WO2019069925A1 - Crosslinked polymer composition containing organic nonlinear optical compound - Google Patents

Abstract

[Problem] To provide a polymer matrix which not only can inhibit an organic nonlinear optical compound from undergoing a relaxation from orientation but also can more highly orient the organic nonlinear optical compound and which renders viscosity regulation easy; and to provide a composition comprising the polymer matrix and an organic nonlinear optical compound and an optical material obtained from the composition. [Solution] A composition which comprises: a norbornene imide copolymer having a structural unit represented by formula [1] and a structural unit represented by formula [2]; and an organic nonlinear optical compound. (In the formulae, R1 represents an optionally substituted C1-12 alkyl group or an optionally substituted C6-10 aryl group and L1 represents a C1-30 divalent organic group.)

Description

Crosslinked polymer composition comprising organic non-linear optical compound

The present invention relates to a polymer composition containing an organic nonlinear optical compound used for optical information processing such as optical switching, light modulation, etc., optical communication, etc. More specifically, the composition in which the organic nonlinear optical compound is dispersed in a crosslinked polymer matrix And optical materials formed from the composition.

In recent years, in the fields of optical information processing, optical communication, and the like, development of various optoelectronic devices using materials containing fluorescent dyes and nonlinear optical materials has been advanced. Of these, nonlinear optical materials are materials that exhibit a polarization response that is proportional to the second-, third-, or higher-order term of the electric field of light, and generate second harmonic generation (SHG) or first-order Applications that produce a second-order non-linear optical effect such as the Pockels effect, which is an electro-optical effect, are considered to be applications such as a light source, an optical switch, and light modulation.

Conventionally, lithium niobate and potassium dihydrogen phosphate are practically used and widely used as inorganic nonlinear optical materials. However, in recent years, organic non-linear optical materials that have advantages such as high non-linear optical performance, inexpensive material costs, high mass productivity, etc. have attracted attention for these inorganic materials, and active research and development toward commercialization are underway. It is

As a method of manufacturing a device using an organic material, a method of using a single crystal of a compound (organic nonlinear optical compound) having nonlinear optical characteristics, a vapor deposition method and an LB film method are known. Furthermore, there is a method of introducing a structure having nonlinear optical properties into the main chain or side chain of a polymer compound, or a method of dispersing a nonlinear optical compound in a polymer matrix. In particular, in the case of a polymer type, the film can be formed by a casting method, a dipping method, a spin coating method or the like, so that the 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 aggregation and is optically uniform.
As the organic nonlinear optical compound to be 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 attracting functional group at the other end is known. There is. For example, Disperse Red 1 (DR1), which has an azobenzene as a π conjugated chain, a diethylamino group as an electron donating group and a nitro group as an electron withdrawing group.

However, such molecules have large intermolecular interaction due to a large dipole moment, and are poorly soluble or dispersible in the medium, and are high in polymethyl methacrylate (PMMA) or the like generally used as a polymer matrix. It was difficult to disperse by concentration. Further, the glass transition temperature of PMMA is as low as about 100 ° C., and the alignment of the organic nonlinear optical compound using PMMA as a polymer matrix is gradually relaxed even at room temperature, and there is a disadvantage that the characteristics thereof deteriorate with time.

For this reason, various polymer matrices as alternatives to 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), and the viscosity can be easily adjusted to a desired viscosity There is a need for polymeric matrices.
Therefore, the present invention provides a polymer matrix capable of highly orienting the organic nonlinear optical compound, facilitating viscosity adjustment, and suppressing the alignment relaxation of the organic nonlinear optical compound, and the polymer matrix and the organic It is an object of the present invention to provide a composition containing a non-linear optical compound, and an optical material obtained using the composition.

As a result of intensive studies to achieve the above object, the present inventors adopt a norbornene imide copolymer in which a crosslinked structure is introduced to the norbornene imide polymer instead of the norbornene imide polymer, and the copolymer and the organic nonlinear optical compound It has been found that the combination not only can suppress the orientation relaxation of the organic nonlinear optical compound but also provides a polymer matrix which can orient the organic nonlinear optical compound to a higher degree and whose viscosity can be easily adjusted. Completed.

That is, the present invention relates to, as a first aspect, a composition comprising a norbornene imide copolymer having a structural unit represented by Formula [1] and a structural unit represented by Formula [2], and an organic nonlinear optical compound.

(Wherein, 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, L ¹ represents a divalent organic group having 1 to 30 carbon atoms.)
As a second aspect, L ¹ is —Z ¹ -L ² -Z ^2- (wherein Z ¹ and Z ² are each independently a cyclohexylene group which may have a substituent, or a substituent The composition according to the first aspect relates to 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 above L ² is —O—L ³ —O— (wherein 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 is a group represented by
As a fourth aspect, the present invention relates to the composition according to any one of the first to third aspects, wherein the organic nonlinear optical compound is a compound having a furan ring represented by the formula [3].

(Wherein, R ⁸ and R ⁹ each independently represent a hydrogen atom, an alkyl group of 1 to 5 carbon atoms, a haloalkyl group of 1 to 5 carbon atoms, or an aryl group of 6 to 10 carbon atoms , ● represents a bond.)
A fifth aspect relates to the composition according to the fourth aspect, wherein the organic nonlinear optical compound is a compound represented by formula [4].

(Wherein, R ² and R ³ each independently represent a hydrogen atom, an alkyl group having 1 to 10 carbon atoms which may have a substituent, or the number of carbon atoms which may have a substituent) And R ⁴ to R ⁷ each 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, or the like Silyloxy group having an alkylcarbonyloxy group of 2 to 11, an aryloxy group of 4 to 10 carbon atoms, an arylcarbonyloxy group of 5 to 11 carbon atoms, an alkyl group of 1 to 6 carbon atoms and / or a phenyl group Or R ⁸ and R ⁹ each independently represent a hydrogen atom, an alkyl group of 1 to 5 carbon atoms, a haloalkyl group of 1 to 5 carbon atoms, or an aryl of 6 to 10 carbon atoms Group It represents, Ar represents a divalent organic group represented by the formula [5] or Formula [6].)

(Wherein, R ¹⁰ to R ¹⁵ each independently represent a hydrogen atom, an alkyl group having 1 to 10 carbon atoms which may have a substituent, or the number of carbon atoms which may have a substituent) 6-10 aryl groups are represented.)
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. Related to things.
As a seventh aspect, the present invention relates to a varnish including the composition according to any one of the first to sixth aspects.
An eighth aspect relates to a thin film formed of the composition according to any one of the first to sixth aspects.
A ninth aspect relates to an electro-optical element including the composition according to any one of the first to sixth aspects.
The present invention relates to, as a tenth aspect, an optical switching element including the composition according to any one of the first to sixth aspects.
As an eleventh aspect, the present invention relates to an organic nonlinear optical material using the composition according to any one of the first to sixth aspects.
A twelfth aspect relates to a norbornene imide copolymer having a structural unit represented by the formula [1] and a structural unit represented by the formula [2].

