JPH0511291A - Organic nonlinear optical material and nonlinear optical element formed by using this material - Google Patents

Abstract

PURPOSE:To obtain the org. nonlinear optical material having the second high frequency generation (SHG) at which a crystal has no inversion symmetrical centers and has no absorption in a long wavelength region by forming the material of a specific compd.; for example, trisbenzamide. CONSTITUTION:The triamide compd. expressed by formula is used as the org. nonlinear optical medium of the semiconductor laser wavelength conversion element consisting of a semiconductor laser beam source, a lens and the nonlinear optical medium. In the formula I, Ar1, to Ar3, are atom groups having pielectron conjugated structures and may be different from each other or may be substd. with an org. substituent. Namely, these groups consist of the pi conjugated atom groups selected from a benzene ring, naphthalene ring, etc., or the pi conjugated atom groups substd. with the substituents selected from a nitro group, cyano group, etc. This org. nonlinear optical material consists of a single crystal of >=1mm square or a film which is dispersed in a transparent high polymer and is oriented in a strong electric field and this material is held in a resonator of light.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an organic non-linear optical material and a non-linear optical element using the same.

[0002]

2. Description of the Related Art In recent years, a nonlinear optical material is a material which exhibits a second-order and third-order nonlinear response due to an electromagnetic field and has element functions such as harmonic generation, optical mixing, optical parametric oscillation, optical modulation, and optical switch. It's getting a lot of attention.

Conventionally, as non-linear optical materials, lithium niobate (LiNbO ₃ ) and potassium dihydrogen phosphate (K
Inorganic crystal materials such as H ₂ PO ₄ ) and gallium arsenide (GaAs) and semiconductor materials have been mainly studied. However, the inorganic crystal material has many problems such as difficulty in modifying the compound, deliquescent crystal, and difficulty in handling, and difficulty in obtaining high-speed response of picosecond or less.

On the other hand, the organic nonlinear material has a high possibility of obtaining a material having a high photoresponse speed because the molecular modification is easy and the nonlinear optical constant is large.

Under these circumstances, in recent years, organic nonlinear optical materials having excellent nonlinear optical characteristics and an extremely fast optical response speed as compared with inorganic materials have been discovered, and development of nonlinear optical elements using them has become active. (JP-A-1-26
8669).

[0006]

In the development of conventional organic nonlinear optical materials, in order to increase the dipole moment of a molecule, the molecule has a π electron conjugated system, and various electron donating groups and electron withdrawing groups are used. Design and synthesis of materials incorporating groups have been carried out. However, the above-mentioned method of molecular design has no absorption in the second harmonic generation region, which is a necessary condition for expressing the second-order nonlinearity, and that the crystal structure does not have an inversion symmetry center. There is a trade-off relationship. That is, in developing an organic nonlinear optical material, it is necessary to sufficiently consider not only the supramolecular polarizability but also the transmittance in the second harmonic generation region and the crystal structure.

[0007] Organic materials are easy to modify, but to obtain crystals without the center of inversion symmetry necessary for the expression of the second-order nonlinear optical effect, and to obtain those with a lower absorption wavelength edge. There are many difficult points. For example, paranitroaniline does not exhibit non-linearity as a crystal although the supramolecular polarizability of the molecule itself is large to some extent. This is because the crystal of paranitroaniline has the center of inversion symmetry. Other examples of this are ortho-nitroaniline,
There are many examples such as 4-dimethylamino-4′-nitrostilbene and paranitro-N-oxide pyridine.

Also, if the nonlinear material has absorption in the second harmonic generation region, the second harmonic generation (SHG) efficiency will be significantly reduced. The wavelength of the output light of the current semiconductor laser is about 85
Since it is 0 to 750 nm, the absorption wavelength edge of the nonlinear material is preferably 450 nm or less. That is, in order to obtain a more effective organic nonlinear optical material, it is necessary that the second-order supramolecular polarizability is large and that the molecule has a crystal structure with an asymmetric center structure. Further, the absorption wavelength edge is desirably 450 nm or less.

It is an object of the present invention to provide an organic non-linear optical material having a large SHG activity in which a crystal does not have an inversion symmetry center and does not absorb in a long wavelength region.

Another object of the present invention is to provide a nonlinear optical element using the above organic nonlinear optical material.

