JPH0580277A - Optical nonlinear main chain type high-polymer material - Google Patents

Abstract

PURPOSE:To obtain the org. nonlinear material having excellent light transmissivity and moldability by forming this material of an optical nonlinear main chain type high polymer having a structure in which the specific structure is incorporated into the main chain of a polymer. CONSTITUTION:The structure in which the structure expressed by formula I is incorporated into the main chain of the polymer selected from polyalkylene, polyamic acid, polyimide, polyamide, and polycarbonate is adopted. In the formula I, R1 and R2 are the same or different and respectively denote an alkyl group or hydrogen atom; Xn=Yn denote the pi conjugation coupler selected from -N=N-, -CH=CH- and -N=CH-; (n) denotes integer 3 to 7; a phenylene ring is substd. with a chlorine atom or is non-substd. This high-polymer material has a cubic nonlinear optical characteristic of high efficiency and has the excellent transmissive and waveguide structure moldability and is, therefore, utilizable as the central blank material of the optical nonlinear element which bears future optical computing and optical exchange technology.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an optical non-linear main chain type polymer material which can be applied to an optical gate element, an optical bistable element and the like which are basic elements of optical computing.

[0002]

2. Description of the Related Art When light is incident on a substance, the electric polarization P of the substance induced by a photoelectric field E is expressed by the general formula (1).
Can be expressed in the form of.

[0003]

## EQU1 ## P = χ ⁽¹⁾ E + χ ⁽²⁾ EE + χ ⁽³⁾ EEE + (1) At this time, χ ⁽ⁱ⁾ (i ≧ 2) is called the i-th order nonlinear susceptibility. The second harmonic generation (SHG) according to the second term and the third harmonic generation (THG) according to the third term are well known as the wavelength conversion effect. The third term is also important as giving a change in the optical constant depending on the light intensity, such as a nonlinear refractive index effect or a nonlinear absorption effect. Among them, the nonlinear refractive index effect is that the refractive index n of a substance changes in proportion to the incident light intensity, and is described by the equation (2).

[0004]

N = n ₀ + n ₂ I (2) n ₀ is the refractive index at weak light intensity, and I is the incident light intensity. n
₂ is the nonlinear refractive index, and n ₂ and the third-order nonlinear susceptibility:
The relation of equation (3) holds between χ ⁽³⁾ (C is the speed of light). Both n ₂ and χ ⁽³⁾ are used as indices indicating the magnitude of the optical nonlinear effect.

[0005]

N ₂ = (16π ² / Cn ₀ ² ) χ ⁽³⁾ (3) Combining a material exhibiting this effect with other optical elements such as an optical resonator, a polarizer or a reflecting mirror results in an optical duplex. Optical nonlinear elements such as stable elements, optical gate elements, and phase conjugate wave generators can be realized. These optical non-linear elements have great expectations as key devices for future optical computing and optical switching technologies (for optical non-linear elements in general,
Literature Conference Lecture of Eye Triple E International Conference Communications (Conf. Rec. IEEE Int.
Conf. Commun. ) 1990 version, 1152
(Detailed in (1990)).

The performance of the optical nonlinear element, that is, the wavelength range used, the intensity of input light required for operation, the response speed, etc., are mostly determined by the characteristics of the constituent materials.

Therefore, the usable wavelength range is wide,
The development of a material having high third-order optical nonlinear efficiency and capable of high-speed response of picosecond or less has been earnestly desired.

Among the materials exhibiting the third-order nonlinear optical effect, an organic material having a π-electron conjugation capable of high-speed response has recently attracted particular attention. Specifically, polydiacetylene,
Examples thereof include π-conjugated polymers such as polyacetylene and polyarylene vinylene. The nonlinear optical effect of organic materials with π-electron conjugation is purely due to electronic polarization, not to the lattice interaction like semiconductors and dielectrics, so the response speed that can follow the intensity change of the optical signal. Is 10 ^-14
It is extremely fast at sec.

However, most of π-conjugated polymers having a large χ ⁽³⁾ are insoluble and infusible and poor in workability. Even if it can be formed into a film, it has low optical transparency due to its rigidity and crystallinity, lacks formability into a desired waveguide structure, and it is extremely difficult to use it as an element as it is. It was In fact, a non-linear optical element using PTS as the element material, which has the largest χ ⁽³⁾ among organic materials, has not yet been realized. For the same reason, devices based on polyacetylene and polyarylene vinylene have not been developed yet.