(Wherein, 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, L ¹ represents a divalent organic group having 1 to 30 carbon atoms.)
As a thirteenth aspect, L ¹ is —Z ¹ -L ² -Z ^2- (wherein Z ¹ and Z ² are each independently a cyclohexylene group which may have a substituent, or a substituent A norbornene imide copolymer according to the twelfth aspect, which is a group represented by phenylene group which may have a group, L ² is a divalent organic group having 1 to 18 carbon atoms) .
As a fourteenth aspect, L ² is —O—L ³ —O— (wherein L ³ represents an alkylene group having 1 to 18 carbon atoms which may contain an ether bond or an ester bond). The norbornene imide copolymer according to the thirteenth aspect, which is a group represented by
The present invention relates, as a fifteenth aspect, to a bis (norbornene dicarboximide) compound represented by the formula [7].

(Wherein, 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 an alkylene group of to 18)

The composition of the present invention can not only suppress the alignment relaxation of the organic nonlinear optical compound by combining a norbornene imide copolymer having a specific structural unit with the organic nonlinear optical compound, but it is also possible to use the organic nonlinear optical compound Higher orientation can be achieved, and viscosity adjustment can be made easier.
In addition, the composition of the present invention is dissolved in a solvent to form a varnish form, and can be easily molded, so that the optical material having high handleability can be suitably used in the field of optoelectronic materials. Be
Furthermore, the organic nonlinear optical material of the present invention has a large nonlinear optical constant, which makes it possible to form an optical device that can be easily formed.

In addition, the norbornene imide copolymer having the specific structural unit of the present invention suppresses relaxation of the alignment of the organic nonlinear optical compound, highly aligns the organic nonlinear optical compound, and facilitates the adjustment of viscosity, so that organic nonlinear It can be suitably used as a polymer matrix of an optical compound.
Furthermore, the bis (norbornene dicarboximide) compound which is a bifunctional monomer of the present invention is useful as a crosslinking agent (crosslinker) for introducing a crosslinking structure into norbornene imide homopolymer, and in particular, the thermal properties of the polymer Also, the compound is useful as a crosslinking agent capable of enhancing the electric field alignment of the organic nonlinear optical compound while maintaining the suppression effect of the alignment relaxation of the organic nonlinear optical compound equally.

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

<A norbornene imide copolymer which has a structural unit represented by a formula [1], and a structural unit represented by a formula [2]>
In the norbornene imide copolymer having a structural unit represented by the following formula [1] and a structural unit represented by the following formula [2] used for the composition of the present invention, the average molecular weight 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. Also, 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 (in terms of polystyrene).
Also, a norbornene imide 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 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. Represent.
Here, the alkyl group having 1 to 12 carbon atoms may have a branched structure or a cyclic structure, and a methyl group, an ethyl group, an n-propyl group, an isopropyl group, a cyclopropyl group, an n-butyl group, Isobutyl, sec-butyl, tert-butyl, n-pentyl, neopentyl, cyclopentyl, n-hexyl, cyclohexyl, n-octyl, n-decyl, n-dodecyl, 1-adamantyl Groups, benzyl group, phenethyl group and the like.
Examples of the aryl group having 6 to 10 carbon atoms include phenyl group and naphthyl group.
Examples of the substituent of the alkyl group having 1 to 12 carbon atoms include a hydroxy group; and a halogen atom such as a fluoro group, a chloro group, a bromo group or an iodo group.
Examples of the substituent of the aryl group having 6 to 10 carbon atoms include alkyl groups such as methyl and ethyl; hydroxyalkyl groups such as hydroxymethyl; hydroxy; alkoxy such as methoxy and octyloxy; fluoro And halogen atoms such as chloro, bromo and iodo.
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, 2,3,4,5,6-pentafluorophenyl group etc. are mentioned.

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

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, and may contain, for example, one or more aromatic rings and / or aliphatic rings, and one or more ether bonds (— A divalent group which may contain a bonding group such as O-) or an ester bond (-COO-), and the total number of carbon atoms constituting the group is at most 30, provided that the ester bond When it is contained, carbon atoms in the ester bond are not included in the above 1 to 30 carbon atoms.
The divalent organic group having 1 to 30 carbon atoms is preferably an alkylene group, an aromatic ring or an aliphatic ring, or both, and may contain an ether bond and / or an ester bond. It is selected from valent hydrocarbon groups.

Among them, the above L ¹ is preferably -Z ¹ -L ² -Z ^2- . Here, each of Z ¹ and Z ² independently represents a cyclohexylene group which may have a substituent, or a phenylene group which may have a substituent, and L ² has 1 to carbon atoms It represents 18 divalent organic groups.
As a substituent of the above-mentioned cyclohexylene group or phenylene group, alkyl group such as methyl group and ethyl group; hydroxyalkyl group such as hydroxymethyl group; hydroxy group; alkoxy group such as methoxy group and octyloxy group; fluoro group, chloro And halogen atoms such as bromo, iodo and the like.
Further, as the above-mentioned divalent organic group having 1 to 18 carbon atoms, an alkylene group having 1 to 18 carbon atoms which may contain an ether bond and / or an ester bond (however, in the case of containing an ester bond, the ester bond may be And the carbon atom of (1) is not included in the above 1 to 18 carbon atoms).

In particular, the above L ² is a group represented by -O-L ³ -O-, that is, the above L ¹ is a group represented by -Z ¹ -O-L ³ -O-Z ^2- Is preferred. 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 a methylene group, an ethylene group, a trimethylene group, a 1-methylethylene group, a tetramethylene group, a 1-methyltrimethylene group 1,1-Dimethylethylene, Pentamethylene, 1-Methyltetramethylene, 2-Methyltetramethylene, 1,1-Dimethyltrimethylene, 1,2-Dimethyltrimethylene, 2,2-Dimethyl Trimethylene, 1-ethyltrimethylene, hexamethylene, 1-methylpentamethylene, 2-methylpentamethylene, 3-methylpentamethylene, 1,1-dimethyltetramethylene, 1,2-dimethyl Tetramethylene, 2,2-dimethyltetramethylene, 1-ethyltetramethylene, 1,1,2-trimethylto Methylene, 1,2,2-trimethyltrimethylene, 1-ethyl-1-methyltrimethylene, 1-ethyl-2-methyltrimethylene, 1,4-cyclohexylene, heptamethylene, octal Methylene, nonamethylene, decamethylene, undecamethylene, dodecamethylene, tridecamethylene, tetradecamethylene, tetradecamethylene, pentadecamethylene, hexadecamethylene, heptadecamethylene, octadecamethylene, etc. Be
Further, as the above-mentioned alkylene group containing an ether bond, 3-oxapentane-1,5-diyl group, 3,6-dioxaoctane-1,8-diyl group and the like can be mentioned.

