nonlinear optical compound used here, a push-pull type π-conjugated compound having an electron-donating functional group at one end of the π-conjugated chain and an electron-withdrawing functional group at the other end is known. There is. For example, Disperse Red 1 (DR1), which has an electron-donating group, diethylamino group, and an electron-withdrawing group, nitro group, in azobenzene as a π-conjugated chain.

However, since such a molecule has a large dipole moment, it has a large intermolecular interaction, has poor solubility or dispersibility in a medium, and is highly compatible with polymethyl methacrylate (PMMA), which is generally used as a polymer matrix. It was difficult to disperse at the concentration. Further, the glass transition temperature of PMMA is as low as about 100 ° C., and the orientation of the organic nonlinear optical compound using PMMA as a polymer matrix is gradually relaxed even at room temperature, and its characteristics are deteriorated with time.

For this reason, various polymer matrices that can replace PMMA have been studied, and for example, it has been reported that a norbornene imide polymer having a high glass transition temperature and capable of dispersing an organic nonlinear optical compound at a high concentration is used as the polymer matrix. (Patent Document 1).

International Publication No. 2013/172342

However, from the viewpoint of practical use, the orientation of the dispersed organic nonlinear optical compound can be further enhanced (that is, a higher electro-optical constant can be obtained), the desired viscosity can be easily adjusted, and the desired film thickness can be easily formed. A polymer matrix is required.
Therefore, the present invention provides a polymer matrix in which the organic nonlinear optical compound is highly oriented, the viscosity can be easily adjusted, and the orientation relaxation of the organic nonlinear optical compound can be suppressed, and the polymer matrix and the organic are provided. It is an object of the present invention to provide a composition containing a nonlinear optical compound and an optical material obtained by using the composition.

As a result of diligent studies to achieve the above object, the present inventors have adopted a norborneneimide copolymer having a crosslinked structure introduced therein instead of the norborneneimide polymer, and have used the copolymer and an organic non-linear optical compound. By combining them, it has been found that not only the relaxation of the orientation of the organic nonlinear optical compound can be suppressed, but also the organic nonlinear optical compound can be more highly oriented and the viscosity can be easily adjusted, resulting in a polymer matrix. Was completed.

That is, the present invention relates to a composition containing a norborneneimide copolymer having a structural unit represented by the formula [1] and a structural unit represented by the formula [2], and an organic nonlinear optical compound, as a first aspect.
(In the formula, R ¹ represents an alkyl group having 1 to 12 carbon atoms which may have a substituent, or an aryl group having 6 to 10 carbon atoms which may have a substituent, and L ¹ represents a divalent organic group having 1 to 30 carbon atoms.)
As a second aspect, the L ¹ is -Z ^1- L ^2- Z ^2- (where Z ¹ and Z ² are independent cyclohexylene groups or substitutions which may have substituents, respectively. The composition according to the first aspect, which represents a phenylene group which may have a group, and L ² represents a divalent organic group having 1 to 18 carbon atoms).
As a third aspect, the L ² is -OL ^3- O- (where L ³ represents an alkylene group having 1 to 18 carbon atoms which may contain an ether bond or an ester bond). The composition according to the second aspect, which is a group represented by.
As a fourth aspect, the composition according to any one of the first aspect to the third aspect, wherein the organic nonlinear optical compound is a compound having a furan ring represented by the formula [3].
(In the formula, R ⁸ and R ⁹ 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. , ● represents a bond.)
As a fifth aspect, the composition according to the fourth aspect, wherein the organic nonlinear optical compound is a compound represented by the formula [4].
(In the formula, R ² and R ³ are independent of each other and may have a hydrogen atom, an alkyl group having 1 to 10 carbon atoms which may have a substituent, or an alkyl group which may have a substituent. Representing an aryl group of 6 to 10, R ^{4 to} R ⁷ independently represent a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, a hydroxy group, an alkoxy group having 1 to 10 carbon atoms, and the number of carbon atoms. An alkylcarbonyloxy group having 2 to 11, 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 halogen atoms, and R ⁸ and R ⁹ are independent hydrogen atoms, alkyl groups having 1 to 5 carbon atoms, haloalkyl groups having 1 to 5 carbon atoms, or aryls having 6 to 10 carbon atoms. Represents a group, and Ar represents a divalent organic group represented by the formula [5] or the formula [6].)
(In the formula, R ^{10 to} R ¹⁵ each independently have a hydrogen atom, an alkyl group having 1 to 10 carbon atoms which may have a substituent, or an alkyl group which may have a substituent. Represents 6 to 10 aryl groups.)
As a sixth aspect, the composition according to any one of the first to fifth aspects, wherein the content of the organic nonlinear optical compound is 1 to 150 parts by mass with respect to 100 parts by mass of the norbornene imide copolymer. Regarding things.
A seventh aspect relates to a varnish containing the composition according to any one of the first to sixth aspects.
As the eighth viewpoint, the present invention relates to a thin film composed of the composition according to any one of the first to sixth viewpoints.
As a ninth aspect, the present invention relates to an electro-optical element containing the composition according to any one of the first to sixth aspects.
As a tenth aspect, the present invention relates to an optical switching device containing the composition according to any one of the first to sixth aspects.
As the eleventh viewpoint, the present invention relates to an organic nonlinear optical material using the composition according to any one of the first to sixth viewpoints.
As a twelfth aspect, it relates to a norborneneimide copolymer having a structural unit represented by the formula [1] and a structural unit represented by the formula [2].
(In the formula, R ¹ represents an alkyl group having 1 to 12 carbon atoms which may have a substituent, or an aryl group having 6 to 10 carbon atoms which may have a substituent, and L ¹ represents a divalent organic group having 1 to 30 carbon atoms.)
As a thirteenth aspect, wherein ^{L 1 is, -Z 1 -L 2 -Z 2 -} ( ^where independently Z 1, ^{Z 2} is optionally substituted cyclohexylene group, or a substituted represents a phenylene group which may have a group, L ² is a group represented by represents.) a divalent organic group having 1 to 18 carbon atoms, about norbornene imide copolymer according to the twelfth aspect ..
As a fourteenth aspect, the L ² is -OL ^3- O- (where L ³ represents an alkylene group having 1 to 18 carbon atoms which may contain an ether bond or an ester bond). It relates to the norborneneimide copolymer according to the thirteenth aspect, which is a group represented by.
As a fifteenth viewpoint, it relates to a bis (norbornene dicarboxymid) compound represented by the formula [7].
(In the formula, Z ¹ and Z ² each independently represent a cyclohexylene group which may have a substituent or a phenylene group which may have a substituent, and L ³ has ³ carbon atoms. Represents ~ 18 alkylene groups.)

The composition of the present invention can not only suppress the relaxation of the orientation of the organic nonlinear optical compound by combining the norborneneimide copolymer having a specific structural unit and the organic nonlinear optical compound, but also obtain the organic nonlinear optical compound. It can be oriented to a higher degree and the viscosity can be easily adjusted.
Further, since the composition of the present invention is dissolved in a solvent to form a varnish and can be easily molded, an effect that it can be suitably used in the field of optoelectronic materials as an optical material with high handleability can be obtained. Be done.
Further, the organic nonlinear optical material of the present invention has a large nonlinear optical constant, and it is possible to form an optical device that can be easily molded.

Further, the norborneneimide copolymer having a specific structural unit of the present invention suppresses the relaxation of the orientation of the organic nonlinear optical compound, highly orients the organic nonlinear optical compound, and can easily adjust the viscosity, so that the organic nonlinear optical compound can be easily adjusted. It can be suitably used as a polymer matrix of optical compounds.
Furthermore, the bifunctional monomer bis (norbornene dicarboxymid) compound of the present invention is useful as a crosslinker (crosslinker) for introducing a crosslinked structure into a norborneneimide homopolymer, and in particular, the thermal properties of the polymer. It is a useful compound as a cross-linking agent capable of enhancing the electric field orientation of the organic nonlinear optical compound while maintaining the same effect of suppressing the orientation relaxation of the organic nonlinear optical compound.