[0011]

In order to achieve the above object, a triamide compound was designed and synthesized, and its non-linearity was evaluated. As a result, in a semiconductor laser wavelength conversion element including a semiconductor laser light source, a lens, and a nonlinear optical medium, the wavelength conversion of the semiconductor laser can be efficiently performed by using the triamide compound represented by the following formula [1] as the nonlinear optical medium. And has reached the present invention. The summary of the present invention is as follows.

(1) An organic nonlinear optical material comprising a compound represented by the formulas [1] to [3].

[0013]

[Chemical 6]

[0014]

[Chemical 7]

[0015]

[Chemical 8]

[However, Ar _{1 to} Ar ₃ may be different from each other in an atomic group having a π-electron conjugated structure, and may be substituted with an organic substituent. ] In the above formula [1], Ar _{1 to} Ar ₃ are benzene ring, naphthalene ring, anthracene ring, benzoquinone ring, naphthoquinone ring, anthraquinone ring, pyrrole ring, imidazole ring, indole ring, quinoline ring, phenazine ring and cinnamyl group. It is a compound represented by a π-conjugated atomic group selected from.

Ar _{1 to} Ar ₃ are nitro group, cyano group, isocyanate group, carboxy group, allyl group, allyloxy group, allylsulfonyl group, allylsulfinyl group, allyloxysulfonyl group, allyloxycarbonyl group, allylthio group. , Acylamino group, acyloxy group, carbamoyl group, sulfamoyl group, carbon number 1-8
Alkyl group, same alkyloxycarbonyl group, same alkylsulfonyl group, same alkylsulfinyl group, same alkyloxysulfonyl group, same alkylthio group, carbon number 1
Is a compound substituted with a substituent selected from an alkoxy group, a hydroxy group, a thiol group, and a halogen atom.

(2) An organic nonlinear optical material comprising a compound represented by the formula [4].

[0019]

[Chemical 9]

[However, A _{1 to} A ₅ , B _{1 to} B ₅ , C _{1 to} C
Is a hydrogen atom, nitro group, cyano group, isocyanate group, carboxy group, allyl group, allyloxy group, allylsulfonyl group, allylsulfinyl group, allyloxysulfonyl group, allyloxycarbonyl group, allylthio group, acylamino group, acyloxy group, Carbamoyl group, sulfamoyl group, alkyl group having 1 to 8 carbon atoms, same alkyloxycarbonyl group, same alkylsulfonyl group, same alkylsulfinyl group, same alkyloxysulfonyl group, same alkylthio group, alkoxy group having 1 to 8 carbon atoms, It is a compound having a substituent selected from a hydroxy group, a thiol group and a halogen atom.

(3) An organic nonlinear optical material comprising a compound represented by the formula [5].

[0022]

[Chemical 10]

[Wherein R _{1 to} R ₃ are hydrogen atoms, nitro groups,
Cyano group, isocyanate group, carboxy group, allyl group, allyloxy group, allylsulfonyl group, allylsulfinyl group, allyloxysulfonyl group, allyloxycarbonyl group, allylthio group, acylamino group, acyloxy group, carbamoyl group, sulfamoyl group, carbon number 1-8 alkyl groups, the same alkyloxycarbonyl groups,
Same alkylsulfonyl group, same alkylsulfinyl group,
The alkyloxysulfonyl group, the alkylthio group, the alkoxy group having 1 to 8 carbon atoms, the hydroxy group, the thiol group, and the halogen atom may be selected and may be different from each other. (4) A film in which the organic nonlinear optical material represented by the above formulas [1] to [5] is a single crystal of 1 mm square or more or an organic nonlinear optical material dispersed in a transparent polymer and oriented in a strong electric field. And a non-linear optical element characterized by being held in an optical resonator.

(5) Light having a light source, a condensing means for condensing light from the light source, and a harmonic generating means for receiving the light condensed by the condensing means to generate a second harmonic In the wavelength conversion device, the second harmonic generation means includes a single crystal of the organic nonlinear optical material represented by the formulas [1] to [5] or a polymer dispersion thereof in the optical path. It is a light wavelength conversion device.

The transparent high molecular polymer in which the organic nonlinear optical material is dispersed is typified by acrylic acid, methyl acrylate, ethyl acrylate, butyl acrylate, methacrylic acid, methyl methacrylate, ethyl methacrylate, cyclohexyl methacrylate, phenyl methacrylate, styrene and the like. A transparent polymer polymer obtained by polymerizing the above-mentioned monomer is used. In particular, the polymer is 40
It is desirable that the polymer has no absorption above 0 nm. Then, the dispersion is oriented in a strong electric field. Further, the dispersion can be obtained by previously dispersing a non-linear medium in the monomer and polymerizing the non-linear medium in the strong electric field while orienting the non-linear material. It can also be obtained by polymerizing a monomer in which the non-linear material is dispersed, heating the polymer to a temperature higher than the glass transition temperature of the polymer, and then gradually cooling the polymer in a strong electric field.