Also in the structural unit represented by the formula [2], the steric configuration is not particularly limited.

In the present invention, the ratio of the structural unit represented by the formula [1] and the structural unit represented by the formula [2] in the norbornene imide copolymer is not particularly limited, and the ratio to the structural unit represented by the formula [1] The mass fraction of the structural unit represented by Formula [2] may be more than 0. For example, the ratio of the structural unit represented by Formula [2] to the structural unit represented by 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 of allowing the organic non-linear optical compound described later to be more highly oriented, the content can be 0.01 to 3% by mass.

The norbornene imide copolymer used in the present invention may have other structural units other than the structural unit represented by the formula [1] and the structural unit represented by the formula [2]. As other structural units, structural units such as norbornene, cyclobutene, cyclopentene, cyclooctene, cyclododecene, 1,5-cyclooctadiene and the like can be mentioned. In the case of having the above other structural units, it is desirable that the structural unit represented by the formula [1] and the structural unit represented by the formula [2] be 50 to 99% by mole based on the whole polymer.
On the other hand, the norbornene imide copolymer is more preferably a polymer comprising only 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 norbornene imide copolymer used in the present invention has 50 to 100% by mole of the structural unit represented by the formula [1] and the structural unit represented by the formula [2].

<Method of producing norbornene imide copolymer having structural unit represented by Formula [1] and structural unit represented by Formula [2]
The norbornene imide copolymer which has a structural unit represented by the said Formula [1] and a structural unit represented by Formula [2] is metal complexes, such as a norbornene imide monomer and a bis (norbornene imide) monomer, a ruthenium catalyst etc., for example Obtained by performing the polymerization reaction in a solvent in the presence of
The norbornene imide copolymer is preferably Macromol. Chem. Phys. The norbornene imide polymer can be synthesized according to the method for producing norbornene imide polymer described in 2002, 203, 1811-1818.

Examples of the above-mentioned bis (norbornene imide) monomers include bis (norbornene dicarboximide) compounds represented by the following formula [7], and the present compound is also an object of the present invention.

In the formula, each of Z ¹ and Z ² independently represents a cyclohexylene group which may have a substituent, or a phenylene group which may have a substituent, and L ³ represents ³ to 6 carbon atoms. Represents 18 alkylene groups.

In the production of a norbornene imide copolymer having a structural unit represented by the above formula [1] and a structural unit represented by the formula [2], each of norbornene imide monomer and bis (norbornene imide) monomer is used alone It may be used in combination of two or more. When two or more norbornene imide monomers and / or bis (norbornene imide) 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.

In addition, as described above, the norbornene imide copolymer having the structural unit represented by the above formula [1] and the structural unit represented by the formula [2] is a structural unit represented by the above formula [1] and the formula [2] In addition to the structural units represented by the above, it may have a structural unit (norbornene, cyclobutene, cyclopentene, cyclooctene, cyclododecene, 1,5-cyclooctadiene, etc.). In that case, in addition to the norbornene imide monomer and bis (norbornene imide) monomer, as other monomers, monomers constituting the 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, relative to all monomers used to obtain a norbornene imide 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 to 50 mol%.

The above other monomers may be used alone or in any combination of two or more. The ratio is also not particularly limited, and can be adjusted according to the structure of the target norbornene imide copolymer.

The metal complex used in the above-mentioned polymerization reaction is not particularly limited, and can be arbitrarily selected and used from various known metal complexes for polymerization. Among them, ruthenium catalysts such as Grubbs catalyst (first generation Grubbs catalyst, second generation Grubbs catalyst) are preferable.
The metal complex can be used at a molar ratio of 5 × 10 ⁻³ to 1 × 10 ⁻² times with respect to the total monomer as the raw material.

The solvent used for 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. In addition, a solvent may be used individually by 1 type, and 2 or more types may be mixed and used by arbitrary combinations.

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

The time of the polymerization reaction is 10 minutes to 10 hours, though it varies depending on the types of monomers and metal complexes used, temperature and pressure at the time of polymerization, and the like. Preferably, it is 20 minutes to 5 hours.

After completion of the polymerization reaction, the obtained norbornene imide copolymer is recovered by any method, and after treatment such as washing is performed if necessary. As a method of recovering a norbornene imide copolymer from a reaction solution, methods such as reprecipitation may be mentioned.

<Organic nonlinear optical compound>
The organic non-linear 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, preferably having a large molecular hyperpolarizability β . Examples of the electron donating group include dialkylamino groups, and examples of the electron withdrawing group include cyano group, nitro group and fluoroalkyl group.
Among them, as the organic nonlinear optical compound used in the present invention, a compound having a furan ring represented by the formula [3] can be mentioned.

In the above formulas, R ⁸ and R ⁹ each independently represent a hydrogen atom, an alkyl group of 1 to 5 carbon atoms, a haloalkyl group of 1 to 5 carbon atoms, or an aryl group of 6 to 10 carbon atoms. Represents, and ● 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 each independently have a hydrogen atom, an alkyl group having 1 to 10 carbon atoms which may have a substituent, or a substituent A good aryl group having 6 to 10 carbon atoms is represented.
Here, the alkyl group having 1 to 10 carbon atoms may have a branched structure or a cyclic structure, and a methyl group, an ethyl group, an n-propyl group, an isopropyl group, a cyclopropyl group, an n-butyl group, Isobutyl, sec-butyl, tert-butyl, n-pentyl, neopentyl, cyclopentyl, n-hexyl, cyclohexyl, n-octyl, n-decyl, 1-adamantyl, benzyl A phenethyl group etc. are mentioned.
Examples of the aryl group having 6 to 10 carbon atoms include phenyl group, tolyl group, xylyl group and naphthyl group.
Examples of the substituent include amino group; hydroxy group; alkoxycarbonyl group such as methoxycarbonyl group and tert-butoxycarbonyl group; trimethylsilyloxy group, tert-butyldimethylsilyloxy group, tert-butyldiphenylsilyloxy group, triphenylsilyl group Silyloxy groups such as oxy group; and halogen atoms such as fluoro group, chloro group, bromo group and iodo group.