FIG. 1 shows the dispersity (Mw / Mn) of the norbornene imide copolymer obtained in Example and the norbornene imide polymer obtained in Comparative Example 1 with respect to the mass ratio of the structural unit derived from the bifunctional monomer in each polymer. It is a figure which shows. FIG. 2 shows the viscosity V of a 10 mass% toluene solution of the norbornene imide copolymer obtained in Example and the norbornene imide polymer obtained in Comparative Example 1 with respect to the mass ratio of the structural unit derived from the bifunctional monomer in each polymer. It is a figure which shows (mPa · s). FIG. 3 shows the glass transition temperature Tg (° C.) of the norborneneimide copolymer obtained in Example and the norborneneimide polymer obtained in Comparative Example 1 with respect to the mass ratio of the structural unit derived from the bifunctional monomer in each polymer. It is a figure which shows. FIG. 4 shows a 5% weight loss temperature Td ₅ (5% weight loss temperature Td ₅ ) of the norbornene imide copolymer obtained in Example and the norbornene imide polymer obtained in Comparative Example 1 with respect to the mass ratio of the structural unit derived from the bifunctional monomer in each polymer. ℃). FIG. 5 shows the electro-optical constant r ₃₃ (pm / pm / of the norbornene imide copolymer obtained in Example and the norbornene imide polymer obtained in Comparative Example 1 with respect to the mass ratio of the structural unit derived from the bifunctional monomer in each polymer. V) (left axis) and dispersion degree (Mw / Mn) (right axis) are shown. FIG. 6 shows the result of the temperature endurance test on the test piece whose electro-optic constant was measured, and shows the rate of change (r ₃₃ / r ₃₃ ) from the initial value (r ₃₃ (0)) of the electro-optic constant r ₃₃ (r ₃₃ / r ₃₃ ). It is a figure which shows 0) × 100) as a function of time (h).

<Norbornene imide copolymer having a structural unit represented by the formula [1] and a structural unit represented by the formula [2]>
The average molecular weight of the norborneneimide copolymer having the structural unit represented by the following formula [1] and the structural unit represented by the following formula [2] used in the composition of the present invention is not particularly limited. For example, the weight average molecular weight is 10,000 to 3,000,000, preferably 10,000 to 1,000,000, and more preferably 20,000 to 500,000. The degree of dispersion (weight average molecular weight / number average molecular weight) is, for example, 1.1 to 80, 1.2 to 20, and can be 1.2 to 10.
The weight average molecular weight and the number average molecular weight in the present invention are measured values by gel permeation chromatography (polystyrene conversion).
Further, a norborneneimide copolymer having a structural unit represented by the above formula [1] and a structural unit represented by the following formula [2] is also an object of the present invention.

In the above formula [1], R ¹ is an alkyl group having 1 to 12 carbon atoms which may have a substituent, or an aryl group having 6 to 10 carbon atoms which may have a substituent. Represent.
Here, the alkyl group having 1 to 12 carbon atoms may have a branched structure or a cyclic structure, and may have a methyl group, an ethyl group, an n-propyl group, an isopropyl group, a cyclopropyl group, an n-butyl group, and the like. Isobutyl group, sec-butyl group, tert-butyl group, n-pentyl group, neopentyl group, cyclopentyl group, n-hexyl group, cyclohexyl group, n-octyl group, n-decyl group, n-dodecyl group, 1-adamantyl Examples include a group, a benzyl group, a phenethyl group and the like.
Examples of the aryl group having 6 to 10 carbon atoms include a phenyl group and a naphthyl group.
Examples of the substituent of the alkyl group having 1 to 12 carbon atoms include a hydroxy group; a halogen atom such as a fluoro group, a chloro group, a bromo group and an iodo group.
Examples of the substituent of the aryl group having 6 to 10 carbon atoms include an alkyl group such as a methyl group and an ethyl group; a hydroxyalkyl group such as a hydroxymethyl group; a hydroxy group; an alkoxy group such as a methoxy group and an octyloxy group; fluoro Examples thereof include halogen atoms such as a group, a chloro group, a bromo group and an iodo group.
Specific examples of R ¹ include cyclohexyl group, 4-hydroxycyclohexyl group, n-octyl group, 1-adamantyl group, phenyl group, 4-tolyl group, 4-hydroxymethylphenyl group, 4-hydroxyphenyl group, Examples thereof include 2,3,4,5,6-pentafluorophenyl groups.

Further, the structural unit represented by the formula [1] may be a cis form or a trans form.

In the above formula [2], L ¹ represents a divalent organic group having 1 to 30 carbon atoms.
The divalent organic group having 1 to 30 carbon atoms is not particularly limited, but may contain, for example, one or more aromatic rings and / or aliphatic rings, and one or more ether bonds (-). A divalent group that may contain a bonding group such as an O-) or an ester bond (-COO-), and a group in which the total number of carbon atoms constituting the group is 30 at the maximum (however, the ester bond is formed. If it is included, the carbon atoms in the ester bond are not included in the number of carbon atoms of 1 to 30 above).
The divalent organic group having 1 to 30 carbon atoms preferably has an alkylene group, an aromatic ring, an aliphatic ring, or both, and may contain an ether bond and / or an ester bond. It is selected from valent hydrocarbon groups.

Above all, it is preferable that L ¹ is −Z ^{1 −} L ² −Z ² −. Here, Z ¹ and Z ² independently represent a cyclohexylene group which may have a substituent or a phenylene group which may have a substituent, and L ² has 1 to 1 carbon atoms. Represents 18 divalent organic groups.
As the substituent of the cyclohexylene group or the phenylene group, an alkyl group such as a methyl group or an ethyl group; a hydroxyalkyl group such as a hydroxymethyl group; a hydroxy group; an alkoxy group such as a methoxy group or an octyloxy group; a fluoro group or a chloro Examples thereof include halogen atoms such as a group, a bromo group and an iodo group.
The divalent organic group having 1 to 18 carbon atoms may include an ether bond and / or an ester bond. An alkylene group having 1 to 18 carbon atoms (however, when an ester bond is contained, the ester bond is in progress). The carbon atom of is not included in the number of carbon atoms of 1 to 18 above).

In particular, the L ² is a group represented by −OL ³ −O−, that is, the L ¹ is a group represented by −Z ¹ −OL ³ −O−Z ^2−. Is preferable. Here, L ³ represents an alkylene group having 1 to 18 carbon atoms which may contain an ether bond or an ester bond (Z ¹ and Z ² are as defined above).
The alkylene group having 1 to 18 carbon atoms may have a branched structure or a cyclic structure, and may have a methylene group, an ethylene group, a trimethylene group, a 1-methylethylene group, a tetramethylene group, or a 1-methyltrimethylene group. , 1,1-dimethylethylene group, pentamethylene group, 1-methyltetramethylene group, 2-methyltetramethylene group, 1,1-dimethyltrimethylene group, 1,2-dimethyltrimethylene group, 2,2-dimethyl Trimethylene group, 1-ethyltrimethylene group, hexamethylene group, 1-methylpentamethylene group, 2-methylpentamethylene group, 3-methylpentamethylene group, 1,1-dimethyltetramethylene group, 1,2-dimethyl Tetramethylene group, 2,2-dimethyltetramethylene group, 1-ethyltetramethylene group, 1,1,2-trimethyltrimethylene group, 1,2,2-trimethyltrimethylene group, 1-ethyl-1-methyltri Methylene group, 1-ethyl-2-methyltrimethylene group, 1,4-cyclohexylene group, heptamethylene group, octamethylene group, nonamethylene group, decamethylene group, undecamethylene group, dodecamethylene group, tridecamethylene group , Tetradecamethylene group, pentadecamethylene group, hexadecamethylene group, heptadecamethylene group, octadecamethylene group and the like.
Examples of the alkylene group containing an ether bond include a 3-oxapentane-1,5-diyl group and a 3,6-dioxaoctane-1,8-diyl group.

Further, the three-dimensional arrangement is not particularly limited in the structural unit represented by the formula [2].

In the present invention, the ratio of the structural unit represented by the formula [1] to the structural unit represented by the formula [2] in the above-mentioned norborneneimide copolymer is not particularly limited, and is relative to the structural unit represented by the formula [1]. The mass ratio of the structural unit represented by the formula [2] may exceed 0. For example, the ratio of the structural unit represented by the formula [2] to the structural unit represented by the formula [1] can be 0.01 to 10% by mass.
From the viewpoint of facilitating viscosity adjustment in the composition of the present invention, the ratio of the structural unit represented by the formula [2] to the structural unit represented by the formula [1] is 0.01 to 5% by mass. From the viewpoint that the organic nonlinear optical compound described later can be oriented to a higher degree, it can be 0.01 to 3% by mass.

