JPH0688977A - Second-order nonlinear optical material and manufacturing method thereof - Google Patents

Abstract

(57) [Abstract] [Purpose] It is easy to form an optically uniform film by suppressing the generation of gel components in the polymer solution for film formation. 2
It is an object of the present invention to provide a non-linear material and a manufacturing method thereof. The present invention relates to at least one compound component represented by the formula (C-1), a compound represented by the formula (C-2) or (C).
-2), wherein at least one of the compound components represented by 2) is bound to a polymer chain together, 2
A non-linear optical material and a manufacturing method thereof are provided. [Chemical 1] [Wherein π ₁ to π _n , π ′ ₁ , π ′ ₂ and π ″ ₁ each represent a π-electron conjugated cyclic compound; X ₁ to X _n−1 ,
X each _'1, from Y ₁ Y _n-1, Y' is _1, CH indicates N or _{N → O; A 1, A} 2 and A ₃ each represents an electron withdrawing group; D _1, D ₂ And D ₃ each represent an electron donating group; n is an integer of 3 or more. ]

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an organic nonlinear optical material, and more particularly to a novel second-order nonlinear optical material and a method for manufacturing the same.

[0002]

2. Description of the Related Art In recent years, a material obtained by subjecting a transparent polymer containing a dye material having a large second-order nonlinear optical characteristic to polarization (hereinafter referred to as a poled polymer) has been an optical modulator. , Has attracted attention as a material for wavelength conversion elements and electric field sensor probes. The chemical structure of the poled polymer is preferably one in which a dye having a large secondary molecule susceptibility (two nonlinear optical characteristics peculiar to the dye molecule) is chemically bonded to the polymer chain at a high concentration, and the dye material is an electron-withdrawing group. A conjugated π-electron system having an electron donating group and is generally used. Specifically, azo dyes were added to the main chain of polymethylmethacrylate (Reference: KD Singer et al., Appl. Phys. Let.
t., 53, 1800 (1988)) and stilbene dyes (reference: GR Mohlmann et al., Synthetic Metals, 37, 207).
(1989)) has been reported to measure the second-order nonlinear optical characteristics, and it is known that the second-order nonlinear optical constant increases with the dye content. In addition, attempts have been made to increase the secondary molecule susceptibility,
It has been reported that a dye molecule composed of a long π-electron conjugated chain having an electron-withdrawing group and an electron-donating group has a large susceptibility to secondary molecules (Reference: JL Oudar et al., J. Chem. Phy.
s., Vol. 67, 446 (1977)). Specifically, in a dye in which three aromatic rings form a conjugated system via an azo group, a secondary molecule susceptibility higher than those of azo dyes and stilbene dyes having two aromatic rings has been obtained (Reference) : M. Amano et al.,
See J. Appl. Phys., 68, 6024 (1990)).

However, in a poled polymer having a large number of conjugated aromatic rings having a large secondary molecule susceptibility, that is, a dye composed of a long π-conjugated chain bonded at a high concentration, an optically uniform film is formed. However, there is a drawback that the transparency and the light transmittance are lowered. This is because the polymer solution for film formation used in the dipping method or the spin coating method easily gels, and it is difficult to form an optically uniform film.

[0004]

The present invention has been made in view of the above problems, and suppresses the generation of gel components in a polymer solution for forming a film, and easily forms an optically uniform film. An object is to provide a second-order nonlinear material and a method for manufacturing the same.

In order to achieve the above object, 2 according to the present invention
The following non-linear optical material contains at least one compound component represented by formula (C-1) and a compound represented by formula (C-2) or (C
-2) 'is characterized in that at least one of the compound components is bound to the polymer chain together.

[Chemical 12] [Wherein π ₁ to π _n , π ′ ₁ , π ′ ₂ and π ″ ₁ each represent a π-electron conjugated cyclic compound; X ₁ to X _n−1 ,
X each _'1, from Y ₁ Y _n-1, Y' is _1, CH indicates N or _{N → O; A 1, A} 2 and A ₃ each represents an electron withdrawing group; D _1, D ₂ And D ₃ each represent an electron donating group; n is an integer of 3 or more. ] Further, according to the present invention, a (N-ethyl) anilinoethyl methacrylate derivative optionally substituted with deuterium, (m + n) mol part, and
A number average molecular weight of 10,0 is obtained by polymerizing a methyl methacrylate derivative which may be substituted with deuterium and (l) a molar part.
00 to 100,000 copolymer, and then
(M) mol part or more of the compound represented by formula (C-16) and (n) mol part or more of the compound represented by formula (C-17) are respectively made into a diazonium salt, and then these diazonium salts are used. There is provided a method for producing a second-order nonlinear optical material, which comprises subjecting a salt and the copolymer to diazo coupling.

[Chemical 13]

In the present invention, the gel component in the polymer solution is reduced to reduce the molecular size in the solution for the purpose of forming an optically uniform film, and
We are trying to reduce the possibility of mutual association of second-order nonlinear optical components. However, these two problems can be achieved by reducing the molecular weight and the abundance of a large-sized second-order nonlinear optical component having a long π-conjugated chain. That is, the reduction of the molecular size in the solution can be realized by reducing the molecular weight or by reducing the abundance of the large-sized second-order nonlinear optical component having a long π-conjugated chain. Further, the possibility of association between the second-order nonlinear optical components can be reduced by reducing the abundance per unit volume of a large-sized second-order nonlinear optical component having a long π-conjugated chain. However, the reduction of the molecular weight deteriorates the film-forming property, the mechanical properties of the film, and the temporal stability of the second-order nonlinear optical property.
The reduction of the second-order nonlinear optical component leads to the reduction of the second-order nonlinear optical effect.