In the above formula [4], R ⁴ to R ⁷ each 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, or 2 to 6 carbon atoms 11 alkylcarbonyloxy group, an aryloxy group having 4 to 10 carbon atoms, an arylcarbonyloxy group having 5 to 11 carbon atoms, a silyloxy group having an alkyl group having 1 to 6 carbon atoms and / or a phenyl group, or Represents a halogen atom.
Here, examples of the alkyl group having 1 to 10 carbon atoms include those exemplified for the aforementioned R ² and R ³ .
Examples of the alkoxy group having 1 to 10 carbon atoms include a group in which the above-mentioned 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 above-mentioned 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 phenoxy group, naphthalen-2-yloxy group, furan-3-yloxy group, thiophene-2-yloxy group and the like.
Examples of the arylcarbonyloxy group having 5 to 11 carbon atoms include benzoyloxy, 1-naphthyloxy, furan-2-carbonyloxy, thiophene-3-carbonyloxy and the like.
Examples of the silyloxy group having an alkyl group having 1 to 6 carbon atoms and / or a phenyl group include trimethylsilyloxy group, tert-butyldimethylsilyloxy group, tert-butyldiphenylsilyloxy group, triphenylsilyloxy group and the like. .
As a halogen atom, a fluoro group, a chloro group, a bromo group, an iodo group etc. are mentioned.

In the above Formula [3] and Formula [4], R ⁸ and R ⁹ each independently represent a hydrogen atom, an alkyl group of 1 to 5 carbon atoms, a haloalkyl group of 1 to 5 carbon atoms, or a carbon atom Represents an aryl group of 6 to 10;
Here, the alkyl group having 1 to 5 carbon atoms may have a branched structure or a cyclic structure, and a methyl group, an ethyl group, an n-propyl group, an isopropyl group, a cyclopropyl group, an n-butyl group, Examples thereof include isobutyl group, sec-butyl group, tert-butyl group, n-pentyl group, neopentyl group and cyclopentyl group.
The haloalkyl group having 1 to 5 carbon atoms may have a branched structure or a cyclic structure, and 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, 2,2,3,3-tetrafluoropropyl, 1,1,2,3,3,3-hexafluoropropyl, 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, perfluoro Roshikuropenchiru group, and the like.
Examples of the aryl group having 6 to 10 carbon atoms include phenyl group, tolyl group, xylyl group and naphthyl group.

In said formula [4], Ar represents the bivalent organic group represented by following formula [5] or Formula [6].

In the above formulas [5] and [6], R ¹⁰ to R ¹⁵ each independently represent 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.
Here, as the alkyl group having 1 to 10 carbon atoms, the aryl group having 6 to 10 carbon atoms, and the substituent, those exemplified for the aforementioned R ² and R ³ can be mentioned.

In the composition of the present invention, the content of the organic nonlinear optical compound is 100 parts by mass of the norbornene imide copolymer having the structural unit represented by the above formula [1] and the structural unit represented by the formula [2] Usually, it is 1 to 150 parts by mass, preferably 10 to 100 parts by mass.
By setting the content of the organic nonlinear optical compound to 1 part by mass or more, a sufficient nonlinear optical effect can be easily obtained, and by setting the content to 150 parts by mass or less, it is easy to form a film, and the mechanical strength of the material is further reduced. 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 of producing the thin film, the composition of the present invention is dissolved in a suitable organic solvent to form a varnish, and the varnish is used as a suitable substrate (eg, silicon / silicon dioxide coated substrate, silicon nitride substrate, metal ( For example, on a substrate such as a substrate coated with aluminum, molybdenum, chromium or the like, a glass substrate, a quartz substrate, an ITO substrate or the like) or a film (for example, a resin film such as a triacetyl cellulose film, a polyester film or an acrylic film) It is preferable to use a wet coating method in which a film is formed by coating by spin coating, flow coating, roll coating, slit coating, spin coating following a slit, inkjet coating, printing or the like.

Here, the solvent used for varnish preparation dissolves the norbornene imide copolymer and the organic nonlinear optical compound having the structural unit represented by the formula [1] and the structural unit represented by the formula [2], and optionally added The type, structure, etc. thereof are not particularly limited as long as they dissolve the later-described additives and the like, and the solvent has such a dissolving ability.
Examples of preferred organic solvents include ethers such as tetrahydrofuran (THF), methyltetrahydrofuran, 1,4-dioxane, diethylene glycol dimethyl ether; ketones such as methyl ethyl ketone (MEK), cyclopentanone, cyclohexanone etc. esters such as ethyl acetate Alcohols such as cyclohexanol and propylene glycol monomethyl ether (PGME); halides such as 1,2-dichloroethane, chloroform and chlorobenzene; aromatic hydrocarbons such as toluene and xylene; N, N-dimethylformamide (DMF), 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 the norbornene imide copolymer having the structural unit represented by the formula [1] and the structural unit represented by the formula [2] And from the viewpoint of good coatability.
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 referred to herein means all the components of the varnish excluding the solvent.
Thus, it is preferable to use the prepared varnish after filtering with a filter having a pore diameter of about 0.2 μm.

The above-mentioned varnish may, if necessary, be an antioxidant such as hydroquinone, an ultraviolet absorber such as benzophenone, a silicone oil, a rheology modifier such as a surfactant, or a silane coupling as long as the effect of the present invention is not impaired. The composition may contain adhesion promoters such as additives, crosslinking agents for polymer matrix, compatibilizers, curing agents, pigments, storage stabilizers, antifoaming agents, and the like.

<Electro-optical element, optical switching element>
The composition of the present invention can be applied as a material of various electro-optical devices proposed conventionally.
A representative example of the electro-optical element is an optical switching element (optical communication element) such as a Mach-Zehnder type optical modulator. In the optical switching element, the composition of the present invention is coated on a substrate such as glass or plastic and then processed by light or electron beam lithography, wet and dry etching, or nanoimprinting to obtain light. An optical waveguide structure capable of transmission is used. Usually, the optical waveguide structure is formed by coating and laminating on a material having a smaller refractive index than the composition, but the present composition is also applicable to other optical waveguide structures without being limited to this structure.
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 exhibit electro-optical characteristics, and light propagated by changing the refractive index Cause a phase change of By changing the light intensity after branching and multiplexing by this phase change, high-speed modulation of light becomes possible.
In addition, the electro-optical element mentioned here is not limited to only phase and intensity modulation, and can be used, for example, as a polarization conversion element, a branching and combining element, and the like.
Furthermore, the composition of the present invention can be used for applications such as an electric field sensor that detects a change in electric field as a change in refractive index, as well as in a communication device.