The norbornene imide copolymer used in the present invention may have a structural unit represented by the formula [1] and a structural unit other than the structural unit represented by the formula [2]. Examples of other structural units include structural units such as norbornene, cyclobutene, cyclopentene, cyclooctene, cyclododecene, and 1,5-cyclooctadiene. When having the above other structural units, it is desirable that the structural units represented by the formula [1] and the structural units represented by the formula [2] are 50 to 99 mol% with respect to the entire polymer.
On the other hand, it is more preferable that the norborneneimide copolymer is a polymer consisting only of the structural unit represented by the formula [1] and the structural unit represented by the formula [2] because the effects of the present invention can be easily exhibited. Therefore, it is desirable that the norborneneimide copolymer used in the present invention has a structural unit represented by the formula [1] and a structural unit represented by the formula [2] in an amount of 50 to 100 mol%.

<Method for producing a norborneneimide copolymer having a structural unit represented by the formula [1] and a structural unit represented by the formula [2]>
The norborneneimide copolymer having the structural unit represented by the above formula [1] and the structural unit represented by the formula [2] is, for example, a metal complex such as a ruthenium catalyst in which a norborneneimide monomer and a bis (norborneneimide) monomer are used. It is obtained by carrying out a polymerization reaction in a solvent in the presence of.
The norbornene imide copolymer was prepared from Macromol. Chem. Phys. It can be synthesized according to the method for producing a norborneneimide polymer described in 2002, 203, 1811-1818.

Examples of the bis (norborneneimide) monomer include bis (norbornene dicarboxymid) compounds represented by the following formula [7], and the present compound is also the subject of the present invention.
In the formula, Z ¹ and Z ² independently represent a cyclohexylene group which may have a substituent or a phenylene group which may have a substituent, and L ³ has 3 to 3 carbon atoms. Represents 18 alkylene groups.

In the production of the norborneneimide copolymer having the structural unit represented by the above formula [1] and the structural unit represented by the formula [2], the norborneneimide monomer and the bis (norborneneimide) monomer are used alone. It may be used, or two or more kinds may be used in combination. When two or more kinds of norborneneimide monomers and / or bis (norborneneimide) monomers are used, the ratio of these monomers is not particularly limited and can be appropriately adjusted according to the structure of the target polymer.

Further, as described above, the norborneneimide copolymer having the structural unit represented by the above formula [1] and the structural unit represented by the formula [2] is the structural unit represented by the above formula [1] and the formula [2]. ], It may have a structural unit (norbornene, cyclobutene, cyclopentene, cyclooctene, cyclododecene, 1,5-cyclooctadiene, etc.) other than the structural unit represented by. In that case, in addition to the norbornene imide monomer / bis (norbornene imide) monomer, as other monomers, a monomer constituting a structural unit other than the structural unit represented by the above formula [1] and the structural unit represented by the formula [2]. Can be used to obtain norbornene imide copolymers.
When other monomers are used, for all the monomers used to obtain the norborneneimide copolymer having the structural unit represented by the formula [1] and the structural unit represented by the formula [2] used in the present invention. , Other monomers can be used in the range of 1-50 mol%.

As for the other monomers, one kind may be used alone, or two or more kinds may be used in any combination. Further, the ratio is not particularly limited, and can be adjusted according to the structure of the target norborneneimide copolymer.

The metal complex used in the above polymerization reaction is not particularly limited, and can be arbitrarily selected and used from various known metal complexes for polymerization. Of these, ruthenium catalysts such as Grubbs catalysts (1st generation Grubbs catalysts, 2nd generation Grubbs catalysts) are preferable.
The metal complex can be used in a molar ratio of 5 × 10 ^-3 to 1 × 10 ⁻² times that of all the raw materials.

The solvent used in the polymerization reaction is not particularly limited as long as it does not inhibit the polymerization reaction, and examples thereof include halogenated hydrocarbons such as methylene chloride, chloroform, 1,2-dichloroethane, and chlorobenzene. One type of solvent may be used alone, or two or more types may be mixed and used in any combination.

The temperature during the polymerization reaction is not particularly limited, but is -50 to 100 ° C. Preferably, it is −50 to 60 ° C. The pressure during the polymerization reaction is not particularly limited, but is usually carried out at normal pressure.

The time of the polymerization reaction varies depending on the type of monomer and metal complex used, the temperature and pressure at the time of polymerization, and the like, but is 10 minutes to 10 hours. It is preferably 20 minutes to 5 hours.

After completion of the polymerization reaction, the obtained norborneneimide copolymer is recovered by an arbitrary method, and if necessary, post-treatment such as washing is performed. Examples of the method for recovering the norborneneimide copolymer from the reaction solution include a method such as reprecipitation.

<Organic nonlinear optical compound>
The organic nonlinear optical compound used in the present invention is a π-conjugated compound having an electron donating group at one end of the π-conjugated chain and an electron-withdrawing group at the other end, and a compound having a large molecular hyperpolarizability β is desirable. .. Examples of the electron donating group include a dialkylamino group, and examples of the electron attracting group include a cyano group, a nitro group and a fluoroalkyl group.
Among them, examples of the organic nonlinear optical compound used in the present invention include a compound having a furan ring represented by the formula [3].

In the above formula, R ⁸ and R ⁹ independently have 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. Represents, ● represents a bond.

Specifically, the organic nonlinear optical compound is preferably a compound represented by the following formula [4].

In the above formula [4], R ² and R ³ may independently have a hydrogen atom, an alkyl group having 1 to 10 carbon atoms which may have a substituent, or a substituent. It represents a good aryl group with 6 to 10 carbon atoms.
Here, the alkyl group having 1 to 10 carbon atoms may have a branched structure or a cyclic structure, and may have a methyl group, an ethyl group, an n-propyl group, an isopropyl group, a cyclopropyl group, an n-butyl group, and the like. Isobutyl group, sec-butyl group, tert-butyl group, n-pentyl group, neopentyl group, cyclopentyl group, n-hexyl group, cyclohexyl group, n-octyl group, n-decyl group, 1-adamantyl group, benzyl group, Examples include a phenethyl group.
Examples of the aryl group having 6 to 10 carbon atoms include a phenyl group, a tolyl group, a xsilyl group, and a naphthyl group.
Examples of the substituent include an amino group; a hydroxy group; an alkoxycarbonyl group such as a methoxycarbonyl group and a tert-butoxycarbonyl group; a trimethylsilyloxy group, a tert-butyldimethylsilyloxy group, a tert-butyldiphenylsilyloxy group and a triphenylsilyl group. Cyriloxy groups such as oxy groups; halogen atoms such as fluoro groups, chloro groups, bromo groups and iodo groups can be mentioned.

In the above formula [4], R ^{4 to} R ⁷ independently represent a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, a hydroxy group, an alkoxy group having 1 to 10 carbon atoms, and 2 to 2 carbon atoms. 11 alkylcarbonyloxy groups, aryloxy groups with 4 to 10 carbon atoms, arylcarbonyloxy groups with 5 to 11 carbon atoms, silyloxy groups with alkyl and / or phenyl groups with 1 to 6 carbon atoms, or Represents a halogen atom.
Examples of the alkyl group having 1 to 10 carbon atoms, for example, include those exemplified in the ^R 2, ^{R 3.}
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 naphthalene-2-yloxy group, a furan-3-yloxy group, and a thiophen-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, a thiophene-3-carbonyloxy group and the like.
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, an iodine group and the like.

In the above formulas [3] and [4], R ⁸ and R ⁹ are independently hydrogen atoms, alkyl groups having 1 to 5 carbon atoms, haloalkyl groups having 1 to 5 carbon atoms, or carbon atoms. Represents an aryl group of number 6-10.
Here, the alkyl group having 1 to 5 carbon atoms may have a branched structure or a cyclic structure, and may have a methyl group, an ethyl group, an n-propyl group, an isopropyl group, a cyclopropyl group, an n-butyl group, and the like. Examples thereof include isobutyl group, sec-butyl group, tert-butyl 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 may have a fluoromethyl group, a trifluoromethyl group, a bromodifluoromethyl group, a 2-chloroethyl group, a 2-bromoethyl group, 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, perfluoropentyl group, perfluorocyclopentyl group and the like can be mentioned. ..
Examples of the aryl group having 6 to 10 carbon atoms include a phenyl group, a tolyl group, a xsilyl group, and a naphthyl group.