Therefore, the inventors have invented a material capable of appropriately reducing the molecular size in a polymer solution without significantly lowering the molecular weight and preventing a decrease in second-order optical nonlinearity. That is, the nonlinear optical component (long-chain component) represented by one or more formulas (C-1) consisting of three or more conjugated π-electron conjugated rings having a large secondary molecular susceptibility and one π-electron conjugate One or more non-linear optical components (short chain components) represented by formula (C-2) or (C-2) 'consisting of a ring or two conjugated π-electron conjugated rings are bound to the polymer main chain It is a material characterized by a copolymer structure. The short-chain component has a smaller molecular size in solution than the long-chain component alone.
The molecular weight is reduced without lowering, and as a result, it helps prevent gelation. In addition, the short-chain component can also serve to suppress gelation from the viewpoint of suppressing the association between the long-chain components. Further, although the short-chain component has a smaller secondary molecule susceptibility than the long-chain component, the deterioration of the second-order nonlinear optical characteristics can be significantly suppressed as compared with the case where the short-chain component is not present.

That is, the material according to the present invention does not deteriorate the film-forming property, the mechanical properties of the film, the stability of the second-order nonlinear optical characteristic over time, and does not significantly reduce the second-order nonlinear optical effect. The feature is that the molecular size in the polymer solution is appropriately reduced, the generation of gel components in the solution is suppressed, and thus an optically uniform film is easily formed. Here, tetrahydrofuran, benzene chloride, methyl isobutyl ketone, methyl ethyl ketone, cellosolve acetate, chloroform, methylene chloride, N, N-dimethylformamide, dimethyl sulfoxide and the like are used as the solvent of the film forming polymer solution.

Here, the polymer structure of the material according to the present invention has a polysiloxane, polymethacrylate, polyester, polyurethane, polyamide, polyimide, polyacrylate, polystyrene, polycarbonate, polyether or a derivative thereof and / or a derivative thereof. A non-linear optical component such as a copolymer is bonded to the polymer main chain.

Further, the material of the present invention, as described above,
It has an electron-withdrawing group and an electron-donating group. _{-NO 2, -CN, -COOH, -COCH} 3 as the electron-withdrawing group, -CH
_{O, -CONH 2, -CH = C} (CN) 2, -C (CN)
= C (CN) _2, a halogen or the like, -SH as the electron donating _{group, -SR q, -OH, -OR r} , -NH 2, -N
R _s R _t, and the like. R _q to R _{t is, - (CH 2) n '} O
_{H, - (CH 2) n} '' NH 2, - (CH 2) n '''SH ( However, n', n '' and n '''are each an integer), an alkyl group, these Functional groups such as deuterium, hydrogen, and deuterium. However, in the case of bonding to a polymer chain through an electron donating group, one of R _q , R _r and R _s , R _t has —OH, —NH ₂ , and —SH bonded to the terminal. Is desirable.

[0011]

EXAMPLE According to the present invention, the compound component (C-1)
Is selected from compounds represented by the following formulas (C-3) to (C-5), and the compound component (C-2) is represented by the following formulas (C-6) to (C-8). Provided is a second order non-linear optical material selected from the represented compounds.

[Chemical 14]

[Chemical 15] [Wherein R ″ _{00 to} R ″ ₅₀ are each —CH ₂ (CH ₂ ) _h CH ₂
Represented by — (wherein h is 0 or an integer), represents an alkylene group which may be substituted with deuterium, R ′ _{0 to} R ′ _5
Are each represented by -C _i H _2i (where i is an integer), and an alkylene group optionally substituted with deuterium, -CH
₂ (CH ₂ ) _{h ′} CH ₂ — (where h ′ is 0 or an integer), which may be substituted with deuterium, an alkylene group, an alkyl group, a deuterated alkyl group, a substituted alkyl group, Represents a deuterated substituted alkyl group, hydrogen, deuterium or halogen, and R _{01 to} R ₅₄ are each an alkyl group, a deuterated alkyl group, a substituted alkyl group, a deuterated substituted alkyl group, hydrogen, a deuterium group. It represents either hydrogen or halogen, and B _{1 to} B ₆ each represent an electron-withdrawing group. ]

Further, the following formulas (C-9) and (C-1
There is provided a second-order nonlinear optical material consisting of three kinds of structural units represented by 0) and (C-11).

[Chemical 16] [Wherein R _{a to} R _c are each an alkyl group, a deuterated alkyl group, a substituted alkyl group, a deuterated substituted alkyl group, hydrogen, deuterium, a phenyl group, a deuterated phenyl group, a substituted phenyl group, Represents a deuterated substituted phenyl group or halogen, and R _d represents a phenyl group, a deuterated phenyl group, a substituted phenyl group, a deuterated substituted phenyl group, a halogen, —COOR _e , or —CONR _f R _g (Wherein each of R _e , R _f and R _g is an alkyl group, a deuterated alkyl group, a substituted alkyl group, a deuterated substituted alkyl group, a phenyl group, a deuterated phenyl group, a substituted phenyl group, Represents any of deuterated substituted phenyl groups, R _j ,
R _k and R _P each represent a group represented by —CH ₂ — or —CD ₂ —). ]

Further, represented by the following formula (C-12),
A second-order nonlinear optical material having a number average molecular weight of 10,000 to 100,000 in which three kinds of structural units are randomly copolymerized is

[Chemical 17] [In the formula, the ratios of l ₀ , m ₀ , and n ₀ are in the ranges of 80 to 90 mol%, 5 to 10 mol%, and 5 to 10 mol%, respectively. ] Optical switches, optical modulators, optical wavelength converters, high-speed IC diagnostics,
It can be used for all applications that utilize the second-order optical nonlinearity such as printed wiring diagnosis, but is particularly suitable for high-speed IC diagnosis and printed wiring diagnosis by the EO sampling method.