<Organic nonlinear optical material>
In the present invention, a poling treatment is required to develop the second-order non-linear optical properties of a material (for example, a thin film) manufactured using the composition. In the poling treatment, the nonlinear optical compound molecules are applied by applying a predetermined electric field while heating the material to a temperature about 25 ° C. lower than the glass transition temperature of the material, preferably about 10 ° C. lower than the melting point. It is an operation for orientation, and the material is cooled while maintaining the electric field, and the orientation is fixed. By this operation, the material can exhibit macroscopic non-linear optical characteristics.
Also in the present invention, the glass of the composition containing the norbornene imide copolymer as a matrix and the organic nonlinear optical compound is that the orientation of the organic nonlinear optical compound molecules is random only by thinning the composition. The temperature is about 25 ° C. lower than the transition temperature, preferably about 10 ° C. lower (about 120 ° C. if the composition does not exhibit a glass transition temperature), heated to a temperature below the melting point, and subjected to poling treatment , Nonlinear optical characteristics.

EXAMPLES Hereinafter, the present invention will be described in more detail by way of examples, but the present invention is not limited to these examples. In addition, each measuring apparatus etc. which were used in the Example are as follows.

(1) ¹ H NMR spectrum apparatus: JNM-LA400 manufactured by JEOL Ltd.
Solvent: CDCl ₃
CD ₃ OD (Example 1)
Internal standard: tetramethylsilane (0.00 ppm)
(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)
Device: LC-2000 manufactured by JASCO Corporation
Column: Tosoh Co., Ltd. TSKgel (registered trademark) G2000H _XL
Eluent: Tetrahydrofuran Detector: RI
Standard sample: Shodex (registered trademark) STANDARD SM-105 manufactured by Showa Denko KK
(4) Glass transition temperature (Tg) measurement device: SII Nano Technology Co., Ltd. differential scanning calorimeter DSC 6220
Measurement conditions: under nitrogen atmosphere Temperature rising rate: 10 ° C / min (50 to 250 ° C)
(5) 5% weight loss temperature (Td ₅ ) measurement device: manufactured by SII Nano Technology Co., Ltd. Differential thermogravimetry simultaneous measurement device TG / DTA 6200
Measurement conditions: under nitrogen atmosphere, temperature rising rate: 10 ° C./min (50 to 450 ° C.)
(6) Measurement of ruthenium content Apparatus: Agilent Technologies ICP-MS Agilent (registered trademark) 7500 cs
(7) Viscosity measurement device: rheometer MCR 302 manufactured by Anton Paar

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]

188.24 g (1.92 mol) of maleic anhydride [manufactured by Tokyo Chemical Industry Co., Ltd.] was dissolved in 200 mL of o-dichlorobenzene, and this solution was refluxed. Thereto was added 128.66 g (0.97 mol) of dicyclopentadiene (manufactured by Tokyo Chemical Industry Co., Ltd.) heated and melted at 50 ° C. in 30 minutes. After completion of the addition, the mixture was further stirred for 1.5 hours under reflux. 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. The crude product was recrystallized several times from hot chlorobenzene to obtain exo-2-norbornene-5,6-dicarboxylic acid anhydride (yield: 48%).

Preparation Example 1-2 Preparation of exo-N- (4-hydroxyphenyl) -2-norbornene-5,6-dicarboximide [9]

33.20 g (0.20 mol) of exo-2-norbornene-5,6-dicarboxylic acid anhydride [8] obtained according to the above-mentioned Preparation 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 dropwise addition, the mixture was further refluxed for 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. The wet product was dried under reduced pressure at 60 ° C. for 12 hours to obtain an amic acid (yield 78%).
75.00 g (0.27 mol) of the amic acid obtained according to the above method were 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 over 10 minutes. After the addition was completed, the mixture was further stirred at 120 ° C. for 3 hours. The reaction mixture was added to deionized water after cooling to room temperature (approximately 23 ° C.). The precipitated white precipitate was collected by filtration and washed with deionized water to obtain a crude product. The crude product is recrystallized several times from a hot ethanol / THF mixture (volume ratio 10: 1) to give exo-N- (4-hydroxyphenyl) -2-norbornene-5,6-dicarboximide as white crystals. (Yield 39%).

Example 1 Preparation of N, N '-((octamethylenebisoxy) bis (4,1-phenylene)) bis (2-norbornene-5,6-dicarboximide) [10]

12.30 g (48.2 mmol) of exo-N- (4-hydroxyphenyl) -2-norbornene-5,6-dicarboximide [9] obtained according to the above Preparation example 1-2, 1,8-dibromooctane [ Dissolve 6.55 g (24.1 mmol) of Tokyo Chemical Industry Co., Ltd., 33.00 g (238.8 mmol) of potassium carbonate [Tokyo Tokyo Chemical Industry Co., Ltd.] in 200 mL of acetonitrile, and reflux this for 48 hours The The reaction mixture was cooled to room temperature (approximately 23 ° C.) and then acetonitrile was distilled off using a rotary evaporator. The residue was added to deionized water and stirred for 1 hour to ensure dissolution of potassium carbonate. The organics were extracted with dichloromethane and washed several times with saturated brine. The organic layer was dried over anhydrous magnesium sulfate (manufactured by Kanto Chemical Co., Ltd.), and then dichloromethane was distilled off to obtain a crude product. The crude product was purified by silica gel column chromatography (ethyl acetate / hexane mixture (volume ratio 1:10)). Furthermore, it is recrystallized from a hot ethanol / THF mixed solution (volume ratio 9: 1), N, N '-((octamethylene bisoxy) bis (4,1-phenylene)) bis (2-norbornene-5,6) (Dicarboximide) was obtained (yield 67%).
¹ H NMR (400 MHz, CD ₃ OD) δ: 7.13 (d, J = 9.2 Hz, 4 H), 7.00 (d, J = 8.7 Hz, 4 H), 6.36 (m, 4 H) , 3.99 (t, J = 6.8 Hz, 4 H), 3. 19 (s, 4 H), 2.8 1 (s, 4 H), 2.50 (m, 4 H), 1.72 (m, 4 H) ), 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.