In the above formula [4], Ar represents a divalent organic group represented by the following formula [5] or the formula [6].

In the above formulas [5] and [6], R ^{10 to} R ¹⁵ each independently have a hydrogen atom, an alkyl group having 1 to 10 carbon atoms which may have a substituent, or a substituent. It represents an aryl group having 6 to 10 carbon atoms which may be possessed.
Wherein the alkyl group having 1 to 10 carbon atoms, for the aryl group, and substituents having 6 to 10 carbon atoms, include those exemplified in the ^R 2, ^{R 3.}

In the composition of the present invention, the content of the organic nonlinear optical compound is based on 100 parts by mass of the norborneneimide copolymer having the structural unit represented by the above formula [1] and the structural unit represented by the formula [2]. It is usually 1 to 150 parts by mass, preferably 10 to 100 parts by mass.
When the content of the organic nonlinear optical compound is 1 part by mass or more, it becomes easy to obtain a sufficient nonlinear optical effect, and when it is 150 parts by mass or less, it is easy to form a film, and the mechanical strength of the material is lowered. Hateful.

<Composition and varnish>
When the composition of the present invention is used as an organic nonlinear optical material, it is generally used in the form of a thin film. As a method for producing the thin film, the composition of the present invention is dissolved in an appropriate organic solvent to form a varnish, and the varnish is used as an appropriate substrate (for example, silicon / silicon dioxide coated substrate, silicon nitride substrate, metal (for example). On a substrate such as a substrate coated with aluminum, molybdenum, chromium, etc.), a glass substrate, a quartz substrate, an ITO substrate, etc.) or a film (for example, a resin film such as a triacetyl cellulose film, a polyester film, an acrylic film). In addition, a wet coating method is preferable in which a film is formed by coating by rotary coating, flow coating, roll coating, slit coating, rotary coating following the slit, inkjet coating, printing, or the like.

Here, the solvent used for preparing the varnish dissolves a norborneneimide copolymer having a structural unit represented by the above formula [1] and a structural unit represented by the formula [2] and an organic nonlinear optical compound, and is added as desired. The type and structure of the solvent are not particularly limited as long as the solvent dissolves the additives described below and has such a dissolving ability.
Examples of preferable organic solvents include ethers such as tetrahydrofuran (THF), methyl tetrahydrofuran, 1,4-dioxane and diethylene glycol dimethyl ether; ketones such as methyl ethyl ketone (MEK), cyclopentanone and cyclohexanone; esters such as ethyl acetate. Alcohols such as cyclohexanol, propylene glycol monomethyl ether (PGME); halides such as 1,2-dichloroethane, chloroform, chlorobenzene; aromatic hydrocarbons such as toluene and xylene; N, N-dimethylformamide (DMF), Examples of amides such as N, N-dimethylacetamide and N-methyl-2-pyrrolidone (NMP); sulfoxides such as dimethyl sulfoxide (DMSO) and the like. These solvents can be used alone or in combination of two or more.
Among these solvents, cyclopentanone, 1,2-dichloroethane, chloroform and the like have high solubility of norborneneimide copolymers having a structural unit represented by the formula [1] and a structural unit represented by the formula [2]. , Preferable from the viewpoint of good coating property.
The solid content concentration in the varnish is, for example, 0.5 to 30% by mass, and for example, 5 to 30% by mass. The solid content as used herein means all the components of the varnish excluding the solvent.
Therefore, it is preferable to use the prepared varnish after filtering it with a filter having a pore size of about 0.2 μm or the like.

The varnish may be an antioxidant such as hydroquinone, an ultraviolet absorber such as benzophenone, a rheology adjuster such as silicone oil or a surfactant, and a silane coupling, if necessary, as long as the effects of the present invention are not impaired. It can contain an adhesion aid such as an agent, a cross-linking agent for a polymer matrix, a compatibilizer, a curing agent, a pigment, a storage stabilizer, an antifoaming agent, and the like.

<Electro-optical element, optical switching element>
The composition of the present invention can be applied as a material for various conventionally proposed electro-optical elements.
Typical examples of electro-optical elements include optical switching elements (optical communication elements) such as Mach-Zehnder type optical modulators. In an optical switching element, the composition of the present invention is applied onto a substrate such as glass or plastic, and then processed by a lithography method using light or an electron beam, a wet and dry etching method, a nanoimprint method, or the like to generate light. It has an optical waveguide structure that allows transmission. An optical waveguide structure is usually formed by applying and laminating on a material having a refractive index lower than that of the composition, but the composition is not limited to this structure and can be applied to other optical waveguide structures.
In a Mach-Zehnder type optical modulator, which is a typical optical switching element, high-frequency voltage is applied to both or one of the branched optical waveguide structures to express electro-optical characteristics, and light propagated by changing the refractive index. Causes a phase change of. By changing the light intensity after branching and merging by this phase change, high-speed modulation of light becomes possible.
Further, the electro-optical element referred to here is not limited to phase and intensity modulation, and can be used, for example, as a polarization conversion element, a demultiplexing element, and a combiner element.
Further, the present composition can be used not only for communication elements but also for electric field sensors that detect changes in the electric field as changes in the refractive index.

<Organic nonlinear optical material>
In the present invention, a polling process is required in order to exhibit the second-order nonlinear optical characteristics of the material (for example, a thin film) produced by using the composition. The polling process is to apply a predetermined electric field to a non-linear optical compound molecule while the material is heated to a temperature about 25 ° C. lower than the glass transition temperature of the material, preferably about 10 ° C. lower or higher and lower than the melting point. It is an alignment operation, and the material is cooled while maintaining the electric field to fix the orientation. By this operation, the material can exhibit macroscopic nonlinear optical properties.
Also in the present invention, since the orientation of the organic nonlinear optical compound molecules is random simply by thinning the composition, the glass of the composition containing the above-mentioned norborneneimide copolymer which is a matrix and the organic nonlinear optical compound. The temperature is about 25 ° C. lower than the transition temperature, preferably about 10 ° C. or higher (about 120 ° C. or higher when the above composition does not show the glass transition temperature), and is heated to a temperature below the melting point and polled. , Non-linear optical characteristics are exhibited.

Hereinafter, the present invention will be described in more detail with reference to Examples, but the present invention is not limited to these Examples. The measuring devices and the like used in the examples are as follows.

(1) ^{1 1} H NMR spectrum device: JNM-LA400 manufactured by JEOL Ltd.
Solvent: CDCl ₃
CD ₃ OD (Example 1)
Internal standard: Tetramethylsilane (0.00ppm)
(2) ¹³ C NMR spectrum device: JNM-LA400 manufactured by JEOL Ltd.
Solvent: CDCl ₃
CD ₃ OD (Example 1)
Internal standard: CDCl ₃ (76.9 ppm)
CD ₃ OD (49.3 ppm) (Example 1)
(3) GPC (Gel Permeation Chromatography)
Equipment: LC-2000 manufactured by JASCO Corporation
Column: TSKgel (registered trademark) G2000H _XL manufactured by Tosoh Corporation
Eluent: Tetrahydrofuran Detector: RI
Standard sample: Showa Denko Corporation Shodex (registered trademark) STANDARD SM-105
(4) Glass transition temperature (Tg) measuring device: Differential scanning calorimeter manufactured by SII Nanotechnology Co., Ltd. DSC6220
Measurement conditions: Under nitrogen atmosphere Temperature rise rate: 10 ° C / min (50-250 ° C)
(5) 5% weight loss temperature (Td ₅ ) measuring device: Differential thermal weight simultaneous measuring device TG / DTA6200 manufactured by SII Nanotechnology Co., Ltd.
Measurement conditions: Under nitrogen atmosphere Temperature rise rate: 10 ° C / min (50-450 ° C)
(6) Ruthenium content measuring device: ICP-MS Agent (registered trademark) 7500cs manufactured by Agilent Technologies, Ltd.
(7) Viscosity measuring device: Rheometer MCR 302 manufactured by Antonio Par

The abbreviations have the following meanings.
DMF: N, N-dimethylformamide EDC: 1,2-dichloroethane THF: tetrahydrofuran

[Production Example 1-1] Production of exo-2-norbornene-5,6-dicarboxylic acid anhydride [8]
Maleic anhydride [manufactured by Tokyo Chemical Industry Co., Ltd.] 188.24 g (1.92 mol) was dissolved in 200 mL of o-dichlorobenzene, and this solution was refluxed. To this, 128.66 g (0.97 mol) of dicyclopentadiene [manufactured by Tokyo Chemical Industry Co., Ltd.] melted by heating to 50 ° C. was added over 30 minutes. After completion of the addition, the mixture was further stirred under reflux for 1.5 hours. The reaction mixture was allowed to cool at room temperature (approximately 23 ° C.). After 24 hours, the precipitated white crystalline solid was filtered under reduced pressure to obtain a crude product. This crude product was recrystallized from hot chlorobenzene several times to obtain exo-2-norbornene-5,6-dicarboxylic acid anhydride (gain rate 48%).