Furthermore, the present invention provides a compound (m ₁ + n ₁ ) represented by the following formula (C-13) and a compound represented by the following formula (C-
14) and a compound (l ₁ ) mol part are polymerized to obtain a copolymer (C-15) having a number average molecular weight of 10,000 to 100,000, and then (m ₁ ) mol part or more. A compound represented by the formula (C-16) and a compound represented by the formula (C-17) in an amount of (n ₁ ) mol parts or more are respectively made into diazonium salts, and then these diazonium salts and copolymers are used. (C-15) Diazo coupling with (C-15) relates to a method for producing a second-order nonlinear optical material.

[Chemical 18]

It should be noted that, represented by the following formula (C-18),
A second-order nonlinear optical material having a number average molecular weight of 10,000 to 100,000 in which three kinds of structural units are randomly copolymerized is

[Chemical 19] [In the formula, the ratios of l ₂ , m ₂ , and n ₂ are in the ranges of 80 to 90 mol%, 5 to 10 mol%, and 5 to 10 mol%, respectively. ] Part of the hydrogen in the molecule is replaced by deuterium, and it is expected that the absorption loss at a wavelength of around 1.3 μm will be extremely low. The present material can be used for all applications utilizing the second-order optical non-linearity such as optical switches, optical modulators, optical wavelength converters, high-speed IC diagnostics, and printed wiring diagnostics.
It can be used as an optical waveguide component material in an optical communication system (particularly as an optical waveguide having an electro-optical effect).

Further, the present invention provides a compound (m ₃ + n ₃ ) mol part represented by the following formula (C-13) and the following formula (C-
19) and a compound (l ₃ ) mol part are polymerized to obtain a copolymer (C-20) having a number average molecular weight of 10,000 to 100,000, and then (m ₃ ) mol part or more. A compound represented by formula (C-16) and a compound represented by formula (C-17) of (n ₃ ) mole parts or more as diazonium salts, and then copolymerized with these diazonium salts. Provided is a method for producing a second-order nonlinear optical material, which comprises diazo coupling with (C-20).

[Chemical 20]

Number average molecular weight 1 in which three kinds of structural units represented by the following formula (C-21) are randomly copolymerized
20,000 to 100,000 second-order nonlinear optical materials are

[Chemical 21] [In the formula, the ratios of l ₄ , m ₄ , and n ₄ are in the ranges of 80 to 90 mol%, 5 to 10 mol%, and 5 to 10 mol%, respectively. ] Part of the hydrogen in the molecule is replaced by deuterium, and it is expected that the absorption loss at a wavelength of around 1.3 μm will be extremely low. The present material can be used for all applications utilizing the second-order optical non-linearity such as optical switches, optical modulators, optical wavelength converters, high-speed IC diagnostics, and printed wiring diagnostics.
It can be used as an optical waveguide component material in an optical communication system (particularly as an optical waveguide having an electro-optical effect).

Further, the present invention is directed to a compound (m ₅ + n ₅ ) represented by the following formula (C-22) and a formula (C-
19) and a compound (l ₅ ) mol part are polymerized to obtain a copolymer (C-23) having a number average molecular weight of 10,000 to 100,000, and then (m ₅ ) mol part or more. A compound represented by the formula (C-16) and a compound represented by the formula (C-17) in an amount of (n ₅ ) or more as a diazonium salt, and then copolymerized with these diazonium salts. Provided is a method for producing a second-order nonlinear optical material, which comprises diazo coupling with (C-23).

[Chemical formula 22]

Polarization treatment is necessary for manifesting the second-order nonlinear optical effect. The polarization treatment can be performed by attaching an electrode to the sample and applying a DC voltage to the sample in the softened state or the flowing state of the sample, or by using the electric charge charged by corona discharge. The solidification of the sample may be performed by cooling or by thermosetting of the polymer, but in any case, it is desirable that the solidification be performed in an electric field applied state or a charged state. The material according to the present invention can be expected to be used as a third-order optical nonlinear material. At this time, the polarization treatment operation is not always required.

Example 1 A material represented by the formula (C-24) was synthesized.

[Chemical formula 23]

The synthesis method is shown below.

[Chemical formula 24]

[Chemical 25]

Synthesis of Compound (C-26) (N-Ethyl) anilinoethanol (157 g) was dissolved in tetrohydrofuran (1000 cc) dried with a molecular sieve for one day and then dried with anhydrous magnesium sulfate. 3000cc with a calcium chloride tube, a dropping funnel and a reflux tube attached together with triethylamine (360g) dried with molecular sieves.
Methacrylic acid chloride (100 g) containing a stabilizer was added dropwise to the 3-necked flask under stirring over 1 hour, and the mixture was further reacted at room temperature for 24 hours, and then heated under reflux for 1 hour. After the reaction, the reaction mixture was mixed with 2000 cc of water, and excess triethylamine was neutralized with hydrochloric acid.
Further from this, the product was extracted with 2000 cc of diethyl ether. The extract was washed with an aqueous solution of sodium hydrogen carbonate, then with distilled water, dried over magnesium sulfate,
The ether was distilled off to obtain the product (C-25). Next, the compound (C-25) (29 g) was mixed with methyl methacrylate (71 g), and 0.1% of these was used as an initiator.
Azobisisobutyronitrile (0.
14 g) and 0.44 μl of t-butyl mercaptan as a chain transfer agent were added, and dissolved oxygen was removed by repeating freeze-deaeration-dissolution three times or more in an ampoule, and the product was sealed in a vacuum. This was polymerized at 65 ° C. for 24 hours. After the reaction, the polymer was dissolved in acetic acid (5000 cc), the insoluble component was filtered, and then methanol (25000 cc)
Compound (C-26) was obtained by reprecipitation from the above. Compound (C
The abundance ratio of methyl methacrylate in −26) was 85 mol% by NMR measurement. Number average molecular weight is 75,000
Met.