Preparation Example 2 Preparation of exo-N-cyclohexyl-2-norbornene-5,6-dicarboximide [11]

100 g (0.61 mol) of exo-2-norbornene-5,6-dicarboxylic acid anhydride [8] obtained according to the above-mentioned Preparation 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 while stirring at room temperature (approximately 23 ° C.). During the dropping, a white precipitate was formed and stirring became difficult, so 100 mL of toluene was further added. After completion of the dropwise addition, the mixture was further stirred at 50 ° C. for 1 hour. The precipitated white precipitate was filtered under reduced pressure and washed with toluene. The wet product was dried under reduced pressure at 70 ° C. for 12 hours to obtain an amic acid (yield: 72%).
50.00 g (0.19 mmol) of the amic acid obtained according to the above method were 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 over 10 minutes. After the addition was completed, the mixture was further stirred at 120 ° C. for 3 hours. The reaction mixture was added to deionized water after cooling to room temperature (approximately 23 ° C.). The precipitated white precipitate was collected by filtration and washed with deionized water to obtain a crude product. The crude product was recrystallized from hot methanol to give exo-N-cyclohexyl-2-norbornene-5,6-dicarboximide (yield 54%).

Example 2a Poly (exo-N-cyclohexyl-2-norbornene-5,6-dicarboximido-co-N, N ′-((octamethylenebisoxy) bis (4,1-phenylene)) bis ( Preparation of 2-Norbornene-5,6-dicarboximide)) [12a]

