JP5205701B2 - Two-photon responsive organic photorefractive material and its electro-optic effect imparting method - Google Patents

Description

  The present invention relates to an organic photorefractive material and a method for imparting an electro-optic effect thereof, and more particularly to a novel photorefractive material having a high two-photon absorption cross section and a method for imparting an electro-optic effect using the two-photon absorption, Optical element, laser wavelength conversion element, optoelectronic switch, spatial light modulation element, four-wave mixing element, photolithography element, optical filter, optical logic gate, optical computing element, phase conjugate element, optical amplification element, optical bistable element, Optical resonance element, optical vibration element, beam amplification element, image correlation processing, associative memory element, imaging from distorted media, real-time holography, super-multiplex hologram recording, optical amplification, nonlinear optical information processing including optical neural network, optical limiter It is applied to storage and storage of high-density optical data.

Conventional examples relating to inorganic photorefractive materials include those disclosed in Patent Documents 1 to 3.
Moreover, the thing of patent document 4 indication is mentioned as a prior art example regarding an organic-inorganic composite photorefractive material.
Moreover, the thing of patent documents 5-17 is mentioned as a prior art example regarding organic photorefractive material.

Conventional photorefractive materials can exhibit an electro-optic effect only in a one-photon process. By utilizing the two-photon absorption phenomenon, it is possible to apply an electro-optical element characterized by extremely high spatial resolution.
In hologram recording using a conventional photorefractive material, recording / reproduction is performed in a one-photon process. Therefore, 1) Photon mode reactions are progressively accumulated even when left indoors, and the signal characteristics of the unrecorded part and the recorded part deteriorate. 2) At the time of volume hologram recording, in one-photon recording, it is difficult for light to reach the inside due to absorption of the recording layer itself, and recording with high spatial resolution and high degree of modulation is difficult.

(Photorefractive material)
A photorefractive material is a material whose refractive index changes when irradiated with light. Such a phenomenon in which the refractive index changes is presumed to be caused by the molecular orientation of molecules having large birefringence being changed by an electric field or by the Pockels effect or the Kerr effect. That is, when light is irradiated, electrons and holes (referred to as carriers) are generated, and a spatial electric field is generated by the movement of the carriers. Then, the refractive index in the material changes corresponding to this spatial electric field, and refractive index modulation becomes possible.

The photorefractive material is irradiated with two coherent light waves to form interference. In a place where the light intensity is strong, electrons in the donor level are excited to the conduction band, move by diffusion or drift, and are captured in a place where the light intensity is low. A positive charge remains in a place where the light intensity is strong, and a negative charge is captured in a place where the light intensity is weak. This creates a space charge distribution and produces an electrostatic field. As a result of the electro-optic effect by the electrostatic field, refractive index modulation corresponding to the spatial electric field occurs and a diffraction grating is formed. The period of this refractive index change is the same as the period of the interference fringes, and this refractive index grating acts as a hologram diffraction grating.
In addition, unlike other diffraction grating formation mechanisms (such as photochromic), the diffraction grating formed by a photorefractive material is out of phase (π / 2) with the intensity distribution of interference light (interference fringes). Energy transfer occurs between one light beam incident on the material and the other light beam. By utilizing this characteristic, application to an optical modulation element that performs nonlinear signal processing on signal light becomes possible.
Further, since the diffracted light generated from the diffraction grating has a phase conjugate, it can also be used as a phase conjugate mirror.

(Two-photon absorption material)
A two-photon absorption material is a material that can excite molecules at a wavelength in the non-resonant region, and has a real excited state at an energy level twice that of the photon used for excitation. is there.
The transition efficiency of two-photon absorption is proportional to the square of the applied photoelectric field (the two-photon absorption square characteristic). For this reason, when a laser is irradiated, two-photon absorption occurs only at a position where the electric field strength is high at the center of the laser spot, and no two-photon absorption occurs at a portion where the electric field strength is weak at the peripheral portion. In the three-dimensional space, two-photon absorption occurs only in a region where the electric field strength at the focal point where the laser light is collected by the lens is large, and no two-photon absorption occurs in the region outside the focal point because the electric field strength is weak. Compared to the linear absorption of one photon where excitation occurs at all positions in proportion to the intensity of the applied photoelectric field, the two-photon absorption is excited only at a pinpoint inside the space due to this square characteristic. Therefore, the spatial resolution is significantly improved.