Synthesis of Compound (C-27) p-Aminobenzaldehyde Monomer (Tokyo Kasei) (2
0 g) (containing 50% of homopolymer), malononitrile (Tokyo Kasei) (5.5 g) and absolute ethanol (dried with molecular sieves) (500 cc), equipped with a calcium chloride tube, a dropping funnel and a reflux tube 3
The solution was placed in a necked flask and stirred to obtain a suspension. Here, piberidine (Tokyo Kasei) (2.0 cc) is added to acetic acid (7 cc)
The solution dissolved in was added dropwise. The mixture was heated under reflux for another 2 hours. After the reaction, ethanol was distilled off, and the reaction product was extracted with diethyl ether. In addition, the part insoluble in ether was removed (unreacted component). The ether extraction component was recrystallized from ethanol to obtain a compound (C-27) (yield 38
%).

Synthesis of Compound (C-28) Compound (C-27) (20 g) was added to acetic acid (500 cc).
Propionic acid (50 cc) was added to and dissolved by heating, and further cooled to 5 ° C or lower. Next, sodium nitrite (8.9 g) was gradually added to 100 cc of sulfuric acid so as not to generate heat and dissolved. This was added to a solution of compound (C-27),
Be careful not to drop the liquid temperature above 10 ° C,
(C-28) was obtained. After the reaction, it was cooled to 5 ° C or lower and stored.

Synthesis of Compound (C-29) While cooling the reaction solution of the compound (C-28) to about 5 ° C., 3,5-xylidine (16 g) and sodium nitrate trihydrate (300 g) were added thereto. ) Was added. Immediately after the reaction, it was colored deep red. The reaction solution was stirred at about 15 ° C. for several hours and then reacted at room temperature for another 12 hours. After the reaction, 2000 cc of water was added to precipitate the reaction product. The precipitate was thoroughly dried in a vacuum dryer and further purified using a silica gel column (flowing out with methylene chloride).

Synthesis of Compound (C-30) Compound (C-29) (2.1 g) was added to acetic acid (100 c
It was dissolved by heating in c) to which propionic acid (10 cc) was added, and further cooled to 5 ° C or lower. Next, sodium nitrite (0.53 g) was gradually added to 20 cc of sulfuric acid while paying attention to heat generation and dissolved. The compound (C-2
To the solution of 9) was added dropwise while paying attention not to let the solution temperature exceed 10 ° C to obtain a compound (C-30). The reaction solution is 5
It was cooled to below ℃ and stored. Synthesis of Compound (C-24) Compound (C-26) (17 g) is dissolved in acetic acid (500 cc) and kept at 15 ° C or lower. Here, the compound (C-30)
Of the compound (C-27) (2.4 g) as a raw material, a solution of the compound (C-28) synthesized according to the method of synthesizing the compound (C-28) is added, and sodium acetate hydrate is further added. (150 g) was added, and the mixture was stirred at room temperature for 24 hours. After the reaction, the solid matter is filtered and the filtrate is methanol (50
Re-precipitation from 00cc). The precipitate was again mixed with acetic acid (500c
c), insoluble matter is filtered, and the filtrate is water (5000c).
Reprecipitation from c) gave a polymer compound (C-24).

The obtained polymer (C-24) was dissolved in benzene chloride to prepare a 20% wt / wt solution. The gel component of this polymer solution was small, and it could be easily removed by filtration with a 1.0 μm mesh filter (differential pressure 1 kg / cm ² ). From this solution, an optically uniform 20 is obtained by both spin coating and doctor blading.
A film having a thickness of μm or more was obtained. In the doctor blade method, the film thickness depends on the distance between the blade and the substrate.
Further, in the spin coating method, the concentration could be adjusted by the concentration of the polymer solution or the rotation speed of the spin coater. For example, 13
A 10% film was obtained by spin coating the% wt / wt solution at 1000 rpm / min.

Electrodes were set on the upper and lower sides of the obtained film,
A voltage of 2.0 MV / cm was applied in an atmosphere of 140 ° C., and the voltage was applied and the temperature was cooled to room temperature. This film exhibited an electro-optical constant of 45 pm / V at a wavelength of 1.3 μm.

Wavelength 1.3 μm for 10 μm thick film
The transmittance in the above was 99% or more.

Example 2 A material represented by the following formula (C-32) was synthesized. The number average molecular weight was 80,000.

[Chemical formula 26]

The synthesis method is shown below.

[Chemical 27]

The obtained polymer was dissolved in benzene chloride and
It was a 0% wt / wt solution. The gel component of this polymer solution was small, and it could be easily removed by filtration with a 1.0 μm mesh filter (differential pressure 1 kg / cm ² ). From this solution, an optically uniform film having a thickness of 20 μm or more was obtained by both the spin coating method and the doctor blade method. The film thickness could be adjusted by the distance between the blade and the substrate in the doctor blade method, and by the concentration of the polymer solution or the rotation speed of the spin coater in the spin coating method. For example, 13% wt /
Spin coating of wt solution at 1000 rpm gives 10
A film of μm was obtained.

Electrodes were set on the upper and lower sides of the obtained film,
A voltage of 1.1 MV / cm was applied in an atmosphere of 140 ° C., and the voltage was applied and the temperature was cooled to room temperature. This film exhibited an electro-optical constant of 40 pm / V at a wavelength of 1.3 μm.

Wavelength 1.3μ with 10 μm thick film
The transmittance at m was 99% or more.

Comparative Example 1 A material represented by the following formula (C-31) was synthesized. The number average molecular weight was 80,000.

[Chemical 28]

The synthesis was carried out according to Example 1 and the compound (C-
26) and the compound (C-30). This compound was apt to gel in benzene chloride, and it was difficult to filter with a 5.0 μm mesh filter. Therefore, 10.
When a solution filtered with a 0 μm mesh filter was spin-coated, an optically uniform film was not obtained, and the thickness was 1
70% transmittance at a wavelength of 1.3 μm with 0 μm film
It was below.