On the other hand, as an organic material having a large nonlinear optical effect other than the π-conjugated polymer, there is a donor-acceptor type π-conjugated molecule. This aims at amplification of a nonlinear optical effect by substituting a donor at one end of a relatively short π-conjugated system and an acceptor at the other, and utilizing an intramolecular charge transfer effect generated between a donor and an acceptor. Specifically, DEANS (diethylaminonitrostilbene) and DEANST (diethylaminonitrostyrene)
Is known (for DEANS, refer to the reference Chemical Physics Letters (Chemcal Phys).
icsLetters) Volume 165, 171 (199)
0), for DEANST, US Pat.
95 (1991)). In both cases, the donor is a diethylamino group, the acceptor is a nitro group, and the π-conjugated system is stilbene for DEANS and styrene for DEANST. χ ⁽³⁾ is at most 10 ^-12 to 10 ^-11 es
u level. In particular, the nitrobenzene solution of DEANST has been tried as an optical gate device experiment as a nonlinear optical medium superior to CS ₂ . In addition, the π-conjugated system is a donor-acceptor type π-conjugated molecule of azobenzene
There is an example in which a side chain type polymer is covalently bonded to (polymethylmethacrylate) to give a photon nonlinear effect and optical transparency (the first example of the photon nonlinear side chain type polymer is described in the literature Applied Physics Letters). (Applied P
hysics Letters) 51, 1 (198)
7)). However, there remains an essential problem that χ ⁽³⁾ is smaller than that of π-conjugated polymer by one digit or more.

As described above, in order to realize a high-speed optical nonlinear device with an organic material, a new material having χ ⁽³⁾ as high as that of a π-conjugated polymer and having both moldability and light transmittance. Development was essential. In order to achieve semiconductor laser operation, χ ⁽³⁾ is at least 10 ^-10 esu or more,
There was a demand to hold 10 ⁻¹² (W / cm ² ) ⁻¹ in terms of n ₂ calculated by the formula (3).

[0012]

As described above, χ
Most of the organic materials with ⁽³⁾ of 10 ^-10 esu or more are π-conjugated polymers, and they are rigid and have high crystallinity and poor workability, so they have low light transmittance and formability into a desired waveguide structure. Is extremely low. On the other hand, also in the optical non-linear side chain type polymer material having a donor-acceptor type π-conjugated molecule as a side chain, the χ ^{(3) of the} donor-acceptor type π-conjugated molecule itself responsible for the optical nonlinearity reaches 10 ^-10 esu. In addition, it was difficult to introduce these molecules at a high concentration. The method for producing the optical nonlinear side chain type polymer includes a radical copolymerization method of a vinyl monomer having a χ ⁽³⁾ substance and a polymer reaction method. In radical polymerization, nitro groups and azo bonds, which are essential for improvement of χ ⁽³⁾ , act as radical inhibitors, so the radical inhibition reaction is more likely to occur as the content of χ ⁽³⁾ substance increases.
Therefore, the degree of polymerization did not increase and the film-forming property of the obtained polymer was low. Therefore, the concentration of χ ⁽³⁾ substance is high,
Moreover, it was difficult to obtain a material having a true film-forming property. For example, the introduction rate of a χ ⁽³⁾ substance having ^three or more rings containing a nitro group and an azo bond in the molecule was limited to 10 to 30 mol%. On the other hand, the introduction rate is 20 even if the polymer reaction is used.
The limit was around mol%. Further, χ ⁽³⁾ of the optical nonlinear side chain type polymer material produced by these methods was at a level of 10 ^-11 esu at most.

As described above, the optical non-linear side chain type polymer material has a high potential for device application because it is based on a polymer having high moldability and light transmissivity such as PMMA, but the important χ ⁽³⁾ There is a definite problem that is smaller than the π-conjugated polymer by about one digit.

Substances having a χ ⁽³⁾ of 10 ^-10 esu or more have high planarity, and if the introduction rate of these substances into the polymer main chain is increased, the solubility in a solvent generally decreases, so spin coating, etc. In many cases, a simple film forming method cannot be used.

Therefore, in order to solve the above-mentioned problems, the object of the present invention is to polymerize a substance having χ ⁽³⁾ , which is comparable to or exceeds the π-conjugated polymer, at a high introduction rate, and has a high light transmittance. -To provide an organic optical nonlinear material having excellent moldability.