Utilizing this characteristic, research on a three-dimensional memory for recording bit data by causing a spectral change, a refractive index change or a polarization change by two-photon absorption at a predetermined position of a recording medium is underway. Since two-photon absorption occurs in proportion to the square of the intensity of light, a memory using two-photon absorption can make the spot size smaller than a memory using one-photon absorption. Super-resolution recording capable of recording small bit data exceeding the normal diffraction limit becomes possible. In addition, from the characteristics of high spatial resolution derived from this square characteristic, development for applications such as a light limiting material, a cured material of a photo-curing resin for stereolithography, and a fluorescent dye material for a two-photon fluorescence microscope is being promoted.
Furthermore, in the case of inducing two-photon absorption, it is possible to use a short-pulse laser in the near-infrared region that has a longer wavelength than the wavelength region in which the linear absorption band of the compound exists and does not have absorption. Since the near-infrared light of the so-called transparent region, which does not have a linear absorption band of the compound, is used, the excitation light can reach the inside of the sample without being absorbed or scattered, and because of the square characteristic of the two-photon absorption, Since pinpoints can be excited with high spatial resolution, two-photon absorption and two-photon emission are also expected in photochemotherapy applications such as two-photon contrast and two-photon photodynamic therapy (PDT) in biological tissues. In addition, research on upconversion lasing has been reported from the viewpoint of a wavelength conversion device because photons with higher energy than the energy of incident photons can be extracted by using two-photon absorption and two-photon emission.

  The photorefractive effect is that the molecular orientation of a molecule having a large birefringence is changed by irradiation with a visible light laser, or the refractive index of a substance is changed by a Pockels effect or a Kerr effect. By using this photorefractive effect, electro-optic elements, laser wavelength conversion elements, optoelectronic switches, spatial light modulation elements, four-wave mixing elements, photolithography elements, optical filters, optical logic gates, optical computing elements, phase conjugate elements , Optical amplification element, optical bistable element, optical resonance element, optical vibration element, beam amplification element, image correlation processing, associative memory element, imaging from distorted medium, real-time holography, super-multiplex hologram recording, optical amplification, optical neural Application to non-linear optical information processing including networks, optical limiting, storage of high-density optical data, etc. is expected, and development of photorefractive materials having a large photorefractive effect is underway.

(Inorganic photorefractive material)
As inorganic photorefractive materials, inorganic ferroelectric crystals such as lithium niobate, lithium tantalate, barium titanate, strontium barium titanate, potassium niobium tantalate, and bismuth silicate are conventionally known. In particular, a lithium niobate single crystal containing a transition metal element (for example, Fe, Rh, Cu, etc.) exhibits a highly sensitive and highly efficient photoinduced refractive index change effect (photorefractive effect). These are studied as light modulation elements that perform nonlinear signal processing, and are also used as materials for studying the mechanism of the expression of photorefractive characteristics.
However, they are often difficult to grow an inorganic single crystal containing a dopant, and their use is limited because they are crystals and are hard and brittle, making them difficult to mold.

  In recent years, therefore, active research and development have been conducted on photorefractive materials using organic materials as photorefractive materials that are easy to produce crystalline materials and have high workability.