Example 3 A material represented by the following formula (C-35) was synthesized. The number average molecular weight was 75,000.

[Chemical 29]

The synthesis was carried out in the following manner according to Example 1.

[Chemical 30]

The obtained polymer was dissolved in benzene chloride and
It was a 0% wt / wt solution. The gel component of this polymer solution was small, and it could be easily removed by filtration with a 0.5 μm mesh filter (differential pressure 1 kg / cm ² ). From this solution, an optically uniform film having a thickness of 20 μm or more was obtained by both the spin coating method and the doctor blade method. The film thickness could be adjusted by the distance between the blade and the substrate in the doctor blade method, and by the concentration of the polymer solution or the rotation speed of the spin coater in the spin coating method. For example, 13% wt /
Spin coating of wt solution at 1500 rpm gives 5μ
m film was obtained.

Electrodes were set on the upper and lower sides of the obtained film,
A voltage of 2.0 MV / cm was applied in an atmosphere of 140 ° C., and the voltage was applied and the temperature was cooled to room temperature. This film exhibited an electro-optical constant of 40 pm / V at a wavelength of 1.3 μm.

A film having a thickness of 5 μm was processed by an oxygen plasma etching method to obtain an optical waveguide having a width of 5 μm. At this time, the epoxy resin was used as the clad. The loss of the optical waveguide is
It was 0.7 dB / cm at 1.3 μm.

Comparative Example 2 A compound represented by the following formula (C-37) was synthesized. The number average molecular weight was 75,000.

[Chemical 31]

The synthesis follows that of Example 3. This compound was easily gelled in benzene chloride, and it was difficult to filter it with a 5.0 μm mesh filter. Therefore, 10.
The solution filtered with a 0 μm mesh filter was spin-coated. When an optical waveguide was manufactured according to Example 3, the loss was 10 dB / cm at a wavelength of 1.3 μm.

Example 4 A compound represented by the following formula (C-38) was synthesized. The number average molecular weight was 75,000.

[Chemical 32]

The synthesis was carried out as follows.

[Chemical 33]

[Chemical 34]

The obtained polymer was dissolved in benzene chloride and
It was a 0% wt / wt solution. The gel component of this polymer solution was small, and it could be easily removed by filtration with a 0.5 μm mesh filter (differential pressure 1 kg / cm ² ). From this solution, an optically uniform film having a thickness of 20 μm or more was obtained by both the spin coating method and the doctor blade method. The film thickness could be adjusted by the distance between the blade and the substrate in the doctor blade method, and by the concentration of the polymer solution or the rotation speed of the spin coater in the spin coating method. For example, 13% wt /
Spin coating of wt solution at 1500 rpm gives 5μ
m film was obtained.

Electrodes were set on the upper and lower sides of the obtained film,
A voltage of 2.0 MV / cm was applied in an atmosphere of 140 ° C., and the voltage was applied and the temperature was cooled to room temperature. This film exhibited an electro-optical constant of 40 pm / V at a wavelength of 1.3 μm.

A film having a thickness of 5 μm was processed by an oxygen plasma etching method to obtain an optical waveguide having a width of 5 μm. At this time, the epoxy resin was used as the clad. The loss of the optical waveguide was 0.3 dB / cm at a wavelength of 1.3 μm.

Comparative Example 3 A compound represented by the formula (C-45) was synthesized. The number average molecular weight was 75,000.

[Chemical 35]

The synthesis follows that of Example 4. This compound was apt to gel in benzene chloride, and it was difficult to filter with a 5.0 μm mesh filter. Therefore, 10.0
The solution filtered with a μm mesh filter was spin-coated. When an optical waveguide was manufactured according to Example 3, the loss was 10 dB / cm or more at a wavelength of 1.3 μm.

Example 5 A compound represented by the following formula (C-46) was synthesized. The number average molecular weight was 70,000.

[Chemical 36]

The synthesis was carried out according to Example 1, using the compound of the following formula.

[Chemical 37]

The obtained polymer was dissolved in benzene chloride and
It was a 0% wt / wt solution. The gel component of this polymer solution was small, and it could be easily removed by filtration with a 0.5 μm mesh filter (differential pressure 1 kg / cm ² ). From this solution, an optically uniform film having a thickness of 20 μm or more was obtained by both the spin coating method and the doctor blade method. The film thickness could be adjusted by the distance between the blade and the substrate in the doctor blade method, and by the concentration of the polymer solution or the rotation speed of the spin coater in the spin coating method. For example, 13% wt /
Spin coating of wt solution at 1500 rpm gives 5μ
m film was obtained.

Electrodes were set on the upper and lower sides of the obtained film,
A voltage of 2.0 MV / cm was applied in an atmosphere of 140 ° C., and the voltage was applied and the temperature was cooled to room temperature. This film exhibited an electro-optical constant of 50 pm / V at 1.3 μm.

A film having a thickness of 5 μm was processed by an oxygen plasma etching method to obtain an optical waveguide having a width of 5 μm. At this time, the epoxy resin was used as the clad. The loss of the optical waveguide was 0.5 dB / cm at a wavelength of 1.3 μm.

Comparative Example 4 A compound represented by the following formula (C-47) was synthesized. The number average molecular weight was 70,000.

[Chemical 38]

The synthesis follows that of Example 1. This compound was apt to gel in benzene chloride, and it was difficult to filter with a 5.0 μm mesh filter. Therefore, 10.0
The solution filtered with a μm mesh filter was spin-coated. When an optical waveguide was manufactured according to Example 3, the loss was 10 dB / cm or more at a wavelength of 1.3 μm.

Example 6 A compound represented by the following formula (C-48) was synthesized.