Further, the organic non-linear optical material of the present invention is used as a non-linear optical element having an optical waveguide in which a single crystal or a polymer dispersion thereof is used as a core and the core is surrounded by a cladding layer.

FIG. 1 is a schematic diagram of an optical wavelength conversion device to which the nonlinear optical element of the present invention is applied. A laser beam 6 from a laser diode 1 (GaAlAs semiconductor laser beam; wavelength 0.88 to 0.8) is applied to an SHG element 5 having a core of the organic nonlinear material or a polymer dispersion thereof and a cladding layer surrounding the core. 75 μm) is transmitted through the collimator 2, the anamorphic prism pair 3 and the condenser lens 4 to obtain blue light (wavelength 0.44 to 0.3).
7 μm) second harmonic can be obtained. By using the SHG element 5 of the present invention, an optical wavelength conversion device having a short cutoff wavelength and excellent laser light resistance can be obtained.

Typical examples of the triamide compound of the present invention include tribenzamide, 4-methyltribenzamide, trinaphthylamide, 4,4'-dimethoxytrinaphthylamide, trianthrylamide and tris-3-.
Bromoanthrylamide, tribenzoquinoylamide,
4- (N, N-dimethylamino) tribenzoquinoylamide, trinaphthoquinoylamide, 6-nitrotrinaphthoquinoylamide, trianthraquinoylamide, 6,
6'-dicyanotrianthraquinoylamide, tripyrrolylamide, 5-chlorotripyrrolylamide, triindolylamide, 5-hydroxytriindolylamide,
Examples thereof include triquinolinolinylamide, 6-phenyltriquinolinolinylamide, triphenazinylamide, 3,3′-dimethylthiotriphenazinylamide, dibenznaphthylamide, and benzdicinnamylamide.

Next, a method for synthesizing the triamide compound will be described. The triamide compound can be easily synthesized by a method of introducing a substituent into the unsubstituted triamide by a chemical reaction or a method represented by the formula [6].

[0030]

[Chemical 11]

In the formula, X is a substituent having a very high leaving ability as represented by a halogen atom. Also, Ar
Represents an atomic group having a π-electron conjugated structure. Examples of the base to be used include organic bases typified by triethylamine and pyridine, organic metal bases typified by n-butyllithium and lithium diisopropylamide, and inorganic bases typified by sodium hydroxide and potassium carbonate.

Further, as the solvent, tetrahydrofuran,
A highly polar solvent typified by diethyl ether, N, N-dimethylformamide, a low polar solvent typified by n-hexane, etc. are used. Further, the reaction temperature at that time is preferably −80 ° C. to + 150 ° C.

The organic nonlinear optical material of the present invention can be synthesized by a known synthesis method other than the above.

[0034]

The organic nonlinear optical properties of the triamide compound of the present invention were investigated variously, such as prediction of the crystal structure by calculation of the hyperpolarizability of the molecule alone, the lowest excitation energy and the intermolecular interaction.

As a result, the organic nonlinear optical material of the present invention exhibits excellent nonlinear characteristics because the hyperpolarizability, which represents the nonlinear optical characteristics of the molecule alone, is sufficient for use in nonlinear optical elements such as wavelength conversion elements. This is because the structure has characteristics and the crystal structure is difficult to have the center of symmetry which is necessary for the development of the second-order nonlinear characteristics. It was also found that the absorption wavelength edge also has sufficient characteristics for a wavelength conversion element of a semiconductor laser.

[0036]

EXAMPLES Next, the present invention will be described with reference to Examples, and its synthetic method,
Detailed explanation including evaluation method.