[0016]

The present invention is different from the side-chain type optical nonlinear polymer material which has been reported in the past, and in the polymer main chain, χ ⁽³⁾ has 10 ^-10 esu or more. The present invention relates to an optical nonlinear main chain type polymer material characterized by incorporating the high χ ⁽³⁾ substance of.

The optical non-linear main chain type polymer material of the present invention has the following general formula (I) (Chemical formula 1) (wherein R ₁ and R ₂ are the same or different and each represents an alkyl group or a hydrogen atom; Xn = Yn represents a π-conjugated bond selected from -N = N-, -CH = CH- and -N = CH-; n represents an integer of 3 or more and 7 or less; the phenylene ring is substituted with a chlorine atom. A structure represented by the formula (1) or (not substituted) has a structure incorporated in the main chain of a polymer selected from polyalkylene, polyamic acid, polyimide, polyamide and polycarbonate.

The optical nonlinear main chain type polymer material of the present invention has the following general formula (II), the following general formula (II) (Chemical formula 2) (wherein R ₁ ′ and R ₂ ′ are the same or different) , Each represents an alkyl group or a hydrogen atom; Xn ′ = Y
n'is -N = N-, -CH = CH- and -N = CH-
R represents an alkyl group; n'represents an integer of 1 or more and 4 or less) selected from polyalkylene, polyamic acid, polyimide, polyamide and polycarbonate. It is characterized by having a structure incorporated in the main chain of the polymer.

The high χ ⁽³⁾ substance used in the present invention is a π-conjugated compound preferably having a central symmetric structure in which both ends of the molecule are substituted with electron donating groups (donors), and χ ⁽³⁾ thereof is
Well over 10 ^-10 esu. Further, by using the main chain type polymer material, the light transmittance and moldability as the polymer material will not be lost even when the introduction rate is 50 mol%.

A compound having a structure similar to the basic structure of the polycyclic azo dye, which is one of the χ ⁽³⁾ expressing substances used in the present invention, is known as a high dichroic dye mixed with liquid crystal (azo dye). The high dichroic ratio dye is described in detail in US Pat. No. 4,128,497 (1978)). However, since these known compounds do not have a hydroxyl group or an amino group at the donor end in the structure as they are, they cannot be used as a raw material for the main chain polymer material. The high χ ⁽³⁾ substance used in the present invention is characterized by expressing χ ⁽³⁾ by a mechanism closer to that of a π-conjugated polymer rather than the conventional donor-acceptor-substituted intramolecular charge transfer compound.

The high χ ⁽³⁾ substance of the present invention can be synthesized mainly by the following two methods. In the first synthesis method, a double equivalent amount of a donor-substituted π-conjugated ring is bound to a π-conjugated system having the same functional group at both ends of the molecule by a substitution reaction or an addition reaction, and —CH═CH—, —CH═N. It is a method of expanding a π-conjugated system by using a connector of −, −N = N−. The second synthetic method is a method in which a donor / acceptor compound having a donor at one end of the molecule and a nitro group at the other end is used as a raw material, and the nitro groups are reductively coupled to each other to form a -N = N- bond. is there. Further, when the π-conjugated ring of the χ ⁽³⁾ substance is replaced with a chlorine group, the solubility is increased and the polymerization reaction is facilitated. Furthermore, since the methoxy group and the chlorine group have the effect of suppressing the association of dyes that cause light scattering and maintaining the uniformity of the film, the composition of the obtained optical nonlinear main chain type polymer material is It is also effective in improving the film properties and light transmittance.

Specific examples of the high χ ⁽³⁾ substance portion incorporated in the main chain of the optical nonlinear main chain type polymer material of the present invention include:
2,5-dichloroterephthalidene-bis [p- (N, N
-Dibutyl) aminoaniline] structure, 4,4'-bis [(p- (N-ethyl) aminophenyl) azo] -azobenzene structure, 4,4'-bis [(p- (N-ethyl))
Aminophenyl) azo] -stilbene structure, 4,4'-
Bis [(p- (N-ethyl) aminophenyl) azo]-
2,2'-dimethoxybiphenyl structure and terephthalidene-bis [(p- (N, N-dimethyl) aminophenyl) azoaniline structure.