[Chemical Formula 39]

The synthesis was carried out according to Example 1. However, instead of the compound (C-29),

[Chemical 40] Was also used in place of compound (C-27).

The obtained polymer was dissolved in benzene chloride and
It was a 0% wt / wt solution. The gel component of this polymer solution was small and could be easily removed by filtration with a filter of 0.1 μm mesh (differential pressure 1 kg / cm ² ). From this solution, an optically uniform film having a thickness of 20 μm or more was obtained by both the spin coating method and the doctor blade method. The film thickness could be adjusted by the distance between the blade and the substrate in the doctor blade method, and by the concentration of the polymer solution or the rotation speed of the spin coater in the spin coating method. For example, 13% wt /
Spin coating of wt solution at 1500 rpm gives 5μ
m film was obtained.

Electrodes were set on the upper and lower sides of the obtained film,
A voltage of 2.0 MV / cm was applied in an atmosphere of 140 ° C., and the voltage was applied and the temperature was cooled to room temperature. This film exhibited an electro-optical constant of 38 pm / V at 1.3 μm.

A film having a thickness of 5 μm was processed by an oxygen plasma etching method to obtain an optical waveguide having a width of 5 μm. At this time, the epoxy resin was used as the clad. The loss of the optical waveguide was 0.3 dB / cm at a wavelength of 1.3 μm.

Comparative Example 5 A compound represented by the formula (C-49) was synthesized.

[Chemical 41]

The synthesis follows that of Example 6. This compound was apt to gel in benzene chloride, and it was difficult to filter with a 5.0 μm mesh filter. Therefore, 10.0
The solution filtered with a μm mesh filter was spin-coated. When an optical waveguide was manufactured according to Example 3, the loss was 10 dB / cm or more at a wavelength of 1.3 μm.

Example 7 A compound represented by the formula (C-50) was synthesized.

[Chemical 42]

The synthesis was carried out as follows.

[Chemical 43]

The obtained polymer was dissolved in benzene chloride and
An 8% wt / wt solution was used. The gel component of this polymer solution was small and could be easily removed by filtration with a filter of 0.1 μm mesh (differential pressure 1 kg / cm ² ). From this solution, an optically uniform film having a thickness of 20 μm or more was obtained by both the spin coating method and the doctor blade method. The film thickness could be adjusted by the distance between the blade and the substrate in the doctor blade method, and by the concentration of the polymer solution or the rotation speed of the spin coater in the spin coating method. For example, 11% wt /
When the wt solution is spin coated at 1000 rpm, 6μ
m film was obtained.

Electrodes were set on the upper and lower sides of the obtained film,
A voltage of 1.5 MV / cm was applied under an atmosphere of 140 ° C., and the voltage was applied and the temperature was cooled to room temperature. This film exhibited an electro-optic constant of 61 pm / V at 1.3 μm. The transmittance of the 10 μm thick film at a wavelength of 1.3 μm was 99% or more.

Comparative Example 6 A compound represented by the following formula (C-55) was synthesized.

[Chemical 44]

When l ₁₂ = 0.9 and n ₁₂ = 0.1, a film similar to that of Example 7 was formed, or the electro-optical constant of 18 pm / V was retained by the polarization treatment under the same conditions.

When l ₁₂ = 0.6 and n ₁₂ = 0.4, gelation occurred and the solution was not obtained. Therefore, no film could be formed.

Example 8 A compound represented by the following formula (C-54) was synthesized.

[Chemical formula 45]

The synthesis was carried out as follows. The compound (C-58) was prepared according to the synthesis of (C-33).

[Chemical formula 46]

[Chemical 47]

The obtained polymer was dissolved in cellosolve acetate to prepare a 18% wt / wt solution. The gel component of this polymer solution was small, and it could be easily removed by filtration with a 0.5 μm mesh filter (differential pressure 1.5 kg / cm ² ). From this solution, an optically uniform film having a thickness of 20 μm or more was obtained by both the spin coating method and the doctor blade method. In the doctor blade method, the film thickness depends on the distance between the blade and the substrate,
In the spin coating method, it could be adjusted by the concentration of the polymer solution or the rotation speed of the spin coater. For example, 18% wt
/ Wt solution spin coated at 600rpm
A film of μm was obtained.

Electrodes were set on the upper and lower sides of the obtained film,
A voltage of 1.5 MV / cm was applied in an atmosphere of 180 ° C., and the temperature was cooled to room temperature with the voltage applied. This film exhibited an electro-optic constant of 71 pm / V at a wavelength of 1.3 μm.

Comparative Example 7 In the compound (C-54), n ₁₃ = 0.5 and m ₁₃ =
When 0, l ₁₃ = 99.5, the film formation was carried out according to Example 8
Was performed in the same manner as in, but with polarization treatment under the same conditions, 30p
It remained at the electro-optic constant of m / V.

Comparative Example 8 In the compound (C-54), n ₁₃ = 15, m ₁₃ = 0,
When l ₁₃ = 85, the polymer solution could not be formed due to gelation, and thus could not form a film.

Example 9 A compound represented by the following formula (C-59) was synthesized.

[Chemical 48]

The synthesis was carried out as follows.

[Chemical 49]

[Chemical 50]

[Chemical 51]

The obtained polymer was dissolved in benzene chloride and
It was a 0% wt / wt solution. The gel component of this polymer solution was small, and it could be easily removed by filtration with a 0.5 μm mesh filter (differential pressure 1 kg / cm ² ). From this solution, an optically uniform film having a thickness of 20 μm or more was obtained by both the spin coating method and the doctor blade method. The film thickness could be adjusted by the distance between the blade and the substrate in the doctor blade method, and by the concentration of the polymer solution or the rotation speed of the spin coater in the spin coating method. For example, 13% wt /
Spin coating of wt solution at 1500 rpm gives 5μ
m film was obtained.