Example 1 Synthesis of Tribenzamide ( A) Benzamide (2.0 g), triethylenediamine (4.
1 g), n-butyllithium hexane solution (24 ml)
And benzoyl chloride (5.6 g) were refluxed for 2 hours with stirring in tetrahydrofuran (THF).
20 ml of water was added to the reaction solution, the resulting product was filtered,
The desired tribenzamide (A) was obtained by purification. Results of [Infrared spectroscopy of the compound (IR) is 3060,1698cm ~ ^1. Example 2 Synthesis of 4-methoxytribenzamide (B) Paramethoxybenzamide (0.5 g), triethylenediamine (0.8 g), n-butyllithium hexane solution (5.0 ml) and benzoyl chloride (1. 1 g) was reacted, filtered and purified in the same manner as in Example 1 to obtain the desired 4-methoxytribenzamide (B). [I
R: 2917, 1698, 1244, 1034 cm- ¹ ] [Example 3] Synthesis of 4,4'-dimethoxytribenzamide (C) Benzamide (0.5 g), triethylenediamine (1.
0 g), n-butyllithium hexane solution (6.6 m
l) and paramethoxybenzoyl chloride (1.7 g)
And 4,4′-dimethoxytribenzamide (C) of interest by reacting, and filtering in the same manner as in Example 1.
Got [IR: 2933, 1694, 1246, 10
28 cm to ¹ ] [Example 4] Synthesis of trisparamethoxybenzamide (D) Paramethoxybenzamide (0.5 g), triethylenediamine (0.8 g), n-butyllithium hexane solution (5.0 ml) and paramethoxybenzoyl Chloride (1.4 g) was treated in the same manner as in Example 1 to obtain the target tris-paramethoxybenzamide (D). [IR: 29
82,1694,1246,1030 cm ~ ¹ ] [Example 5] Synthesis of 4-methyltribenzamide (E) Paramethylbenzamide (0.5 g), triethylenediamine (0.9 g), n-butyllithium hexane solution (5 0.4 ml) and benzoyl chloride (1.3 g) were treated in the same manner as in Example 1 to obtain the desired 4-methyltribenzamide (E). [IR: 2925, 1701 cm
~ ¹ ] [Example 6] Synthesis of 4,4'-dimethyltribenzamide (F) Benzamide (0.5 g), triethylenediamine (1.
0 g), n-butyllithium hexane solution (6.6 m
l) and paramethylbenzoyl chloride (1.5 g) were treated in the same manner as in Example 1 to obtain the desired 4,4′-dimethyltribenzamide (F). [IR: 2925, 1
700 cm- ¹ ] [Example 7] Synthesis of trisparamethylbenzamide (G) Paramethylbenzamide (0.5 g), triethylenediamine (0.9 g), n-butyllithium hexane solution (5.4 ml) and paramethylbenzoyl Chloride (1.
4 g) in the same manner as in Example 1 to obtain the target tris-paramethylbenzamide (G). [IR: 2923, 1
698 cm ~ ¹ ].