(Organic photorefractive material)
From such a background, a photorefractive material (hereinafter referred to as an organic photorefractive material) using an amorphous organic compound that is low in cost and excellent in moldability is demanded. Organic photorefractive materials using the Pockels effect or Kerr effect include organic photoconductive materials or charge generation materials and charge transport materials for forming a spatial electric field, and nonlinear optical materials that generate a refractive index change corresponding to the spatial electric field. Is essential. In addition, polymeric substrates that support these materials, sensitizers to efficiently absorb irradiated light, charge-trapping materials for efficiently capturing charges, improved moldability, and changes in substrate properties Therefore, it is composed of a plasticizer and a compatibilizer. In addition, one component may play a plurality of roles such as a charge transfer material / polymer base material, an electron accepting material / charge trap material, and a charge trap material / polymer base material.
Up to now, mainly non-linear optical material blended with polymer having photoconductive function, conversely, non-linear optical material-containing polymer blended with photoconductive function as low molecular weight compound, and photorefractive In terms of properties, a compound obtained by blending an inert polymer compound with a photoconductive function and a nonlinear optical dye with a low molecular weight has been proposed. Both respond with only one-photon absorption.
In addition to the Pockels effect, birefringence due to molecular orientation contributes to refractive index modulation. For this reason, organic photorefractive materials having a low glass transition temperature do not limit the molecular motion of nonlinear optical materials even near room temperature, and some exhibit high photorefractive characteristics that exceed those of inorganic materials.
As the organic material-based photorefractive material, the above-described conventional techniques (see Patent Documents 5 to 17) have been proposed.

(Hologram recording)
In recent years, an optical information recording apparatus is known as an apparatus for recording a large amount of information such as a moving image or a high-density image. Conventionally, as an optical information recording device, a magnetic tape medium that cannot be randomly accessed and a hard disk that is not replaceable and easily damaged, and a compact and inexpensive optical recording medium that is replaceable and randomly accessible, has attracted more attention. Magneto-optical information recording devices, optical phase change information recording devices, CD-Rs and DVD-Rs have been put into practical use.
By the way, in the rapid trend of highly information-oriented society, even in consumer use, high-density recording media for recording image information of 100 GB or more at low cost and in business use such as computer backup use and broadcast backup use. There is a need for an ultra-high-density recording medium capable of recording large-capacity information of about 1 TB or more at high speed and low cost, and existing two-dimensional optical recording media cannot meet future demands based on physical principles. .
Therefore, a three-dimensional optical recording medium that performs recording in the film thickness direction has attracted attention as an ultra-high density recording medium. Unlike conventional surface optical recording, a volume phase hologram recording system using a hologram, particularly a digital volume hologram, has attracted attention as a three-dimensional optical recording medium that effectively uses the film thickness direction of the recording medium.

In the organic photorefractive material, carriers are generated from the photoconductive material or the charge generation material by absorption of light, and an internal electric field is generated by being positively and negatively separated by the photoconductive material or the charge transfer material and the charge trapping material. This internal electric field generates an electro-optic effect of the nonlinear optical material, and changes the refractive index distribution in the substrate. By applying this phenomenon, it is considered that volume hologram recording with a high recording density is possible in principle.
A hologram that records interference fringes by absorption is called an amplitude hologram, and a hologram that records by surface relief or refractive index modulation is called a phase hologram. Amplitude holograms are not preferred in terms of light utilization efficiency because light diffraction efficiency or reflection efficiency is significantly reduced due to light absorption, and phase holograms are usually preferred.
In a volume phase hologram, the phase of light can be modulated without absorbing light by forming many interference fringes with different refractive indexes in the hologram recording material instead of optical absorption.
In particular, reflective volume phase holograms, also called Lippmann holograms, are capable of full color, white reproduction and high resolution with high diffraction efficiency due to wavelength selective reflection by black diffraction, and high resolution full color 3D display. Application to is also possible.
In a holographic memory using a volume phase hologram recording material, two-dimensional digital information (referred to as signal light) using a spatial light modulation element (SLM) such as DMD or LCD instead of object light reflected from a three-dimensional object. Will be recorded a lot. At the time of recording, multiplex recording such as angle multiplexing, phase multiplexing, wavelength multiplexing, and shift multiplexing is performed, so that the capacity can be increased to 1 TB. In addition, a CCD, CMOS, or the like is usually used for reading, and the parallel transfer and reading thereof can increase the transfer rate up to 1 Gbps.