1.00 g (4.08 mmol) of exo-N-cyclohexyl-2-norbornene-5,6-dicarboximide [11] obtained according to the above Preparation example 2 and N, N '-( Schlenk tube of (octamethylenebisoxy) bis (4,1-phenylene)) bis (2-norbornene-5,6-dicarboximide) [10] 2 mg (0.2 mass% with respect to compound [11]) And purged with nitrogen. Here, 20 mL of chloroform was injected by a syringe. After stirring this solution for 10 minutes, a solution of 67 mg (81.6 μmol) of Grubbs first generation catalyst (manufactured by SIGMA-ALDRICH) dissolved 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., Ltd.] was injected by a syringe to quench the reaction. Furthermore, it stirred at room temperature (about 23 degreeC) for 1 hour. The reaction mixture was concentrated and then dissolved in chloroform and added to methanol to reprecipitate the polymer. Chloroform-methanol reprecipitation was repeated several more times. The polymer is filtered off and washed with methanol, and the desired product poly (exo-N-cyclohexyl-2-norbornene-5,6-dicarboximido-co-N, N '-((octamethylene bisoxy) is obtained. Bis (4,1-phenylene)) bis (2-norbornene-5,6-dicarboximide)) was obtained.
The peak top molecular weight Mp of the obtained norbornene imide copolymer measured by polystyrene conversion by GPC is 35,000, the number average molecular weight Mn is 21,000, the weight average molecular weight Mw is 25,000, and the dispersion degree Mw / Mn is 1 It was .2. Further, the glass transition temperature Tg was 209 ° C., the 5% weight loss temperature Td ₅ was 410 ° C., and the viscosity in a 10% by mass toluene solution was 5.9 mPa · s.
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 Preparation of Compound [12b] The same procedure as in Example 2a was repeated, except that the amount of compound [10] used was changed to 6 mg (0.6 mass% with respect to compound [11]). An imide copolymer was obtained.
The peak top molecular weight Mp of the obtained norbornene imide copolymer as measured by polystyrene conversion by GPC is 24,000, the number average molecular weight Mn is 21,000, the weight average molecular weight Mw is 28,000, and the dispersion degree Mw / Mn is 1 It was .4. Further, the glass transition temperature Tg was 209 ° C., the 5% weight loss temperature Td ₅ was 410 ° C., and the viscosity in a 10% by mass toluene solution was 4.2 mPa · s.
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 Preparation of Compound [12c] The procedure of Example 2a was repeated except that the amount of compound [10] used was changed to 8 mg (0.8 mass% with respect to compound [11]), norbornene An imide copolymer was obtained.
The peak top molecular weight Mp of the obtained norbornene imide copolymer measured by polystyrene conversion by GPC is 24,000, the number average molecular weight Mn is 21,000, the weight average molecular weight Mw is 30,000, and the dispersion degree Mw / Mn is 1 It was .4. Further, the glass transition temperature Tg was 210 ° C., the 5% weight loss temperature Td ₅ was 418 ° C., and the viscosity in a 10% by mass toluene solution was 8.4 mPa · s.
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 Preparation of Compound [12d] A norbornene imide copolymer is operated in the same manner as in Example 2a except that the amount of compound [10] used is changed to 10 mg (1 mass% with respect to compound [11]). I got
The peak top molecular weight Mp of the obtained norbornene imide copolymer measured by polystyrene conversion by GPC is 26,000, the number average molecular weight Mn is 26,000, the weight average molecular weight Mw is 42,000, and the dispersion degree Mw / Mn is 1 It was .6. The glass transition temperature Tg was 208 ° C., the 5% weight loss temperature Td ₅ was 362 ° C., the viscosity in a 10% by mass toluene solution was 8.3 mPa · s, and the ruthenium content derived from the residual catalyst was 980 ppm.
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] The same operation as in Example 2a except that the amount of compound [10] used was changed to 14 mg (1.4 mass% with respect to compound [11]), norbornene An imide copolymer was obtained.
The peak top molecular weight Mp of the obtained norbornene imide copolymer as measured by polystyrene conversion by GPC is 25,000, the number average molecular weight Mn is 24,000, the weight average molecular weight Mw is 46,000, and the dispersion degree Mw / Mn is 1 .9. Further, the glass transition temperature Tg was 208 ° C., the 5% weight loss temperature Td ₅ was 399 ° C., and the viscosity in a 10% by mass toluene solution was 3.8 mPa · s.
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 2 f Preparation of Compound [12 f] The procedure of Example 2a was repeated, except that the amount of compound [10] used was changed to 16 mg (1.6 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 polystyrene conversion by GPC is 25,000, the number average molecular weight Mn is 26,000, the weight average molecular weight Mw is 60,000, and the dispersion degree 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% by mass toluene solution was 5.2 mPa · s, and the ruthenium content derived from the residual catalyst was 1,100 ppm.
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] Preparation of compound [12g] The same procedure as in Example 2a was repeated except that the amount of compound [10] used was changed to 18mg (1.8% by mass relative to compound [11]), norbornene An imide copolymer was obtained.
The peak top molecular weight Mp of the obtained norbornene imide copolymer measured by polystyrene conversion by GPC is 31,000, the number average molecular weight Mn is 27,000, the weight average molecular weight Mw is 75,000, and the dispersion degree Mw / Mn is 2 It was .8. Further, the glass transition temperature Tg was 212 ° C., the 5% weight loss temperature Td ₅ was 405 ° C., and the viscosity in a 10% by mass toluene solution was 5.8 mPa · s.
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] Preparation of compound [12h] The same operation as in Example 2a except that the amount of compound [10] used was changed to 20 mg (2.0 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 polystyrene conversion by GPC is 29,000, the number average molecular weight Mn is 28,000, the weight average molecular weight Mw is 102,000, and the dispersion degree Mw / Mn is 3 It was .6. Further, the glass transition temperature Tg was 207 ° C., the 5% weight loss temperature Td ₅ was 365 ° C., the viscosity in a 10% by mass toluene solution was 5.1 mPa · s, and the ruthenium content derived from the residual catalyst was 1,000 ppm.
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 Preparation of Compound [12i] The same procedure as in Example 2a was repeated except that the amount of compound [10] used was changed to 22 mg (2.2 mass% with respect to compound [11]), norbornene An imide copolymer was obtained.
The peak top molecular weight Mp of the obtained norbornene imide copolymer as measured by polystyrene conversion by GPC is 28,000, the number average molecular weight Mn is 31,000, the weight average molecular weight Mw is 122,000, and the dispersion degree Mw / Mn is 3 .9. Further, the glass transition temperature Tg was 211 ° C., the 5% weight loss temperature Td ₅ was 406 ° C., and the viscosity in a 10% by mass toluene solution was 6.5 mPa · s.
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 Preparation of Compound [12j] The procedure of Example 2a was repeated except that the amount of compound [10] used was changed to 24 mg (2.4 mass% with respect to compound [11]), norbornene An imide copolymer was obtained.
The peak top molecular weight Mp of the obtained norbornene imide copolymer measured by polystyrene conversion by GPC is 28,000, the number average molecular weight Mn is 35,000, the weight average molecular weight Mw is 146,000, and the dispersion degree Mw / Mn is 4 It was .2. In addition, the glass transition temperature Tg was 212 ° C., the 5% weight loss temperature Td ₅ was 408 ° C., and the viscosity in a 10% by mass toluene solution was 8.0 mPa · s.
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 Preparation of Compound [12k] The same procedure as in Example 2a was repeated, except that the amount of compound [10] used was changed to 26 mg (2.6 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 polystyrene conversion by GPC is 27,000, the number average molecular weight Mn is 32,000, the weight average molecular weight Mw is 155,000, and the dispersion degree Mw / Mn is 4 It was .8. Further, the glass transition temperature Tg was 213 ° C., the 5% weight loss temperature Td ₅ was 358 ° C., and the viscosity in a 10% by mass toluene solution was 7.9 mPa · s.
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 Preparation of Compound [12l] The procedure of Example 2a was repeated except that the amount of compound [10] used was changed to 28 mg (2.8 mass% with respect to compound [11]), norbornene An imide copolymer was obtained.
The peak top molecular weight Mp of the obtained norbornene imide copolymer measured by polystyrene conversion by GPC is 27,000, the number average molecular weight Mn is 32,000, the weight average molecular weight Mw is 191,000, and the dispersion degree Mw / Mn is 5 .9. Further, the glass transition temperature Tg was 213 ° C., the 5% weight loss temperature Td ₅ was 410 ° C., and the viscosity in a 10% by mass toluene solution was 7.7 mPa · s.
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 Preparation of Compound [12m] A norbornene imide copolymer is operated in the same manner as Example 2a except that the amount of compound [10] used is changed to 30 mg (3 mass% with respect to compound [11]). I got
The peak top molecular weight Mp of the obtained norbornene imide copolymer as measured by polystyrene conversion by GPC is 737,000, the number average molecular weight Mn is 35,000, the weight average molecular weight Mw is 155,000, and the dispersion degree Mw / Mn is 7 It was .3. Further, the glass transition temperature Tg was 213 ° C., the 5% weight loss temperature Td ₅ was 391 ° C., and the viscosity in a 10% by mass toluene solution was 8.4 mPa · s.
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 2 n Preparation of Compound [12n] The same procedure as in Example 2a was repeated, except that the amount of compound [10] used was changed to 34 mg (3.4 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 polystyrene conversion by GPC 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. Further, the glass transition temperature Tg was 215 ° C., the 5% weight loss temperature Td ₅ was 402 ° C., and the viscosity in a 10% by mass toluene solution was 151.4 mPa · s.
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] Preparation of compound [12o] The procedure of Example 2a was repeated except that the amount of compound [10] used was changed to 38 mg (3.8 mass% with respect to compound [11]), norbornene An imide copolymer was obtained.
The peak top molecular weight Mp of the obtained norbornene imide copolymer as measured by polystyrene conversion by GPC is 853,000, the number average molecular weight Mn is 44,000, the weight average molecular weight Mw is 815,000, and the dispersion degree Mw / Mn is 18 It was .6. Further, the glass transition temperature Tg was 215 ° C., the 5% weight loss temperature Td ₅ was 382 ° C., and the viscosity in a 10% by mass toluene solution was 281.4 mPa · s.
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 Preparation of Compound [12p] The same procedure as in Example 2a was repeated, except that the amount of compound [10] used was changed to 44 mg (4.4 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 polystyrene conversion by GPC is 716,000, the number average molecular weight Mn is 43,000, the weight average molecular weight Mw is 2,026,000, and the dispersion degree Mw / Mn Was 47.2. In addition, the glass transition temperature Tg was 216 ° C., the 5% weight loss temperature Td ₅ was 384 ° C., and the viscosity at a 10 mass% toluene solution was 343.1 mPa · s.
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 2 q Preparation of Compound [12q] The same procedure as in Example 2a was repeated, except that the amount of compound [10] used was changed to 46 mg (4.6 mass% with respect to compound [11]). An imide copolymer was obtained.
The peak top molecular weight Mp of the obtained norbornene imide copolymer as measured by polystyrene conversion by GPC is 906,000, the number average molecular weight Mn is 29,000, the weight average molecular weight Mw is 2,135,000, the dispersion degree Mw / Mn Was 73.5. Further, the glass transition temperature Tg was 213 ° C., the 5% weight loss temperature Td ₅ was 381 ° C., and the viscosity in a 10% by mass toluene solution was 538.7 mPa · s.
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 Preparation of Poly (exo-N-cyclohexyl-2-norbornene-5,6-dicarboximide) [13]

A norbornene imide polymer was obtained in the same manner as in Example 2a except that the compound [10] was not used.
The peak top molecular weight Mp of the obtained norbornene imide polymer as measured by polystyrene conversion by GPC is 25,000, the number average molecular weight Mn is 20,000, the weight average molecular weight Mw is 23,000, and the dispersion degree 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% by mass toluene solution was 5.3 mPa · s, and the ruthenium content derived from the residual catalyst was 910 ppm.
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.