[0023]

[Function] The high χ ⁽³⁾ substance with centrosymmetric substitution used for the production of the optical nonlinear main chain type polymer material of the present invention is
Since the donors at both ends of the molecule are manufactured to have a hydroxyl group or an amino group, the main chain polymer material having a polyalkylene structure, a polyamic acid structure, a polyimide structure, or a polyamide structure can be easily obtained. That is, when a hydroxyl group is contained in the donors at both ends of the molecule of the high χ ⁽³⁾ substance, a polycarbonate is obtained by reacting the hydroxyl group with phosgene gas. A polyamic acid is obtained by reacting with a tetracarboxylic dianhydride such as meritic acid. A polyimide is obtained by subjecting this polyamic acid to ring closure by heating. Further, a polyamide can be obtained by reacting this amino group with a dibasic acid or a salt thereof. The polyalkylene derivative may be incorporated into the polyalkylene backbone using the previously formed high χ ⁽³⁾ material, but as shown in Examples 1 and 2 below, a suitable alkylenediamine and tetracarboxylic acid are added. Conveniently, it is used to carry out polymer backbone formation and formation of high χ ⁽³⁾ material in one step. Many of the optical nonlinear main chain type polymer materials of the present invention are chemically stable except polyamic acid. Further, since the non-linear polymer material of the present invention has a high χ ⁽³⁾ substance bound by a molecular chain having a relatively high solubility, many materials that can be spin-coated as they are when they are made into a thin film are formed by the spin-coating method. Thus, a waveguide thin film having excellent light transmittance can be easily manufactured. Furthermore, by selecting the starting material and copolymerizing by adding a diol or a diamine, it is possible to arbitrarily control the light transmissivity and the moldability of the waveguide structure.

[0024]

EXAMPLES The present invention will be described in more detail below with reference to examples.

First, the high χ ⁽³⁾ substance A used in the present invention,
Synthetic examples will be described for A ', B, B', C, C ', D, D', E and E '.

Synthesis Example 1 Synthesis of high χ ⁽³⁾ substance A 4- (N-butyl-N-butanol) aminoaniline 1
Mol and 0.5 mol of dichloroterephthalaldehyde were dissolved in tetrahydrofuran, and a catalytic amount of p-toluenesulfonic acid was dropped, and the mixture was heated under reflux for 24 hours. The precipitated product was purified by recrystallization to obtain 2,5-dichloroterephthalidene-bis [p- (N-butyl-N-butanol) aminoaniline] [high χ ⁽³⁾ substance A] used in the present invention. Obtained.

Synthesis Example 2 Synthesis Method of High χ ⁽³⁾ Substance A ′ 4- (N-butyl-N-aminobutyl) aminoaniline (1 mol) and dichloroterephthalaldehyde (0.5 mol) were dissolved in tetrahydrofuran to prepare p-toluene. After adding a catalytic amount of sulfonic acid, the mixture was heated under reflux for 24 hours. The precipitated product was purified by recrystallization and used in the present invention 2,5-dichloroterephthalidene-bis [p- (N-4-aminobutyl-N-butyl) aminoaniline] [high χ ⁽³⁾ substance. A ′] was obtained.

Synthesis Example 3 Synthesis Method of High χ ⁽³⁾ Substance B 1 mol of 4,4'-diaminoazobenzene was dissolved in acetic acid. To this, a sulfuric acid solution of sodium nitrite was added dropwise at 5 ° C or lower. A water-ethanol (1: 1) mixed solution at 5 ° C or lower was added, and a saturated aqueous solution of sodium acetate was further added.
H = 4. At 0 ° C., an ethanol solution of 2 mol of N-ethanolaminoaniline was poured into this. While gradually returning the reaction solution temperature to room temperature, the reaction was carried out overnight. The ethanol was distilled off under reduced pressure, and the precipitated product was isolated and purified by column chromatography (carrier: dry silica gel, solvent: chloroform), and 4,4'-bis [p- (N-
2-Hydroxyethyl) aminophenyl) azo] -azobenzene [high χ ⁽³⁾ substance B] was obtained.