(Hologram recording material)
The following are known as hologram recording materials.
<Hologram type><Modulationtype><Recordingmaterial>
Hologram--Phase type --- Refractive index modulation ---- Silver salt emulsion
│ │ ├-Dichromated gelatin
│ │ ├-Photopolymer
│ │ ├-Photorefractive crystal
│ │ └-Photorefractive material
│ └-Unevenness modulation ――┬-Photoresist
│ └-Thermoplastic
└―Amplitude type ――――――――――― ┬-Silver emulsion
└—Photochromic materials

  Although silver salt emulsions have high sensitivity, wet processing is necessary, bleaching processing is complicated, scattering is large, light resistance is poor and shelf life is short, and dichromated gelatin also has high diffraction efficiency and low noise. On the other hand, it has drawbacks such as poor storage stability, requires wet processing, and extremely low recording sensitivity, and has many problems as a hologram recording material.

Photopolymers (JP-A-6-43634 of Patent Document 18, JP-A-8-16078 of Patent Document 19, JP-A-11-51247 of Patent Document 20, JP-A-2001-523842 of Patent Document 21) The system (see Japanese Patent Laid-Open Publication) can achieve both high diffraction efficiency and dry processing, but has a fatal drawback of low recording sensitivity and large volume shrinkage. Although the volume shrinkage ratio is improved by changing from radical polymerization to cation polymerization, there is basically no prospect of achieving both high sensitivity, low shrinkage, and storage stability.
The photorefractive crystal has many problems as a practical hologram recording material application because it is difficult to produce a medium with a large area, is expensive, has poor light resistance, and has a short shelf life.
Photoresists and thermoplastics are not suitable for volume holograms due to uneven modulation.
Photochromic polymers (see WO97 / 044365 of Patent Document 22 and JP-A-2005-266610 of Patent Document 23) are rewritable, but have low recording sensitivity, volume shrinkage problems, and record storage stability. Unfortunately, it is not a practical material.

Under such circumstances, photorefractive materials are attracting attention.
A photorefractive material is a material that generates carriers (electrons, holes) by light irradiation, generates an internal electric field due to the movement of the carriers, and changes the refractive index due to the nonlinear optical effect caused by it. The only thing that moves is the carrier, which has the advantage that volume shrinkage due to optical recording does not occur. Furthermore, since the generated internal electric field can be erased, it has great potential as a rewritable hologram recording material and multilayer optical recording material. (Refer to known technology described in the above patent document)

(Two-photon responsive organic photorefractive material)
None of the conventional techniques can be found at present, such as a two-photon responsive organic photorefractive material, a method of imparting an electro-optic effect with two photons, and a method of recording a hologram with two photons on an organic photorefractive material.

Moreover, as a prior art example of forming a hologram in a two-photon process, there is one disclosed in ISOM / ODS 2005 MB1 “Holographic storage without holography: Optical data storage by localized alteration of a format hologram” in Non-Patent Document 1. The recording material is a photopolymer, not an organic photorefractive material.
“Hologram recording method and hologram recording material” disclosed in Japanese Patent Application Laid-Open No. 2005-99416 of Patent Document 24: The recording material configuration is (1) a two-photon absorbing dye and (2) a material system that reacts via the excitation energy of the dye ( And the recording material is not an organic photorefractive material.

Japanese Patent Laid-Open No. 7-306425 JP-A-9-179478 JP-A-11-30791 JP-A-11-31815 Japanese Patent Publication No. 6-55901 Japanese Patent No. 3721396 Japanese Patent Laid-Open No. 11-38457 JP 2000-256320 A JP 2000-319234 A JP 2003-202607 A JP 2003-322886 A JP 2004-212576 A JP 2004-258604 A JP 2004-317868 A JP 2005-157254 A JP 2005-316278 A JP 2006-18112 A JP-A-6-43634 JP-A-8-16078 Japanese National Patent Publication No. 11-512847 JP-T-2001-523842 WO97 / 044365 JP 2005-266610 A JP 2005-99416 A ISOM / ODS 2005 MB1 “Holographic storage without holography: Optical data storage by localized alteration of a format hologram”

  In view of the above prior art, the present invention provides a two-photon responsive organic photorefractive material, and enables an electro-optic element characterized by extremely high spatial resolution. In addition, a two-photon recording volume hologram capable of recording / reproducing with high reliability, high spatial resolution, and high modulation degree is realized.