[Production Example 1-2] Production of exo-N- (4-hydroxyphenyl) -2-norbornene-5,6-dicarboxymid [9]
33.20 g (0.20 mol) of exo-2-norbornene-5,6-dicarboxylic acid anhydride [8] obtained according to Production Example 1-1 was dissolved in 200 mL of THF. To this, 20.96 g (0.19 mol) of 4-aminophenol [manufactured by Tokyo Chemical Industry Co., Ltd.] was added dropwise at room temperature (approximately 23 ° C.) with stirring. After completion of the dropping, the mixture was refluxed for another 4 hours. The reaction mixture was allowed to cool at room temperature (approximately 23 ° C.). The precipitated white precipitate was filtered under reduced pressure and washed with cold THF. This wet product was dried under reduced pressure at 60 ° C. for 12 hours to obtain amic acid (gain rate 78%).
75.00 g (0.27 mol) of amic acid obtained according to the above method was dissolved in 300 mL of anhydrous DMF. To this, 41.65 g (0.41 mol) of triethylamine [manufactured by Tokyo Chemical Industry Co., Ltd.] was added in 10 minutes. After completion of the addition, the mixture was further stirred at 120 ° C. for 3 hours. The reaction mixture was cooled to room temperature (approximately 23 ° C.) and then added to deionized water. The precipitated white precipitate was collected by filtration and washed with deionized water to obtain a crude product. This crude product was recrystallized several times from a hot ethanol / THF mixed solution (volume ratio 10: 1) to form white crystals of exo-N- (4-hydroxyphenyl) -2-norbornene-5,6-dicarboxymid. Was obtained (acquisition rate 39%).

[Example 1] Production of N, N'-((octamethylenebisoxy) bis (4,1-phenylene)) bis (2-norbornene-5,6-dicarboxymid) [10]
Exo-N- (4-hydroxyphenyl) -2-norbornene-5,6-dicarboxymid [9] 12.30 g (48.2 mmol), 1,8-dibromooctane [9] obtained according to Production Example 1-2. Tokyo Chemical Industry Co., Ltd.] 6.55 g (24.1 mmol) and potassium carbonate [Tokyo Chemical Industry Co., Ltd.] 33.00 g (238.8 mmol) were dissolved in 200 mL of acetonitrile and refluxed for 48 hours. It was. The reaction mixture was cooled to room temperature (approximately 23 ° C.) and then acetonitrile was distilled off using a rotary evaporator. This residue was added to deionized water and stirred for 1 hour to ensure that potassium carbonate was dissolved. The organic matter was extracted with dichloromethane and washed several times with saturated brine. The organic layer was dried over anhydrous magnesium sulfate [manufactured by Kanto Chemical Co., Inc.], and then dichloromethane was distilled off to obtain a crude product. This crude product was purified by silica gel column chromatography (ethyl acetate / hexane mixed solution (volume ratio 1:10)). Furthermore, it was recrystallized from a hot ethanol / THF mixed solution (volume ratio 9: 1), and N, N'-((octamethylenebisoxy) bis (4,1-phenylene)) bis (2-norbornene-5,6). -Dicarboxymid) was obtained (profit rate 67%).
^{1 1} H NMR (400 MHz, CD ₃ OD) δ: 7.13 (d, J = 9.2 Hz, 4H), 7.00 (d, J = 8.7 Hz, 4H), 6.36 (m, 4H) , 3.99 (t, J = 6.8Hz, 4H), 3.19 (s, 4H), 2.81 (s, 4H), 2.50 (m, 4H), 1.72 (m, 4H) ), 1.42 (m, 8H) ppm.
¹³ C NMR (125 MHz, CD ₃ OD) δ: 189.59, 170.96, 150.32, 140.71, 137.25, 127.16, 80.25, 59.97, 57.45, 55. 21,41.23, 41.10, 37.95 ppm.

[Production Example 2] Production of Exo-N-cyclohexyl-2-norbornene-5,6-dicarboxymid [11]
100 g (0.61 mol) of exo-2-norbornene-5,6-dicarboxylic acid anhydride [8] obtained according to Production Example 1-1 was dissolved in 400 mL of toluene. To this, 60.85 g (0.61 mol) of cyclohexylamine [manufactured by Tokyo Chemical Industry Co., Ltd.] was added dropwise over 1 hour with stirring at room temperature (about 23 ° C.). During the dropping, a white precipitate was formed and it became difficult to stir, so 100 mL of toluene was further added. After completion of the dropping, the mixture was further stirred at 50 ° C. for 1 hour. The precipitated white precipitate was filtered under reduced pressure and washed with toluene. This wet product was dried under reduced pressure at 70 ° C. for 12 hours to obtain an amic acid (gain rate 72%).
50.00 g (0.19 mmol) of amic acid obtained according to the above method was dissolved in 300 mL of anhydrous DMF. To this, 28.78 g (0.28 mol) of triethylamine [manufactured by Tokyo Chemical Industry Co., Ltd.] was added in 10 minutes. After completion of the addition, the mixture was further stirred at 120 ° C. for 3 hours. The reaction mixture was cooled to room temperature (approximately 23 ° C.) and then added to deionized water. The precipitated white precipitate was collected by filtration and washed with deionized water to obtain a crude product. This crude product was recrystallized from hot methanol to obtain exo-N-cyclohexyl-2-norbornene-5,6-dicarboxymid (gain rate 54%).

[Example 2a] Poly (exo-N-cyclohexyl-2-norbornene-5,6-dicarboxymid-co-N, N'-((octamethylenebisoxy) bis (4,1-phenylene)) bis ( 2-Norbornene-5,6-dicarboxymid))] [12a]
1.00 g (4.08 mmol) of exo-N-cyclohexyl-2-norbornene-5,6-dicarboxymid [11] obtained according to Production Example 2 above, and N, N'-(produced according to Example 1 above). (Octamethylenebisoxy) Bis (4,1-phenylene)) Bis (2-norbornene-5,6-dicarboxymid) [10] 2 mg (0.2% by mass based on compound [11]) in Schlenk tube And purged with nitrogen. To this, 20 mL of chloroform was injected with a syringe. After stirring this solution for 10 minutes, a solution prepared by dissolving 67 mg (81.6 μmol) of Grabs 1st generation catalyst [manufactured by SIGMA-ALDRICH] in 2 mL of chloroform was quickly added. After further stirring for 3 hours, 2 mL of degassed ethyl vinyl ether [manufactured by Kanto Chemical Co., Inc.] was injected with a syringe to quench the reaction. Further, the mixture was stirred at room temperature (approximately 23 ° C.) for 1 hour. The reaction mixture was concentrated, then dissolved in chloroform and added to methanol to reprecipitate the polymer. Reprecipitation with chloroform-methanol was repeated several more times. The polymer is filtered off, washed with methanol, and the desired poly (exo-N-cyclohexyl-2-norbornene-5,6-dicarboxymid-co-N, N'-((octamethylenebisoxy)). Bis (4,1-phenylene)) Bis (2-norbornene-5,6-dicarboxymid)) was obtained.
The peak top molecular weight Mp of the obtained norbornene imide copolymer measured by GPC in terms of polystyrene is 35,000, the number average molecular weight Mn is 21,000, the weight average molecular weight Mw is 25,000, and the dispersity Mw / Mn is 1. It was .2. The glass transition temperature Tg was 209 ° C., the 5% weight loss temperature Td ₅ was 410 ° C., and the viscosity in a 10 mass% toluene solution was 5.9 mPa · s.
^{1 1} H NMR (400 MHz, CDCl ₃ ) δ: 5.73, 5.51, 3.87, 3.48, 3.26, 2.92, 2.65, 2.11, 1.79, 1.59 , 1.21 ppm.