Example 8 Of 4,4′-dimethyl-4 ″ -methoxybenzamide
(H) Synthetic paramethoxybenzamide (0.5 g), triethylenediamine (0.8 g), n-butyllithium hexane solution (5.0 ml) and paramethylbenzoyl chloride (1.2 g) were prepared in the same manner as in Example 1. The purpose 4,
4'-Dimethyl-4 ''-methoxybenzamide (H)
Got [ ¹ H-NMR: 7.87 (d, 2H), 7.7
9 (d, 4H), 7.23 (d, 4H), 6.91 (d,
2H), 3.85 (s, 3H), 2.39 (d, 6H)] [Example 9] 4,4'-dimethoxy-4 ''-methyltribenzami
Synthesis of de (I) Paramethylbenzamide (0.5 g), triethylenediamine (0.9 g), n-butyllithium hexane solution (5.4 ml) and paramethoxybenzoyl chloride (1.5 g) were used in Example 1. Similarly, the purpose of 4,
4'-Dimethoxy-4 ''-methyltribenzamide (I) was obtained. [ ¹ H-NMR: 7.87 (d, 4H),
7.79 (d, 2H), 7.23 (d, 2H), 6.91
(D, 4H), 6.06 (s, 6H), 3.00 (s, 3
H)] [Example 10] of 4-methyl-4'-methoxytribenzamide (J)
Synthetic benzamide (1.0 g), triethylenediamine (2.
0 g), n-butyllithium hexane solution (12 ml)
And para-methoxybenzoyl chloride (1.7 g) were refluxed in THF for 1 hour with stirring, then para-methylbenzoyl chloride (1.5 g) was added and further refluxed for 1 hour, and 20 ml of water was added to the reaction solution. The resulting product is filtered and purified to give the desired 4-methyl-4'-
Methoxytribenzamide (J) was obtained. [ ¹ H-NM
R: 7.90 (d, 2H), 7.87 (d, 2H), 7.
56 (t, 2H), 7.43 (dd, 2H), 7.24
(D, 2H), 6.92 (d, 2H), 3.84 (s, 3
H), 2.39 (s, 3H)] [Example 11] Synthesis of tris-metamethoxybenzamide (K) Metamethoxybenzamide (0.5 g), triethylenediamine (0.8 g), n-butyllithium hexane solution ( (5.0 ml) and metamethoxybenzoyl chloride (1.4 g) were treated in the same manner as in Example 1 to obtain the target tris-metamethoxybenzamide (K). [Elemental analysis: C; 68.87%, H; 4.88%, N; 3.37
%] [Example 12] Synthesis of 4-bromotribenzamide (L ) A chloroform solution of benzoyl chloride (1.17 g) is cooled to -60 ° C, and pyridine (1.7 ml) is added. Parabromobenzamide (0.83) was added to this solution.
g) is added and stirred for 30 hours. Ethanol (2 ml)
After adding, the reaction solution is washed with 1N hydrochloric acid, 0.5N sodium hydroxide solution and water. After evaporating the solvent, the target 4-bromotribenzamide (L) was obtained. [IR: 2
925,1692 cm ~ ¹ ] [Example 13] Synthesis of 4,4'-dibromotribenzamide (M) Parabromobenzoyl chloride (1.0 g), pyridine (1 ml), benzamide (0.30 g) The desired 4,4′-dibromotribenzamide (M) is obtained by reacting and purifying in the same manner as in 12.
[IR: 2921,1694 cm ~ ¹ ] [Example 14] Synthesis of tris-para-bromobenzamide (N) Para-bromobenzoyl chloride (1.0 g), pyridine (1 ml), para-bromobenzamide (0.50 g)
In the same manner as in Example 12, the target trisparabromobenzamide (N) is obtained. [Elemental analysis: C; 44.
70%, H; 1.91%, N; 2.52%] [Example 15] Synthesis of 4-chlorotribenzamide (O) Benzoyl chloride (7.1 g), pyridine (5 m
l) and parachlorobenzamide (3.8 g) were treated in the same manner as in Example 12 to obtain the desired 4-chlorotribenzamide (O). [Elemental analysis: N; 3.84%] [Example 16] Synthesis of trisparachlorobenzamide (P) Parachlorobenzoyl chloride (2.5 g), pyridine (3 ml), and parachlorobenzamide (1.0 g) were used. The target tris-parachlorobenzamide (P) was obtained in the same manner as in Example 12. [Elemental analysis: C; 58.1
5%, H; 2.68%, N; 3.20%] [Example 17] Synthesis of trisparaiodobenzamide (Q) Paraiodobenzoyl chloride (3.3 g), pyridine (4 ml), paraiodobenzamide ( 1.6 g) in the same manner as in Example 12 to obtain the target tris-paraiodobenzamide (Q). [Elemental analysis: C; 35.3
8%, H; 1.54%, N; 2.13%] [Example 18] Synthesis of tris metabromobenzamide (R) metabromobenzoyl chloride (1.0 g), pyridine (1 ml), metabromobenzamide ( 0.50g)
In the same manner as in Example 12, the target tris-metabromobenzamide (R) was obtained. [Elemental analysis: C; 44.
70%, H; 2.17%, N; 2.45%] [Example 19] Synthesis of 3 -nitrotribenzamide (S) Tribenzamide (0.5 g) synthesized in Example 1 and nitronium tetrafluoro The reaction product is reacted with borate (0.32 g) in sulfolane, and after completion of the reaction, the reaction solution is poured into ice water and the product is filtered and purified to obtain the desired 3-nitrotribenzamide (S). [IR: 2930,
1696, 1520, 1352 cm ~ ¹ ] [Example 20] 3 , Synthesis of 3'- dinitrotribenzamide (T) Tribenzamide (0.5 g) synthesized in Example 1 and nitronium tetrafluoroborate (0.64 g) Are reacted in sulfolane in the same manner as in Example 11, followed by post-treatment, filtration, and purification to obtain the desired 3,3′-dinitrotribenzamide (T). [IR: 2926,169
5,1518,1349 cm ~ ¹ ] [Example 21] Synthesis of tris- metanitrobenzamide (U) Tribenzamide (0.5 g) synthesized in Example 1 and nitronium tetrafluoroborate (0.96 g) in sulfolane. Then, the target tris-metanitrobenzamide (U) is obtained in the same manner as in Example 11. [IR: 29
23, 1963, 1522, 1355 cm ~ ¹ ] [Example 22] Synthesis of tris-2-naphthamide (V) Naphthoyl chloride (0.95 g), pyridine (1 m
l) and naphthamide (0.43 g) were treated in the same manner as in Example 12 to obtain the target tris-2-naphthamide (V). [Elemental analysis: C; 82.53%, H; 4.42%,
N; 3.04%] [Example 23] Synthesis of benzdicinnamamide ( W) Benzamide (0.6 g), triethylenediamine (1.
1 g), n-butyllithium hexane solution (7.9 m
l) and cinnamoyl chloride (1.8 g) were treated in the same manner as in Example 1 to obtain the desired benzdicinnamamide (W).
Got [IR: 1650, 1300, 962 cm ~ ¹ ] [Example 24] Hyperpolarizability β of the triamide compound of the above (A) to (W)
Was calculated by the Ab initio method. Furthermore, the cutoff wavelengths of these compounds were measured in a saturated solution of methanol. Table 1 shows the calculation results and the measurement results.