As a result of intensive studies, the present inventors have found that a material system having a specific structure has a function as a photoconductive material and a photocharge generation material, and also has a large two-photon absorption cross-sectional area. It came to the present invention in which the above-mentioned subject was solved.
That is, according to the present invention, a photoconductive material or charge generation material having a two-photon absorption ability and a nonlinear optical material coexist to constitute an organic photorefractive material. In order to further enhance the electro-optic effect, an electron accepting compound, a charge trapping material, and a charge transport material are mixed as appropriate. In addition, it is composed of a polymer base material that supports these materials, a sensitizer to improve the efficiency of absorption of irradiation light, a plasticizer, a compatibilizer, etc. to change the physical properties of the base material. Is done. In addition, one component may play a plurality of roles such as a charge transfer material / polymer base material, an electron accepting material / charge trap material, and a charge trap material / polymer base material.
The organic photorefractive material configured as described above can impart an electro-optic effect not only by a normal one-photon process but also by a two-photon absorption process.
As the photoconductive material or charge generation material, an arylamine polymer compound having the following specific structure can be used, but a material having both the function as a photoconductive material or charge generation material and the two-photon absorption ability Any of them can be applied.
The organic photorefractive material of the present invention has a large two-photon absorption cross section in a wavelength region approximately twice the maximum absorption wavelength of the photoconductive material or charge generation material, and exhibits high sensitivity and electro-optic effect by the two-photon absorption process. It can be given.
By applying an electro-optic effect to organic photorefractive materials in a two-photon process, it can be pinpointed inside the space peculiar to two-photon absorption, and features extremely high spatial resolution that cannot be achieved with conventional one-photon processes. Application to an electro-optic element is possible.
Furthermore, by applying this phenomenon to hologram recording, there is no deterioration in the signal characteristics of the unrecorded part and recorded part due to the accumulation of photon mode reaction when left indoors (one-photon absorption is a light-shielding structure) with high reliability. In addition, since there is no attenuation of light due to absorption of the recording layer itself as in one-photon recording, volume holographic recording is possible with extremely high spatial resolution and high modulation degree.

That is, according to the present invention, (1) "an organic photorefractive material composed of a photoconductive material having two-photon absorption ability and a nonlinear optical material",
(2) "Organic photorefractive material composed of a photoconductive material having two-photon absorption ability, an electron accepting material and a nonlinear optical material",
(3) "Organic photorefractive material composed of a photoconductive material having two-photon absorption ability, a charge trapping material, and a nonlinear optical material",
(4) "Organic photorefractive material composed of a charge generation material having two-photon absorption ability, a charge transport material and a nonlinear optical material",
(5) "Organic photorefractive material composed of coexistence of charge generating material having two-photon absorption ability, charge transporting material, electron accepting material and nonlinear optical material",
(6) "Organic photorefractive material composed of coexistence of charge generation material having two-photon absorption ability, charge transport material, charge trapping material, and nonlinear optical material",
(7) The organic photorefractive material according to any one of (1) to (6), wherein the photoconductive material and the charge generation material are made of a two-photon absorption material represented by the following general formula (I): ;

Ａｒ_１は置換又は無置換の芳香族炭化水素基であり、
Ａｒ_２及びＡｒ_３はそれぞれ独立に置換又は無置換の芳香族炭化水素基の二価基でありかつ、Ａｒ_４は置換若しくは無置換の、チオフェン、ビフェニル、フルオレン又はアントラセンの二価基であり、
Ａｒ_５及びＡｒ_６はそれぞれ独立に置換又は無置換の芳香族炭化水素基である。」、
（８）「光導電性材料及び電荷発生材料が、下記一般式（II）である二光子吸収材料からなる前記第（１）項乃至第（６）項の何れかに記載の有機フォトリフラクティブ材料；

Ar ₁ is a substituted or unsubstituted aromatic hydrocarbon group,
Ar ₂ and Ar ₃ are each independently a divalent group of a substituted or unsubstituted aromatic hydrocarbon group, and Ar ₄ is a substituted or unsubstituted divalent group of thiophene, biphenyl, fluorene or anthracene,
Ar ₅ and Ar ₆ are each independently a substituted or unsubstituted aromatic hydrocarbon group. "
(8) The organic photorefractive material according to any one of (1) to (6), wherein the photoconductive material and the charge generation material are made of a two-photon absorption material represented by the following general formula (II): ;