Electrodes were set on the upper and lower sides of the obtained film,
A voltage of 2.0 MV / cm was applied in an atmosphere of 140 ° C., and the voltage was applied and the temperature was cooled to room temperature. This film exhibited an electro-optical constant of 38 pm / V at 1.3 μm.

A film having a thickness of 5 μm was processed by an oxygen plasma etching method to obtain an optical waveguide having a width of 5 μm. At this time, the epoxy resin was used as the clad. The loss of the optical waveguide was 0.2 dB / cm at a wavelength of 1.3 μm.

Comparative Example 9 The following formula (C-64) was synthesized.

[Chemical 52]

The synthesis followed that of Example 9. This compound was easily gelled in benzene chloride, and it was difficult to filter it with a 5.0 μm mesh filter. Therefore, 10.
When an optical waveguide was prepared according to Example 9 in which the solution filtered with a 0 μm mesh filter was spin-coated, the loss was 10 dB / cm or more at a wavelength of 1.3 μm.

Example 10 A compound represented by the following formula (C-65) was synthesized.

[Chemical 53]

The synthesis was carried out as follows.

[Chemical 54]

[Chemical 55]

The obtained polymer was dissolved in benzene chloride and
It was a 5% wt / wt solution. The gel component of this polymer solution was small, and it could be easily removed by filtration with a 0.5 μm mesh filter (differential pressure 1.5 kg / cm ² ). An optically uniform film having a thickness of 10 μm or more was obtained from this solution by both spin coating and doctor blade method. In the doctor blade method, the film thickness depends on the distance between the blade and the substrate,
In the spin coating method, it could be adjusted by the concentration of the polymer solution or the rotation speed of the spin coater. For example, 10% wt
/ Μt solution spin coated at 600 rpm gives 7μ
m film was obtained.

Electrodes were set on the upper and lower sides of the obtained film,
A voltage of 1.5 MV / cm was applied in an atmosphere of 180 ° C., and the temperature was cooled to room temperature with the voltage applied. This film exhibited an electro-optical constant of 90 pm / V at a wavelength of 1.55 μm. The wavelength of this film with a thickness of 10 μm is 1.55 μ
The transmittance at m was 99% or more.

Comparative Example 10 In the compound of Example 10, l ₁₄ = 6, m ₁₄ = 0, n
_{When 14} = 2, it is difficult to filter with a 0.5 μm mesh, and as a result of filtering with a 10 μm mesh, the transmittance of a 10 μm thick film at a wavelength of 1.55 μm was 90% or less.

Example 11 A compound represented by the following formula (C-77) was synthesized.

[Chemical 56] The synthesis was performed as follows. The compound (C-82) is
It was carried out according to the synthesis of compound (C-33).

[Chemical 57]

The obtained polymer was dissolved in methyl isobutyl ketone to prepare a 18% wt / wt solution. The gel component of this polymer solution was small, and it could be easily removed by filtration with a 0.5 μm mesh filter (differential pressure 1.5 kg / cm ² ). From this solution, an optically uniform solution was obtained by spin coating or doctor blade method.
A film having a thickness of 0 μm or more was obtained. The film thickness could be adjusted by the distance between the blade and the substrate in the doctor blade method, and by the concentration of the polymer solution or the rotation speed of the spin coater in the spin coating method. For example,
A 15% wt / wt solution was spin coated at 2000 rpm to give a 9 μm film.

Electrodes were set on the upper and lower sides of the obtained film,
A voltage of 1.5 MV / cm was applied in an atmosphere of 180 ° C., and the temperature was cooled to room temperature with the voltage applied. This film exhibited an electro-optical constant of 96 pm / V at a wavelength of 1.55 μm. The wavelength of this film is 10 μm and the wavelength is 1.55 μ.
The transmittance at m was 99% or more. Comparative Example 11 In the compound (C-77), m ₁₅ = 0, l ₁₅ = 90,
When n ₁₅ = 10, the spin coating solution was not obtained due to gelation, and film formation could not be performed.

[0093]

Industrial Applicability As described above, the material according to the present invention is a poled polymer which has a large second-order optical non-linear effect in the prior art but is poor in optically uniform film formation. The applicability of the poled polymer having a large second-order optical non-linear effect can be remarkably enhanced since the optically uniform film-forming property can be enhanced without deteriorating the non-linear effect and its stability over time.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁵ Identification code Internal reference number FI Technical display location C08F 220/36 MMQ 7242-4J 220/38 MMU 7242-4J C08G 18/40 NER 8620-4J 63 / 685 NNK 7107-4J 64/12 NQA 9362-4J 69/02 NRB 9286-4J 73/10 NTF 9285-4J 77/388 NUF 8319-4J (72) Inventor Toshikuni Kano 1-6 Uchiyuki-cho, Chiyoda-ku, Tokyo No. Japan Telegraph and Telephone Corp. (72) Inventor Yoshito Suto 1-1-6 Uchisaiwaicho, Chiyoda-ku, Tokyo Nihon Telegraph and Telephone Corp.