[0039]

[Table 1]

From the calculation results shown in Table 1, it is shown that the compound of the present invention has a non-zero hyperpolarizability β and can be used as a nonlinear optical material.

Furthermore, the second harmonic generation of the compound (A) of Example 1 was measured by the powder method, and it was found that the compound (A) had SHG activity twice that of urea. Also, as is clear from Table 1, the cutoff wavelength is very short at the absorption wavelength edge of 350 nm or less.

The compound of the present invention can be used as a material for a nonlinear optical element of a wavelength conversion device by single crystal or by dispersing in a transparent polymer as in Example 25 below and orienting in a strong electric field. .

[Example 25] The tris-paramethoxybenzamide (D) obtained in Example 4 was mixed with a methyl methacrylate monomer and polymerized by heating. A solution of the polymer in chloroform was spin-coated to form a film, and the film was corona-poled. In addition, in the above corona poling, the distance between the electrodes is 1c.
m and an applied voltage of 7 kV and heating at 110 ° C. for 1 hour,
It was cooled to room temperature while voltage was applied.

When the nonlinear optical element of the wavelength conversion device was formed by using the above-mentioned nonlinear optical material, the same second harmonic as in the case of using the single crystal was obtained.

[0045]

The organic nonlinear material of the present invention has excellent nonlinear characteristics.

A laser beam having a wavelength in the visible region can be obtained by using the organic nonlinear material and combining it with a semiconductor laser.

Furthermore, a semiconductor laser wavelength converter using the organic nonlinear optical material, an optical functional element such as an optical switch operates efficiently, and has excellent nonlinear characteristics.

[Brief description of drawings]

FIG. 1 is a schematic configuration diagram of an example of a wavelength conversion device using the compound of the present invention.

[Explanation of symbols]

1 ... Laser diode, 2 ... Collimator, 3 ... Anamorphic prism pair, 4 ... Focusing lens, 5 ... SH
G element, 6 ... Laser light.

   ─────────────────────────────────────────────────── ─── Continued front page    (72) Inventor Hiroshi Terao             4026 Kujimachi, Hitachi City, Ibaraki Japan             Tachi Works Hitachi Research Laboratory (72) Inventor Tomoyuki Hamada             4026 Kujimachi, Hitachi City, Ibaraki Japan             Tachi Works Hitachi Research Laboratory (72) Inventor Masakazu Sagawa             4026 Kujimachi, Hitachi City, Ibaraki Japan             Tachi Works Hitachi Research Laboratory (72) Inventor Shintaro Hattori             4026 Kujimachi, Hitachi City, Ibaraki Japan             Tachi Works Hitachi Research Laboratory (72) Inventor Atsushi Tsunoda             4026 Kujimachi, Hitachi City, Ibaraki Japan             Tachi Works Hitachi Research Laboratory

Claims (11)