[Example 2b] Production of compound [12b] Norbornene was operated in the same manner as in Example 2a except that the amount of compound [10] used was changed to 6 mg (0.6% by mass with respect to compound [11]). An imide copolymer was obtained.
The peak top molecular weight Mp of the obtained norbornene imide copolymer measured by GPC in terms of polystyrene is 24,000, the number average molecular weight Mn is 21,000, the weight average molecular weight Mw is 28,000, and the dispersity Mw / Mn is 1. It was 0.4. The glass transition temperature Tg was 209 ° C., the 5% weight loss temperature Td ₅ was 410 ° C., and the viscosity in a 10 mass% toluene solution was 4.2 mPa · s.
^{1 1} H NMR (400 MHz, CDCl ₃ ) δ: 5.73, 5.51, 3.87, 3.48, 3.26, 2.92, 2.65, 2.11, 1.79, 1.59 , 1.21 ppm.

[Example 2c] Production of compound [12c] Norbornene was operated in the same manner as in Example 2a except that the amount of compound [10] used was changed to 8 mg (0.8% by mass with respect to compound [11]). An imide copolymer was obtained.
The peak top molecular weight Mp of the obtained norbornene imide copolymer measured by GPC in terms of polystyrene is 24,000, the number average molecular weight Mn is 21,000, the weight average molecular weight Mw is 30,000, and the dispersity Mw / Mn is 1. It was 0.4. The glass transition temperature Tg was 210 ° C., the 5% weight loss temperature Td ₅ was 418 ° C., and the viscosity in a 10 mass% toluene solution was 8.4 mPa · s.
^{1 1} H NMR (400 MHz, CDCl ₃ ) δ: 7.12, 6.93, 5.73, 5.51, 3.87, 3.48, 3.26, 2.92, 2.65, 2.11. , 1.79, 1.59, 1.21 ppm.

[Example 2d] Production of compound [12d] The norbornene imide copolymer was operated in the same manner as in Example 2a except that the amount of compound [10] used was changed to 10 mg (1% by mass based on compound [11]). Got
The peak top molecular weight Mp of the obtained norbornene imide copolymer measured by GPC in terms of polystyrene is 26,000, the number average molecular weight Mn is 26,000, the weight average molecular weight Mw is 42,000, and the dispersity Mw / Mn is 1. It was 0.6. The glass transition temperature Tg was 208 ° C., the 5% weight loss temperature Td ₅ was 362 ° C., the viscosity in a 10 mass% toluene solution was 8.3 mPa · s, and the ruthenium content derived from the residual catalyst was 980 ppm.
^{1 1} H NMR (400 MHz, CDCl ₃ ) δ: 7.12, 6.93, 5.73, 5.51, 3.87, 3.48, 3.26, 2.92, 2.65, 2.11. , 1.79, 1.59, 1.21 ppm.

[Example 2e] Production of compound [12e] Norbornene was operated in the same manner as in Example 2a except that the amount of compound [10] used was changed to 14 mg (1.4% by mass with respect to compound [11]). An imide copolymer was obtained.
The peak top molecular weight Mp of the obtained norbornene imide copolymer measured by GPC in terms of polystyrene is 25,000, the number average molecular weight Mn is 24,000, the weight average molecular weight Mw is 46,000, and the dispersity Mw / Mn is 1. It was 9.9. The glass transition temperature Tg was 208 ° C., the 5% weight loss temperature Td ₅ was 399 ° C., and the viscosity in a 10 mass% toluene solution was 3.8 mPa · s.
^{1 1} H NMR (400 MHz, CDCl ₃ ) δ: 7.12, 6.93, 5.73, 5.51, 3.87, 3.48, 3.26, 2.92, 2.65, 2.11. , 1.79, 1.59, 1.21 ppm.

[Example 2f] Production of compound [12f] Norbornene was operated in the same manner as in Example 2a except that the amount of compound [10] used was changed to 16 mg (1.6% by mass with respect to compound [11]). An imide copolymer was obtained.
The peak top molecular weight Mp of the obtained norbornene imide copolymer measured by GPC in terms of polystyrene is 25,000, the number average molecular weight Mn is 26,000, the weight average molecular weight Mw is 60,000, and the dispersity Mw / Mn is 2. It was .1. The glass transition temperature Tg was 210 ° C., the 5% weight loss temperature Td ₅ was 398 ° C., the viscosity in a 10 mass% toluene solution was 5.2 mPa · s, and the ruthenium content derived from the residual catalyst was 1,100 ppm.
^{1 1} H NMR (400 MHz, CDCl ₃ ) δ: 7.12, 6.93, 5.73, 5.51, 3.87, 3.48, 3.26, 2.92, 2.65, 2.11. , 1.79, 1.59, 1.21 ppm.

[Example 2g] Production of compound [12g] Norbornene was operated in the same manner as in Example 2a except that the amount of compound [10] used was changed to 18 mg (1.8% by mass with respect to compound [11]). An imide copolymer was obtained.
The peak top molecular weight Mp of the obtained norbornene imide copolymer measured by GPC in terms of polystyrene is 31,000, the number average molecular weight Mn is 27,000, the weight average molecular weight Mw is 75,000, and the dispersity Mw / Mn is 2. It was 8.8. The glass transition temperature Tg was 212 ° C., the 5% weight loss temperature Td ₅ was 405 ° C., and the viscosity in a 10 mass% toluene solution was 5.8 mPa · s.
^{1 1} H NMR (400 MHz, CDCl ₃ ) δ: 7.12, 6.93, 5.73, 5.51, 3.87, 3.48, 3.26, 2.92, 2.65, 2.11. , 1.79, 1.59, 1.21 ppm.

[Example 2h] Production of compound [12h] Norbornene was operated in the same manner as in Example 2a except that the amount of compound [10] used was changed to 20 mg (2.0% by mass with respect to compound [11]). An imide copolymer was obtained.
The peak top molecular weight Mp of the obtained norbornene imide copolymer measured by GPC in terms of polystyrene is 29,000, the number average molecular weight Mn is 28,000, the weight average molecular weight Mw is 102,000, and the dispersity Mw / Mn is 3. It was 0.6. The glass transition temperature Tg was 207 ° C., the 5% weight loss temperature Td ₅ was 365 ° C., the viscosity in a 10 mass% toluene solution was 5.1 mPa · s, and the ruthenium content derived from the residual catalyst was 1,000 ppm.
^{1 1} H NMR (400 MHz, CDCl ₃ ) δ: 7.12, 6.93, 5.73, 5.51, 3.87, 3.48, 3.26, 2.92, 2.65, 2.11. , 1.79, 1.59, 1.21 ppm.

[Example 2i] Production of compound [12i] Norbornene was operated in the same manner as in Example 2a except that the amount of compound [10] used was changed to 22 mg (2.2% by mass based on compound [11]). An imide copolymer was obtained.
The peak top molecular weight Mp of the obtained norborneneimide copolymer measured by GPC in terms of polystyrene is 28,000, the number average molecular weight Mn is 31,000, the weight average molecular weight Mw is 122,000, and the dispersity Mw / Mn is 3. It was 9.9. The glass transition temperature Tg was 211 ° C., the 5% weight loss temperature Td ₅ was 406 ° C., and the viscosity in a 10 mass% toluene solution was 6.5 mPa · s.
^{1 1} H NMR (400 MHz, CDCl ₃ ) δ: 7.12, 6.93, 5.73, 5.51, 3.87, 3.48, 3.26, 2.92, 2.65, 2.11. , 1.79, 1.59, 1.21 ppm.

[Example 2j] Production of compound [12j] Norbornene was operated in the same manner as in Example 2a except that the amount of compound [10] used was changed to 24 mg (2.4% by mass with respect to compound [11]). An imide copolymer was obtained.
The peak top molecular weight Mp of the obtained norborneneimide copolymer measured by GPC in terms of polystyrene is 28,000, the number average molecular weight Mn is 35,000, the weight average molecular weight Mw is 146,000, and the dispersity Mw / Mn is 4. It was .2. The glass transition temperature Tg was 212 ° C., the 5% weight loss temperature Td ₅ was 408 ° C., and the viscosity in a 10 mass% toluene solution was 8.0 mPa · s.
^{1 1} H NMR (400 MHz, CDCl ₃ ) δ: 7.12, 6.93, 5.73, 5.51, 3.87, 3.48, 3.26, 2.92, 2.65, 2.11. , 1.79, 1.59, 1.21 ppm.