Synthesis Example 4 Synthesis Method of High χ ⁽³⁾ Substance B ′ 0.5 mol of 4,4′-diaminoazobenzene was dissolved in acetic acid. To this, a sulfuric acid solution of sodium nitrite was added dropwise at 5 ° C or lower. A water-ethanol (1: 1) mixed solution at 5 ° C or lower was added, and a saturated sodium acetate aqueous solution was further added to adjust the pH to 4. An ethanol solution of 1 mol of N-ethanolaminoaniline was poured into this at 0 ° C. While gradually returning the reaction solution temperature to room temperature, the reaction was carried out overnight. The ethanol was distilled off under reduced pressure, and the precipitated product was isolated and purified by column chromatography to obtain 4,4′-bis [p- (N-2-aminoethyl) aminophenyl) azo] -azobenzene [high χ ⁽³⁾ Material B ′] was obtained.

Synthesis Example 5 Synthesis Method of High χ ⁽³⁾ Substance C 0.5 mol of 4,4'-diaminostilbene was dissolved in acetic acid. To this, a sulfuric acid solution of sodium nitrite was added dropwise at 5 ° C or lower. A water-ethanol (1: 1) mixed solution at 5 ° C or lower was added, and a saturated sodium acetate aqueous solution was further added,
The pH was set to 4. An ethanol solution of 1 mol of N-ethanolaminoaniline was poured into this at 0 ° C. While gradually returning the reaction solution temperature to room temperature, the reaction was carried out overnight. Ethanol was distilled off under reduced pressure, and the precipitated product was isolated and purified by column chromatography to obtain 4,4'-bis [p-
(N-2-hydroxyethyl) aminophenyl) azo]
-Stilbene [high χ ⁽³⁾ substance C] was obtained.

Synthesis Example 6 Synthesis Method of High χ ⁽³⁾ Substance C ′ 0.5 mol of 4,4′-diaminostilbene was dissolved in acetic acid. To this, a sulfuric acid solution of sodium nitrite was added dropwise at 5 ° C or lower. A water-ethanol (1: 1) mixed solution at 5 ° C or lower was added, and a saturated sodium acetate aqueous solution was further added,
The pH was set to 4. An ethanol solution of 1 mol of N-ethanolaminoaniline was poured into this at 0 ° C. The reaction was carried out overnight while gradually returning the temperature of the reaction solution to room temperature. Ethanol was distilled off under reduced pressure, and the precipitated product was isolated and purified by column chromatography to obtain 4,4'-bis [p-
(N-aminoethyl) aminophenyl) azo] -stilbene [high χ ⁽³⁾ substance C '] was obtained.

Synthesis Example 7 Synthesis Method of High-χ ⁽³⁾ Substance D 0.1 mol of 4,4'-diamino-3,3'-dimethoxybiphenyl was dissolved in acetic acid. To this, a sulfuric acid solution of sodium nitrite was added dropwise at 5 ° C or lower. A water-ethanol (1: 1) mixed solution at 5 ° C or lower was added, and a saturated sodium acetate aqueous solution was further added to adjust the pH to 4. To this, 0 ℃
Then, an ethanol solution of 0.2 mol of N-ethanolaminoaniline was poured. While gradually returning the reaction solution temperature to room temperature, the reaction was carried out overnight. Ethanol was distilled off under reduced pressure, and the precipitated product was isolated and purified by column chromatography to obtain 4,4'-bis [p- (N-2-hydroxyethyl) aminophenyl) azo] -2,2 '. -Dimethoxybiphenyl [high χ ⁽³⁾ substance D] was obtained.

Synthesis Example 8 Synthesis Method of High χ ⁽³⁾ Substance D'4,4'-Diamino-3,3'-dimethoxybiphenyl 0.1 mol was dissolved in acetic acid. To this, a sulfuric acid solution of sodium nitrite was added dropwise at 5 ° C or lower. A water-ethanol (1: 1) mixed solution at 5 ° C or lower was added, and a saturated sodium acetate aqueous solution was further added to adjust the pH to 4. To this, 0 ℃
Then, an ethanol solution of 0.2 mol of N-ethanolaminoaniline was poured. While gradually returning the reaction solution temperature to room temperature, the reaction was carried out overnight. Ethanol was distilled off under reduced pressure, and the precipitated product was isolated and purified by column chromatography to obtain 4,4'-bis [p- (N-2-aminoethyl).
Aminophenyl) azo] -2,2'-dimethoxybiphenyl [high χ ⁽³⁾ substance D '] was obtained.