[Claims] 1. An organic nonlinear optical material comprising a compound represented by the formula [1]. [Chemical 1] [However, Ar _{1 to} Ar ₃ may be different from each other in an atomic group having a π-electron conjugated structure, and may be substituted with an organic substituent. ] 2. In the formula [1], Ar _{1 to} Ar ₃ are
Characterized by a π-conjugated atomic group selected from benzene ring, naphthalene ring, anthracene ring, benzoquinone ring, naphthoquinone ring, anthraquinone ring, pyrrole ring, imidazole ring, indole ring, quinoline ring, phenazine ring and cinnamyl group The organic nonlinear optical material according to claim 1. 3. In the above formula [1], Ar _{1 to} Ar ₃ are
Nitro group, cyano group, isocyanate group, carboxy group, allyl group, allyloxy group, allylsulfonyl group,
Allylsulfinyl group, allyloxysulfonyl group, allyloxycarbonyl group, allylthio group, acylamino group, acyloxy group, carbamoyl group, sulfamoyl group, alkyl group having 1 to 8 carbon atoms, the same alkyloxycarbonyl group, the same alkylsulfonyl group, Alkylsulfinyl group, same alkyloxysulfonyl group, same alkylthio group, alkoxy group having 1 to 8 carbon atoms, hydroxy group,
The organic nonlinear optical material according to claim 2, which is substituted with a substituent selected from a thiol group and a halogen atom. 4. An organic nonlinear optical material comprising a compound represented by the formula [2]. [Chemical 2] [However, Ar ₁ and Ar ₂ may be different from each other in an atomic group having a π electron conjugated structure, and may be substituted with an organic substituent. A _{1 to} A ₅ may be different from each other in H and an organic substituent. ] 5. An organic nonlinear optical material comprising a compound represented by the formula [3]. [Chemical 3] [However, Ar ₁ may be substituted by an organic substituent with an atomic group having a π electron conjugated structure. A _{1 to} A ₅ , B ₁
To B ₅ may be different from each other in H and an organic substituent. ] 6. An organic nonlinear optical material comprising a compound represented by the formula [4]. [Chemical 4] [However, A _{1 to} A ₅ , B _{1 to} B ₅ , and C _{1 to} C ₅ may be different from each other in H and an organic substituent. ] 7. In the above formula [2], [3] or [4], A _{1 to} A ₅ , B _{1 to} B ₅ and C _{1 to} C are hydrogen atoms, nitro groups, cyano groups, isocyanate groups and carboxy groups. Group, allyl group, allyloxy group, allylsulfonyl group, allylsulfinyl group, allyloxysulfonyl group, allyloxycarbonyl group, allylthio group, acylamino group, acyloxy group, carbamoyl group, sulfamoyl group, alkyl group having 1 to 8 carbon atoms, A substituent selected from the same alkyloxycarbonyl group, the same alkylsulfonyl group, the same alkylsulfinyl group, the same alkyloxysulfonyl group, the same alkylthio group, an alkoxy group having 1 to 8 carbon atoms, a hydroxy group, a thiol group, and a halogen atom. The organic nonlinear optical material according to claim 4, 5 or 6, characterized in that it is present. 8. An organic nonlinear optical material comprising a compound represented by the formula [5]. [Chemical 5] [Wherein R _{1 to} R ₃ are hydrogen atom, nitro group, cyano group, isocyanate group, carboxy group, allyl group, allyloxy group, allylsulfonyl group, allylsulfinyl group, allyloxysulfonyl group, allyloxycarbonyl group,
Allylthio group, acylamino group, acyloxy group, carbamoyl group, sulfamoyl group, alkyl group having 1 to 8 carbon atoms, same alkyloxycarbonyl group, same alkylsulfonyl group, same alkylsulfinyl group, same alkyloxysulfonyl group, same alkylthio group, It is selected from an alkoxy group having 1 to 8 carbon atoms, a hydroxy group, a thiol group and a halogen atom, and may be different from each other. ] 9. The organic nonlinear optical material represented by the above formulas [1] to [5] is a single crystal of 1 mm square or more, or the organic nonlinear optical material is dispersed in a transparent high molecular weight polymer and oriented in a strong electric field. A non-linear optical element, which is made of a film made of a material and is held in an optical resonator. 10. The nonlinear optical element according to claim 9, wherein the transparent high molecular weight polymer in which the organic nonlinear optical material is dispersed is a polymer having no absorption at 400 nm or more. 11. An optical wavelength having a light source, a condensing means for condensing the light from the light source, and a harmonic generating means for receiving the light condensed by the condensing means to generate a second harmonic. In the conversion device, the second harmonic generation means includes a single crystal of the organic nonlinear optical material represented by the formulas [1] to [5] or a polymer dispersion thereof in an optical path. Optical wavelength conversion device.