[Example 2k] Production of compound [12k] Norbornene was operated in the same manner as in Example 2a except that the amount of compound [10] used was changed to 26 mg (2.6% by mass with respect to compound [11]). An imide copolymer was obtained.
The peak top molecular weight Mp of the obtained norborneneimide copolymer measured by GPC in terms of polystyrene is 27,000, the number average molecular weight Mn is 32,000, the weight average molecular weight Mw is 155,000, and the dispersity Mw / Mn is 4. It was 8.8. The glass transition temperature Tg was 213 ° C., the 5% weight loss temperature Td ₅ was 358 ° C., and the viscosity in a 10 mass% toluene solution was 7.9 mPa · s.
^{1 1} H NMR (400 MHz, CDCl ₃ ) δ: 7.12, 6.93, 5.73, 5.51, 3.87, 3.48, 3.26, 2.92, 2.65, 2.11. , 1.79, 1.59, 1.21 ppm.

[Example 2l] Production of compound [12l] Norbornene was operated in the same manner as in Example 2a except that the amount of compound [10] used was changed to 28 mg (2.8% by mass with respect to compound [11]). An imide copolymer was obtained.
The peak top molecular weight Mp of the obtained norborneneimide copolymer measured by GPC in terms of polystyrene is 27,000, the number average molecular weight Mn is 32,000, the weight average molecular weight Mw is 191,000, and the dispersity Mw / Mn is 5. It was 9.9. The glass transition temperature Tg was 213 ° C., the 5% weight loss temperature Td ₅ was 410 ° C., and the viscosity in a 10 mass% toluene solution was 7.7 mPa · s.
^{1 1} H NMR (400 MHz, CDCl ₃ ) δ: 7.12, 6.93, 5.73, 5.51, 3.87, 3.48, 3.26, 2.92, 2.65, 2.11. , 1.79, 1.59, 1.21 ppm.

[Example 2m] Production of compound [12m] Norbornene imide copolymer was operated in the same manner as in Example 2a except that the amount of compound [10] used was changed to 30 mg (3% by mass based on compound [11]). Got
The peak top molecular weight Mp of the obtained norborneneimide copolymer measured by GPC in terms of polystyrene is 737,000, the number average molecular weight Mn is 35,000, the weight average molecular weight Mw is 155,000, and the dispersity Mw / Mn is 7. It was 3.3. The glass transition temperature Tg was 213 ° C., the 5% weight loss temperature Td ₅ was 391 ° C., and the viscosity in a 10 mass% toluene solution was 8.4 mPa · s.
^{1 1} H NMR (400 MHz, CDCl ₃ ) δ: 7.12, 6.93, 5.73, 5.51, 3.87, 3.48, 3.26, 2.92, 2.65, 2.11. , 1.79, 1.59, 1.21 ppm.

[Example 2n] Production of compound [12n] Norbornene was operated in the same manner as in Example 2a except that the amount of compound [10] used was changed to 34 mg (3.4% by mass with respect to compound [11]). An imide copolymer was obtained.
The peak top molecular weight Mp of the obtained norbornene imide copolymer measured by GPC in terms of polystyrene is 828,000, the number average molecular weight Mn is 40,000, the weight average molecular weight Mw is 408,000, and the dispersion degree Mw / Mn is 10. It was .2. The glass transition temperature Tg was 215 ° C., the 5% weight loss temperature Td ₅ was 402 ° C., and the viscosity in a 10 mass% toluene solution was 151.4 mPa · s.
^{1 1} H NMR (400 MHz, CDCl ₃ ) δ: 7.12, 6.93, 5.73, 5.51, 3.87, 3.48, 3.26, 2.92, 2.65, 2.11. , 1.79, 1.59, 1.21 ppm.

[Example 2o] Production of compound [12o] Norbornene was operated in the same manner as in Example 2a except that the amount of compound [10] used was changed to 38 mg (3.8% by mass with respect to compound [11]). An imide copolymer was obtained.
The peak top molecular weight Mp of the obtained norborneneimide copolymer measured by GPC in terms of polystyrene is 853,000, the number average molecular weight Mn is 44,000, the weight average molecular weight Mw is 815,000, and the dispersity Mw / Mn is 18. It was 0.6. The glass transition temperature Tg was 215 ° C., the 5% weight loss temperature Td ₅ was 382 ° C., and the viscosity in a 10 mass% toluene solution was 281.4 mPa · s.
^{1 1} H NMR (400 MHz, CDCl ₃ ) δ: 7.12, 6.93, 5.73, 5.51, 3.87, 3.26, 2.92, 2.65, 2.11.1.79 , 1.59, 1.21 ppm.

[Example 2p] Production of compound [12p] Norbornene was operated in the same manner as in Example 2a except that the amount of compound [10] used was changed to 44 mg (4.4% by mass with respect to compound [11]). An imide copolymer was obtained.
The peak top molecular weight Mp of the obtained norbornene imide copolymer measured by GPC in terms of polystyrene is 716,000, the number average molecular weight Mn is 43,000, the weight average molecular weight Mw is 2,026,000, and the degree of dispersion Mw / Mn. Was 47.2. The glass transition temperature Tg was 216 ° C., the 5% weight loss temperature Td ₅ was 384 ° C., and the viscosity in a 10 mass% toluene solution was 343.1 mPa · s.
^{1 1} H NMR (400 MHz, CDCl ₃ ) δ: 7.12, 6.93, 5.73, 5.51, 3.87, 3.26, 2.92, 2.65, 2.11.1.79 , 1.59, 1.21 ppm.

[Example 2q] Production of compound [12q] Norbornene was operated in the same manner as in Example 2a except that the amount of compound [10] used was changed to 46 mg (4.6% by mass with respect to compound [11]). An imide copolymer was obtained.
The peak top molecular weight Mp of the obtained norborneneimide copolymer measured by GPC in terms of polystyrene is 906,000, the number average molecular weight Mn is 29,000, the weight average molecular weight Mw is 2,135,000, and the dispersity Mw / Mn. Was 73.5. The glass transition temperature Tg was 213 ° C., the 5% weight loss temperature Td ₅ was 381 ° C., and the viscosity in a 10 mass% toluene solution was 538.7 mPa · s.
^{1 1} H NMR (400 MHz, CDCl ₃ ) δ: 7.12, 6.93, 5.73, 5.51, 3.87, 3.26, 2.92, 2.65, 2.11.1.79 , 1.59, 1.21 ppm.

[Comparative Example 1] Production of poly (exo-N-cyclohexyl-2-norbornene-5,6-dicarboxymid) [13]
The same procedure as in Example 2a was carried out except that compound [10] was not used to obtain a norbornene imide polymer.
The peak top molecular weight Mp of the obtained norbornene imide polymer measured by GPC in terms of polystyrene is 25,000, the number average molecular weight Mn is 20,000, the weight average molecular weight Mw is 23,000, and the dispersity Mw / Mn is 1. It was .2. The glass transition temperature Tg was 203 ° C., the 5% weight loss temperature Td ₅ was 365 ° C., the viscosity in a 10 mass% toluene solution was 5.3 mPa · s, and the ruthenium content derived from the residual catalyst was 910 ppm.
^{1 1} H NMR (400 MHz, CDCl ₃ ) δ: 5.73, 5.51, 3.87, 3.48, 3.26, 2.92, 2.65, 2.11, 1.79, 1.59 , 1.21 ppm.

In the case of the mass ratio of the structural unit derived from the compound [10] in each polymer of the norborneneimide copolymers obtained in Examples 2a to 2q and the norborneneimide polymer obtained in Comparative Example 1 (for example, in the case of compound [12a]). Dispersity with respect to 2 mg ÷ (1,000 mg + 2 mg) × 100 = 0.20%) is shown in FIG. 1, the viscosity of the 10 mass% toluene solution is shown in FIG. 2, Tg is shown in FIG. 3, and Td ₅ is shown in FIG. 4, respectively. Also shown.