Synthesis Example 9 Synthesis Method of High χ ⁽³⁾ Substance E Dichloro-terephthalaldehyde and 4-fold equivalent of 4-
[P- (N-Butyl-N-butanol) aminophenylazo] -1-aminobenzene was dissolved in tetrahydrofuran, a catalytic amount of benzenesulfonic acid was added, and the mixture was heated under reflux for 5 hours with stirring. The product was separated by column to obtain terephthalidene-bis [(p- (N-4-hydroxybutyl-N-butyl) aminophenyl) azoaniline] [high χ ⁽³⁾ substance E].

Synthesis Example 10 Synthesis Method of High χ ⁽³⁾ Substance E ′ Dichloroterephthalaldehyde and 4-fold equivalent of 4-
[(P- (N-Butyl-N-butylamino) aminophenyl) azo] -1-aminobenzene was dissolved in tetrahydrofuran, a catalytic amount of benzenesulfonic acid was added, and the mixture was heated under reflux with stirring for 5 hours. The product was column separated and terephthalidene-bis [(p- (N-4-aminobutyl-N-butyl) aminophenyl) azoaniline]
[High χ ⁽³⁾ substance E ′] was obtained.

Regarding the polyalkyl derivative of the material of the present invention shown in the examples, the method of synthesizing other materials of the present invention, polycarbonate, polyamic acid, polyimide, and polycarbonate derivative (high χ ⁽³⁾ substance was previously synthesized, and difunctional In contrast to the synthetic method of polycondensation with organic materials to polymerize), the polycondensation of the starting materials results in the formation of a polymer backbone that already incorporates a high χ ⁽³⁾ material in shape.

The high χ ⁽³⁾ substance A obtained in the above synthesis example,
The structural formulas of A ', B, B', C, C ', D, D', E and E'are as follows.

High χ ⁽³⁾ substance A:

[0039]

[Chemical 3]

High χ ⁽³⁾ substance A ':

[0041]

[Chemical 4]

High χ ⁽³⁾ substance B:

[0043]

[Chemical 5]

High χ ⁽³⁾ substance B ':

[0045]

[Chemical 6]

High χ ⁽³⁾ substance C:

[0047]

[Chemical 7]

High χ ⁽³⁾ substance C ':

[0049]

[Chemical 8]

High χ ⁽³⁾ substance D:

[0051]

[Chemical 9]

High χ ⁽³⁾ substance D ':

[0053]

[Chemical 10]

High χ ⁽³⁾ substance E:

[0055]

[Chemical 11]

High χ ⁽³⁾ substance E ′:

[0057]

[Chemical formula 12]

Next, Examples 1 and 2 will be described with reference to the polyalkylene derivative of the present invention. Furthermore, in Examples 3 to 22, the high χ ⁽³⁾ substances A, A ′, which have the above-mentioned symmetric substitution,
The optical nonlinear main chain of the present invention comprising a polyamic acid derivative, a polyimide derivative, a polyamide derivative or a polycarbonate derivative in which any one of B, B ', C, C', D, D ', E and E'is incorporated in the main chain. Shows a polymeric material. In Examples 1 and 2, the symmetric substitution high χ ⁽³⁾ substance incorporated is A '.

(Example 1) 1 mol of N, N'-C, 4-aminophenyl-N, N'-dimethyl-1,4-butylenediamine and 1 mol of dichloroterephthalaldehyde were reacted in tetrahydrofuran. P-Toluenesulfonic acid was used as a catalyst. The reaction solution was poured into a large amount of hexane to obtain a polyalkylene derivative, which is a target optical nonlinear main chain type polymer material. This was again reprecipitated and purified to give an anisole solution, which was applied to a quartz substrate to give a reddish purple thickness of 20.
A 0Å polymer film was obtained. Χ ^{(3) of} this film
Is the THG (third harmonic generation) -maker fringe method, that is, χ ⁽³⁾ is a method for simultaneously measuring THG of known fused silica and determining χ ⁽³⁾ from the THG ratio of the fused silica and the sample. I asked. chi ⁽³⁾ The value fundamental wavelength 1.
It was about 5 × 10 ⁻¹¹ at 6 μm.