The mass ratio of the norbornene imide copolymer obtained in Examples 2a to 2q and the norbornene imide polymer obtained in Comparative Example 1 from the compound [10] in each polymer (for example, in the case of the compound [12a]) For 2 mg ÷ (1,000 mg + 2 mg) x 100 = 0.20%), the degree of dispersion is shown in Figure 1, the viscosity of the 10 mass% toluene solution is shown in Figure 2, Tg is in Figure 3, Td ₅ is in Figure 4 It shows together.

As shown in FIG. 1, it was confirmed that the molecular weight distribution (dispersion degree) of the obtained norbornene polymer can be dramatically increased by the copolymerization of a minute amount of the bifunctional monomer (compound [10]).
Further, as shown in FIG. 2, the viscosity of a 10 mass% toluene solution of the norbornene polymer obtained can be increased by the copolymerization of a small amount of a bifunctional monomer (compound [10]), which is suitable for film formation. It was confirmed that the viscosity can be freely adjusted.
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 has been suggested that even when a bifunctional monomer (compound [10]) is copolymerized to form a crosslinked polymer, the properties against heat are not affected.

Reference Example 1 Production of Organic Nonlinear Optical Compound [FTC] The following compound [FTC] was used as an organic nonlinear optical compound. The compound is X.1. M. Zhang et al., Tetrahedron Lett. , 51, p 5873 (2010).

[Examples 3c, 3f, 3h, Comparative Example 2] Preparation of composition and electro-optical properties 65 mg of the norbornene imide (co) polymer described 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.

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

The electro-optical constant of each test piece was determined using C.I. C. Teng et al., Appl. Phys. Lett. , 56, p 1734 (1990), and Y.P. Shuto et al. Appl. Phys. , 77, p 4632 (1995). In the electric field alignment process, each test piece is heated and held at a predetermined temperature on a hot plate, and voltage application is performed at a field strength described in Table 1 via a gold electrode and an ITO electrode, and poling treatment is performed for about 1 minute. Did. Then, after rapidly cooling to fix the polarization orientation, voltage application was stopped. The test pieces for which the poling treatment was completed were subjected to the evaluation of the electro-optical characteristics.
The values of the electro-optic constant r ₃₃ obtained from each test piece are shown together with the temperature at which the electric field alignment treatment was performed and the electric field strength in Table 1. The value of electro-optic constant r ₃₃ (as well as the degree of dispersion) of the compound in the polymer [10] a graph plotted against the mass ratio of the structural unit derived from, shown in FIG.

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 norbornene imide polymer by copolymerization of bifunctional monomers. That was confirmed. That is, the effect of enhancing the electric field alignment of the organic nonlinear optical compound was observed. Although the reason is not elucidated, it is presumed that the introduction of the cross-linked structure increased the amorphism of the polymer.

[Example 4h, Comparative Example 3] Temperature Durability Test A temperature durability test was conducted on the test pieces for which the electro-optic constant was measured in Example 3h and Comparative Example 2. Each test piece was kept at 85 ° C., and the relaxation characteristics of the electro-optical constant from immediately after poling to after 500 hours were measured. 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 relaxation of the alignment of the nonlinear optical compound is generally liable to occur 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 to have the same thermal stability (Example 4h: 79%, Comparative Example 3: 77%) as the low-quality homopolymer.

Claims (15)

1. A composition comprising a norbornene imide 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.
   

   

   (Wherein, 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, L ¹ represents a divalent organic group having 1 to 30 carbon atoms.)
2. L ¹ is —Z ¹ -L ² -Z ^2- (wherein Z ¹ and Z ² are each independently a cyclohexylene group which may have a substituent, or a substituent The composition according to claim 1, which is a phenylene group which may be substituted, and L ² is a group represented by a C 1-18 divalent organic group).
3. The group represented by the above L ² is —O—L ³ —O— (wherein 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 claim 2, which is
4. 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].
   

   

   (Wherein, R ⁸ and R ⁹ each independently represent a hydrogen atom, an alkyl group of 1 to 5 carbon atoms, a haloalkyl group of 1 to 5 carbon atoms, or an aryl group of 6 to 10 carbon atoms , ● represents a bond.)
5. The composition according to claim 4, wherein the organic nonlinear optical compound is a compound represented by the formula [4].
   

   

   (Wherein, R ² and R ³ each independently represent a hydrogen atom, an alkyl group having 1 to 10 carbon atoms which may have a substituent, or the number of carbon atoms which may have a substituent) And R ⁴ to R ⁷ each 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, or the like Silyloxy group having an alkylcarbonyloxy group of 2 to 11, an aryloxy group of 4 to 10 carbon atoms, an arylcarbonyloxy group of 5 to 11 carbon atoms, an alkyl group of 1 to 6 carbon atoms and / or a phenyl group Or R ⁸ and R ⁹ each independently represent a hydrogen atom, an alkyl group of 1 to 5 carbon atoms, a haloalkyl group of 1 to 5 carbon atoms, or an aryl of 6 to 10 carbon atoms Group It represents, Ar represents a divalent organic group represented by the formula [5] or Formula [6].)
   

   

   (Wherein, R ¹⁰ to R ¹⁵ each independently represent a hydrogen atom, an alkyl group having 1 to 10 carbon atoms which may have a substituent, or the number of carbon atoms which may have a substituent) 6-10 aryl groups are represented.)
6. 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.
7. A varnish comprising the composition according to any one of claims 1 to 6.
8. A thin film comprising the composition according to any one of claims 1 to 6.
9. An electro-optical device comprising the composition according to any one of claims 1 to 6.
10. The optical switching element containing the composition as described in any one of Claims 1 thru | or 6.
11. An organic nonlinear optical material using the composition according to any one of claims 1 to 6.
12. A norbornene imide copolymer having a structural unit represented by Formula [1] and a structural unit represented by Formula [2].
    

    

    (Wherein, 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, L ¹ represents a divalent organic group having 1 to 30 carbon atoms.)
13. L ¹ is —Z ¹ -L ² -Z ^2- (wherein Z ¹ and Z ² are each independently a cyclohexylene group which may have a substituent, or a substituent The norbornene imide copolymer according to claim 12, wherein L represents an optionally substituted phenylene group, and L ² represents a divalent organic group having 1 to 18 carbon atoms.
14. The group represented by the above L ² is —O—L ³ —O— (wherein L ³ represents an alkylene group having 1 to 18 carbon atoms which may contain an ether bond or an ester bond). The norbornene imide copolymer according to claim 13, which is
15. The bis (norbornene dicarboximide) compound represented by Formula [7].
    

    

    (Wherein, 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 an alkylene group of to 18)

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