As shown in FIG. 1, it was confirmed that the molecular weight distribution (dispersity) of the obtained norbornene polymer can be dramatically increased by copolymerizing a minute amount of the bifunctional monomer (compound [10]).
Further, as shown in FIG. 2, the viscosity of the obtained 10% by mass toluene solution of the norbornene polymer can be increased by copolymerizing a minute amount of the bifunctional monomer (compound [10]), which is suitable for film formation. It was confirmed that the viscosity can be adjusted freely.
On the other hand, as shown in FIGS. 3 to 4, the glass transition temperature and the 5% weight loss temperature are around 210 ° C. and 390 ° C., respectively, regardless of the copolymerization amount of the bifunctional monomer (compound [10]). It was almost constant. That is, it was suggested that even if the bifunctional monomer (compound [10]) was copolymerized to form a crosslinked polymer, the properties against heat were not affected.

[Reference Example 1] Production of Organic Nonlinear Optical Compound [FTC] The following compound [FTC] was used as the organic nonlinear optical compound. This compound is described in X.I. M. Zhang et al., Tetrahedron Letter. , 51, p5873 (2010), manufactured by the same method as that disclosed.

[Example 3c, 3f, 3h, Comparative Example 2] Preparation of composition and electro-optical characteristics 65 mg of the norborneneimide (co) polymer shown in Table 1, 35 mg of the organic nonlinear optical compound [FTC] produced in Reference Example 1, and 1 mL of EDC was mixed and stirred at room temperature (approximately 23 ° C.) for 12 hours.

This solution was filtered through a filter having a pore size of 0.20 μm, and then spin-coated (1,000 rpm × 30 seconds) on an ITO substrate of 20 mm × 20 mm. The coating was heated on a hot plate at 85 ° C. for 30 minutes and further in a vacuum oven at 85 ° C. for 24 hours. The film thickness of the obtained thin film is also shown in Table 1.
A gold electrode having a diameter of 4 mm and a thickness of 200 nm was prepared by sputtering on this thin film to obtain a test piece.

The electro-optic constant of each test piece was determined by using a semiconductor laser having a wavelength of 1.31 μm as a light source. C. Teng et al., Apple. Phys. Lett. , 56, p1734 (1990), and Y. et al. Shuto et al., J. Mol. Apple. Phys. , 77, p4632 (1995), and the measurement was performed by the same method as that disclosed. In the electric field alignment treatment, each test piece is heated and held at a predetermined temperature on a hot plate, a voltage is applied through a gold electrode and an ITO electrode at the electric field strength shown in Table 1, and polling treatment is performed for about 1 minute. Was done. Then, after quenching to fix the polarization orientation, the voltage application was stopped. The test piece that had been polled was used for evaluation of electro-optical characteristics.
The values of the electro-optical constant r ₃₃ obtained from each test piece are also shown in Table 1 together with the temperature and electric field strength at which the electric field orientation treatment was performed. Further, FIG. 5 shows a graph in which the value (and the degree of dispersion) of the electro-optical constant r ₃₃ is plotted against the mass ratio of the structural unit derived from the compound [10] in each polymer.

As shown in Table 1 and FIG. 5, the electro-optical constant of the composition of the present invention is increased from 63 pm / V to 78 pm / V by introducing a crosslinked structure into the norborneneimide polymer by copolymerization of bifunctional monomers. It was confirmed that. That is, the effect of enhancing the electric field orientation of the organic nonlinear optical compound was recognized. The reason has not been clarified, but it is presumed that the introduction of the crosslinked structure increased the amorphousness of the polymer.

[Example 4h, Comparative Example 3] Temperature endurance test A temperature endurance test was performed on the test pieces whose electro-optical constants were measured in Example 3h and Comparative Example 2. Each test piece was held at 85 ° C., and the relaxation characteristics of the electro-optical constant were measured from immediately after polling to after 500 hours. FIG. 6 shows the rate of change (r ₃₃ / r ₃₃ (0) × 100) from the initial value (r ₃₃ (0)) of the electro-optical constant r ₃₃ as a function of time (h).

In an amorphous host, the orientation of the nonlinear optical compound is generally relaxed by heat, and the electro-optical constant decreases with time. However, as shown in FIG. 6, the electro-optical constant of the composition of the present invention is amorphous. It was confirmed that the homopolymer had the same thermal stability as the low-grade homopolymer (Example 4h: 79%, Comparative Example 3: 77%).

Claims (15)

A composition containing a norborneneimide copolymer having a structural unit represented by the formula [1] and a structural unit represented by the formula [2], and an organic nonlinear optical compound.
(In the formula, R ¹ represents an alkyl group having 1 to 12 carbon atoms which may have a substituent, or an aryl group having 6 to 10 carbon atoms which may have a substituent, and L ¹ represents a divalent organic group having 1 to 30 carbon atoms.) The L ¹ has -Z ^1- L ^2- Z ^2- (where Z ¹ and Z ² each have a cyclohexylene group or a substituent which may have a substituent independently of each other. The composition according to claim 1, wherein L ² represents a optionally phenylene group, and L ² represents a divalent organic group having 1 to 18 carbon atoms). Group wherein ^{L 2} is, ^-O-L 3 -O- (wherein, ^{L 3} is also contain an ether bond or an ester bond represents an alkylene group having 1 to 18 carbon atoms.) Represented by The composition according to claim 2. The composition according to any one of claims 1 to 3, wherein the organic nonlinear optical compound is a compound having a furan ring represented by the formula [3].
(In the formula, R ⁸ and R ⁹ 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. , ● represents a bond.) The composition according to claim 4, wherein the organic nonlinear optical compound is a compound represented by the formula [4].
(In the formula, R ² and R ³ are independent of each other and may have a hydrogen atom, an alkyl group having 1 to 10 carbon atoms which may have a substituent, or an alkyl group which may have a substituent. Representing an aryl group of 6 to 10, R ^{4 to} R ⁷ independently represent a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, a hydroxy group, an alkoxy group having 1 to 10 carbon atoms, and the number of carbon atoms. An alkylcarbonyloxy group having 2 to 11, 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 halogen atoms, and R ⁸ and R ⁹ are independent hydrogen atoms, alkyl groups having 1 to 5 carbon atoms, haloalkyl groups having 1 to 5 carbon atoms, or aryls having 6 to 10 carbon atoms. Represents a group, and Ar represents a divalent organic group represented by the formula [5] or the formula [6].)
(In the formula, R ^{10 to} R ¹⁵ each independently have a hydrogen atom, an alkyl group having 1 to 10 carbon atoms which may have a substituent, or an alkyl group which may have a substituent. Represents 6 to 10 aryl groups.) The composition according to any one of claims 1 to 5, wherein the content of the organic nonlinear optical compound is 1 to 150 parts by mass with respect to 100 parts by mass of the norbornene imide copolymer. A varnish containing the composition according to any one of claims 1 to 6. A thin film comprising the composition according to any one of claims 1 to 6. An electro-optical element comprising the composition according to any one of claims 1 to 6. An optical switching device comprising the composition according to any one of claims 1 to 6. An organic nonlinear optical material using the composition according to any one of claims 1 to 6. A norborneneimide copolymer having a structural unit represented by the formula [1] and a structural unit represented by the formula [2].
(In the formula, R ¹ represents an alkyl group having 1 to 12 carbon atoms which may have a substituent, or an aryl group having 6 to 10 carbon atoms which may have a substituent, and L ¹ represents a divalent organic group having 1 to 30 carbon atoms.) The L ¹ has -Z ^1- L ^2- Z ^2- (where Z ¹ and Z ² each have a cyclohexylene group or a substituent which may have a substituent independently of each other. represents a phenylene group which may, L ² is a group represented by represents.) a divalent organic group having 1 to 18 carbon atoms, norbornene imide copolymer of claim 12. Group wherein ^{L 2} is, ^-O-L 3 -O- (wherein, ^{L 3} is also contain an ether bond or an ester bond represents an alkylene group having 1 to 18 carbon atoms.) Represented by The norborneneimide copolymer according to claim 13. A bis (norbornene dicarboxymid) compound represented by the formula [7].
(In the formula, Z ¹ and Z ² each independently represent a cyclohexylene group which may have a substituent or a phenylene group which may have a substituent, and L ³ has ³ carbon atoms. Represents ~ 18 alkylene groups.)