In the case of the above-mentioned polymer, the organic solvent was low, and the film thickness could be produced only up to several thousand angstroms by spin coating. Therefore, during the above reaction, the reaction solution was GP
Using C (gel permeation chromatography), an intermediate product having a molecular weight of about 2000 and about 2-3 trimers was separated. This intermediate product was soluble in the organic solvent tetrahydrofuran and could be dissolved up to 10% by weight. Using this solution, a thin film was formed on a glass substrate by spin coating. Then, heat the film together with the substrate to 100 ° C.,
A 1 μm film was obtained. The membrane was insoluble in THF solvent. A laser beam having a wavelength longer than the absorption edge wavelength of 1.3 μm was transmitted through the prism coupling and the loss was measured. As a result, a waveguide loss of 1 dB / cm or less was obtained.

Example 2 1 mol of N, N '-(4'-aminophenyl) -1,4-butylenediamine and 1 mol of dichloroterephthalaldehyde were reacted in tetrahydrofuran. P-Toluenesulfonic acid was used as a catalyst. The reaction solution was poured into a large amount of hexane to obtain a polyalkyl derivative which was a target optical nonlinear main chain type polymer material. This was again pillow-refined to obtain an anisole solution, which was applied to a quartz substrate to obtain a red-purple polymer film having a thickness of 200Å. Χ ⁽³⁾ of this film is a THG manufacturer
It was determined by the fringe method. The χ ⁽³⁾ value was about 10 ^-10 esu when the fundamental wavelength was 1.6 μm. Also in the case of this polymer, the solubility in an organic solvent was low as in Example 1, and spin coating could produce a film thickness of only up to several thousand angstroms. Therefore, in the same manner as in Example 1, a thin film was formed on the glass substrate by spin coating using the intermediate product. Thereafter, the film together with the substrate was heated to 100 ° C. to obtain a 1 μm film. The membrane was insoluble in THF solvent. When a loss measurement was performed by transmitting 1.3 μm of laser light having a wavelength longer than the absorption edge wavelength of this film by prism coupling, a waveguide loss of 1 dB / cm or less was obtained.

(Example 3) 2,5-dichloro-terephthalidene-bis- [4- (p- (N-butyl-N-butanol) aminophenyl) aniline] [high χ ⁽³⁾ substance A]
1 mol was dissolved in pyridine, a small amount of triethylamine was mixed as a catalyst, the atmosphere in the reaction vessel was replaced with nitrogen, and then phosgene gas was flown into this solution. After reacting for a whole day and night, the reaction solution was poured into a large amount of hexane to obtain a polycarbonate derivative as an intended optical nonlinear main chain type polymer material. This was reprecipitated and purified again to give a butyl acetate solution, which was applied to a quartz substrate to obtain a reddish purple film having a thickness of 200 Å. Χ ⁽³⁾ of this film was found by THG (third harmonic generation) -Manufacturer-Fringe method, and ^{-10 -10} e
The value of su was obtained. The waveguide loss on the longer wavelength side than the absorption edge wavelength was 1 dB / cm or less.

(Example 4) 2,5-dichloro-terephthalidene rubis- [4- (p- (N-butyl-N-butylamino) aminophenyl) aniline] [high χ ⁽³⁾ substance A ' ] 1 mol and pyromellitic dianhydride 1 mol were made to react in anhydrous dimethylacetamide at room temperature for 3 hours. The reaction solution was spin-coated on a quartz substrate. The spin-coated film was put in a drier at 90 ° C. and the solvent was sufficiently evaporated to obtain a reddish purple polyamic acid film. The film thickness was controllable from 200Å to 2μ depending on the reaction solution concentration.

Χ ⁽³⁾ of this film is for THG manufacturers
It was determined by the fringe method. The χ ⁽³⁾ value was about 5 × 10 ^-11 esu when the fundamental wavelength was 1.6 μm. When 1.3 μm of laser light having a wavelength longer than the absorption edge wavelength was passed through the film having a thickness of 1 μm by prism coupling and the loss was measured, a waveguide loss of 1 dB / cm or less was obtained.

Example 5 A polyamic acid film prepared in the same manner as in Example 3 was heated at 180 ° C. for 30 minutes and then 260 times.
A corresponding polyimide thin film was obtained by heating and dehydration at 30 ° C. for 30 minutes. Χ ⁽³⁾ of this film was determined by the THG maker fringe method. The χ ⁽³⁾ value was about 5 × 10 ^-11 esu when the fundamental wavelength was 1.6 μm. When 1.3 μm of laser light having a wavelength longer than the absorption edge wavelength was transmitted through a film having a thickness of 1 μm by prism coupling and the loss was measured, a waveguide loss of 1 dB / cm or less was obtained.