Claims (10)

[Claims] 1. At least one type of compound component represented by formula (C-1) and formula (C-2) or (C-
At least one kind of the compound component represented by 2) ′ is bound to a polymer chain together, 2
Non-linear optical material. [Chemical 1] [Wherein π ₁ to π _n , π ′ ₁ , π ′ ₂ and π ″ ₁ each represent a π-electron conjugated cyclic compound; X ₁ to X _n−1 ,
X each _'1, from Y ₁ Y _n-1, Y' is _1, CH indicates N or _{N → O; A 1, A} 2 and A ₃ each represents an electron withdrawing group; D _1, D ₂ And D ₃ each represent an electron donating group; n is an integer of 3 or more. ] 2. The compound component (C-1) is selected from compounds represented by the following formulas (C-3) to (C-5), and the compound component (C-2) is Formula (C-6)
The secondary non-linear optical material according to claim 1, which is selected from compounds represented by (C-8). [Chemical 2] [Chemical 3] [Wherein R ″ _{00 to} R ″ ₅₀ are each —CH ₂ (CH ₂ ) _h CH ₂
Represented by — (wherein h is 0 or an integer), represents an alkylene group which may be substituted with deuterium, R ′ _{0 to} R ′ _5
Are each represented by -C _i H _2i (where i is an integer), and an alkylene group optionally substituted with deuterium, -CH
₂ (CH ₂ ) _{h ′} CH ₂ — (where h ′ is 0 or an integer), which may be substituted with deuterium, an alkylene group, an alkyl group, a deuterated alkyl group, a substituted alkyl group, Represents a deuterated substituted alkyl group, hydrogen, deuterium or halogen, and R _{01 to} R ₅₄ are each an alkyl group, a deuterated alkyl group, a substituted alkyl group, a deuterated substituted alkyl group, hydrogen, a deuterium group. It represents either hydrogen or halogen, and B _{1 to} B ₆ each represent an electron-withdrawing group. ] 3. A compound comprising three types of structural units represented by the following formulas (C-9), (C-10) and (C-11), wherein the structural unit (C-11) is the compound component. (C-1)
And the structural unit (C-10) contains the compound component (C
The second-order nonlinear optical material according to claim 1, containing -2). [Chemical 4] [Wherein R _{a to} R _c are each an alkyl group, a deuterated alkyl group, a substituted alkyl group, a deuterated substituted alkyl group, hydrogen, deuterium, a phenyl group, a deuterated phenyl group, a substituted phenyl group, Represents a deuterated substituted phenyl group or halogen, and R _d represents a phenyl group, a deuterated phenyl group, a substituted phenyl group, a deuterated substituted phenyl group, a halogen, —COOR _e , or —CONR _f R _g (Wherein each of R _e , R _f and R _g is an alkyl group, a deuterated alkyl group, a substituted alkyl group, a deuterated substituted alkyl group, a phenyl group, a deuterated phenyl group, a substituted phenyl group, Represents any of deuterated substituted phenyl groups, R _j ,
R _k and R _P each represent a group represented by —CH ₂ — or —CD ₂ —). ] 4. A number average molecular weight of 1, in which three structural units represented by the following formula (C-12) are randomly copolymerized.
20,000 to 100,000, 2 according to claim 3.
Non-linear optical material. [Chemical 5] [In the formula, the ratios of l ₀ , m ₀ , and n ₀ are in the ranges of 80 to 90 mol%, 5 to 10 mol%, and 5 to 10 mol%, respectively. ] 5. A (N-ethyl) anilinoethylmethacrylate derivative, which may be substituted with deuterium, (m + n).
A molar part, a methyl methacrylate derivative which may be substituted with deuterium, and (l) a molar part are polymerized to form a copolymer having a number average molecular weight of 10,000 to 100,000, and then (m) a molar part. The compound represented by the above formula (C-16) and the compound represented by the formula (C-17) in (n) mole parts or more are each made into a diazonium salt, and then these diazonium salt and the above-mentioned copolymer A method for producing a second-order nonlinear optical material, which comprises diazo coupling with a united body. [Chemical 6] 6. A compound (m ₁ + n ₁ ) mol part represented by the following formula (C-13) and a compound (l ₁ ) mol part represented by the following formula (C-14): Polymerized to give a copolymer having a number average molecular weight of 10,000 to 100,000 (C-1
5) and then (m ₁ ) mol part or more of the formula (C-1)
A compound represented by 6), (n ₁₎ parts by mole or more of the formula (C
Each of the compound represented by -17) is a diazonium salt, and then the diazonium salt and the copolymer (C-1) are used.
5) and diazo coupling with
The method for manufacturing the second-order nonlinear optical material according to claim 5. [Chemical 7] 7. A number average molecular weight of 1, wherein three structural units represented by the following formula (C-18) are randomly copolymerized.
20,000 to 100,000, 2 according to claim 3.
Non-linear optical material. [Chemical 8] [In the formula, the ratios of l ₂ , m ₂ , and n ₂ are in the ranges of 80 to 90 mol%, 5 to 10 mol%, and 5 to 10 mol%, respectively. ] 8. A compound (m ₃ + n ₃ ) mol part represented by the following formula (C-13) and a compound (l ₃ ) mol part represented by the following formula (C-19): A copolymer having a number average molecular weight of 10,000 to 100,000 (C-2
0), and then the formula (C-1) of (m ₃ ) mol part or more.
A compound represented by 6), (n ₃₎ parts by mole or more of the formula (C
Each of the compound represented by -17) is a diazonium salt, and these diazonium salt and a copolymer (C-2
0) and diazo coupling
The method for manufacturing the second-order nonlinear optical material according to claim 5. [Chemical 9] 9. A number average molecular weight of 1, in which three structural units represented by the following formula (C-21) are randomly copolymerized.
20,000 to 100,000, 2 according to claim 3.
Non-linear optical material. [Chemical 10] [In the formula, the ratios of l ₄ , m ₄ , and n ₄ are in the ranges of 80 to 90 mol%, 5 to 10 mol%, and 5 to 10 mol%, respectively. ] 10. A compound (m ₅ + n ₅ ) mol part represented by the following formula (C-22) and a compound (l ₅ ) mol part represented by the following formula (C-19): A copolymer having a number average molecular weight of 10,000 to 100,000 (C-2
3), and then the formula (C-1) of (m ₁ ) mol part or more.
A compound represented by 6), (n ₁₎ parts by mole or more of the formula (C
Each of the compound represented by -17) is a diazonium salt, and these diazonium salt and a copolymer (C-2
3) is characterized by diazo coupling with
The method for manufacturing the second-order nonlinear optical material according to claim 5. [Chemical 11]