Example 6 2,5-Dichloro-terephthalidene-bis- [4- (p- (N-butyl-N-butylamino) aminophenyl) aniline] [high χ ⁽³⁾ substance A ' ] 1 mol and 1 mol of adipic acid chloride were reacted in THF, and the reaction solution was poured into a large amount of hexane to obtain a target polyamide derivative which is an optical nonlinear main chain type polymer material. This was reprecipitated and purified again to give a butyl acetate solution, which was applied to a quartz substrate to obtain a reddish purple film having a thickness of 200 Å. Χ ⁽³⁾ of this film was found by THG (third harmonic generation) -Manufacturer-Fringe method, and ^{-10 -10} e
The value of su was obtained. The waveguide loss on the longer wavelength side than the absorption edge wavelength was 1 dB / cm or less.

(Examples 7 to 22) High χ incorporated into the main chain
^{(3) The} substance A or A'is replaced by B, B'C, C ', D, D',
A main chain type polymer was obtained in the same manner as in Examples 3 to 6 except that E or E ′ was changed, and this was made into a thin film, and χ ⁽³⁾ of the obtained film was similarly obtained by the THG maker fringe method. It was The results obtained are shown in Table 1.

[0068]

INDUSTRIAL APPLICABILITY As described above, the optical non-linear main chain type polymer material of the present invention has highly efficient third-order non-linear optical characteristics, and is excellent in light transmission and waveguiding structure moldability, and therefore will be used in the future. It can be widely used as a central material for optical nonlinear devices that are responsible for the optical computing and optical switching technologies of For example, when compared with the organic nonlinear optical material DEANST used in the nonlinear optical device described in US Pat. No. 4,997,595, its excellentness can be confirmed. First, while DEANST is used in a solution state, the material of the present invention can use a single spin coat film. Further 30 wt% DEAN
Χ including the molecular rotation effect of ST-nitrobenzene solution
Whereas ⁽³⁾ was 3.6 × 10 ^-12 esu, χ ⁽³⁾ of the material of the present invention is 10 ^-10 esu or more, which is about 30 times that of DEANST.

As a material for an optical gate optical switch element, a low χ ⁽³⁾ material such as DEANST needs to be elongated and cannot be used unless the waveguide loss is extremely low. On the other hand, a material with a large χ ⁽³⁾ requires only a short optical path length, so that the requirement for waveguide loss is moderate.

Since the waveguide loss of this material is about 1 to 2 dB / cm, about 50% of χ ⁽³⁾ can be effectively used if the optical path length is 1 cm. If a waveguide having a cross-sectional area of 3 μm ^{2 and} a length of about 1 cm is manufactured, an optical gate optical switch device that is sufficiently driven by a semiconductor laser can be realized.

Regarding the device operation speed, picosecond switching operation has already been confirmed in the DEANST solution containing the speed molecular rotation effect, and operation of picosecond or less is possible in this material system without molecular rotation. Furthermore, it can be applied not only to the optical gate optical switching device but also to other important optical nonlinear devices such as an optical bistable device and an optical limiter device.

[0072]

[Table 1]

Claims (2)

[Claims] 1. The following general formula (I): (In the formula, R ₁ and R ₂ are the same or different and each represents an alkyl group or a hydrogen atom; Xn = Yn is selected from -N = N-, -CH = CH- and -N = CH-. represents a π-conjugated bond; n represents an integer of 3 or more and 7 or less; the phenylene ring is substituted with a chlorine atom or unsubstituted) is a polyalkylene,
An optical nonlinear main chain type polymer material characterized by having a structure incorporated in the main chain of a polymer selected from polyamic acid, polyimide, polyamide and polycarbonate. 2. The following general formula (II): In the formula, R ₁ ′ and R ₂ ′ are the same or different and each represents an alkyl group or a hydrogen atom; Xn ′ = Y
n'is -N = N-, -CH = CH- and -N = CH-
R represents an alkyl group; n'represents an integer of 1 or more and 4 or less) selected from polyalkylene, polyamic acid, polyimide, polyamide and polycarbonate. An optical non-linear main chain type polymer material having a structure incorporated in a main chain of a polymer.