Ａｒ_１は置換又は無置換の芳香族炭化水素基であり、
Ａｒ_４は置換若しくは無置換の、チオフェン、ビフェニル、フルオレン又はアントラセンの二価基であり、ｘ及びｙは１以上４以下の整数であり、
Ａｒ_５及びＡｒ_６はそれぞれ独立に置換又は無置換の芳香族炭化水素基であり、
Ｒ_１及びＲ_２はそれぞれ独立に、水素原子、ハロゲン基、置換若しくは無置換のアルキル基、置換若しくは無置換のアルコキシ基又は置換若しくは無置換のアルキルチオ基であり、かつ、前記ｘ及び／又は前記ｙが２ 以上である場合、複数個の前記Ｒ_１及び前記Ｒ_２は、それぞれ独立している。」、
（９）「光導電性材料及び電荷発生材料が、下記一般式（III）である二光子吸収材料からなる前記第（１）項乃至第（６）項の何れかに記載の有機フォトリフラクティブ材料；

Ar ₁ is a substituted or unsubstituted aromatic hydrocarbon group,
Ar ₄ is a substituted or unsubstituted divalent group of thiophene, biphenyl, fluorene, or anthracene, x and y are integers of 1 or more and 4 or less,
Ar ₅ and Ar ₆ are each independently a substituted or unsubstituted aromatic hydrocarbon group,
R ₁ and R ₂ are each independently a hydrogen atom, a halogen group, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkoxy group, or a substituted or unsubstituted alkylthio group, and the above x and / or the above When y is 2 or more, the plurality of R ₁ and R ₂ are independent of each other. "
(9) The organic photorefractive material according to any one of (1) to (6), wherein the photoconductive material and the charge generation material are made of a two-photon absorption material represented by the following general formula (III): ;

Ａｒ_４は置換若しくは無置換の、チオフェン、ビフェニル、フルオレン又はアントラセンの二価基であり、
Ａｒ_５及びＡｒ_６はそれぞれ独立に置換又は無置換の芳香族炭化水素基であり、
ｘ及びｙは１以上４以下の整数であり、ｚは１以上５以下の整数であり、
Ｒ_１及びＲ_２はそれぞれ独立に水素原子、ハロゲン基、置換若しくは無置換のアルキル基、置換若しくは無置換のアルコキシ基又は置換若しくは無置換のアルキルチオ基であり、
Ｒ_３は水素基、ハロゲン基、置換若しくは無置換のアルキル基、置換若しくは無置換のアルコキシ基、置換若しくは無置換のアルキルチオ基又は置換若しくは無置換のアリール基であり、かつ、前記ｘ、前記ｙ及び前記ｚが２以上である場合、複数個の前記Ｒ_１、前記Ｒ_２及び前記Ｒ_３はそれぞれ独立している。」、
（１０）「光導電性材料及び電荷発生材料が、下記一般式（IV）である二光子吸収材料からなる前記第（１）項乃至第（６）項の何れかに記載の有機フォトリフラクティブ材料；

Ar ₄ is a substituted or unsubstituted divalent group of thiophene, biphenyl, fluorene or anthracene,
Ar ₅ and Ar ₆ are each independently a substituted or unsubstituted aromatic hydrocarbon group,
x and y are integers of 1 or more and 4 or less, z is an integer of 1 or more and 5 or less,
R ₁ and R ₂ are each independently a hydrogen atom, a halogen group, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkoxy group, or a substituted or unsubstituted alkylthio group,
R ₃ is a hydrogen group, a halogen group, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkoxy group, a substituted or unsubstituted alkylthio group, or a substituted or unsubstituted aryl group, and the above x, y And when z is 2 or more, the plurality of R ₁ , R ₂ and R ₃ are independent of each other. "
(10) The organic photorefractive material according to any one of (1) to (6), wherein the photoconductive material and the charge generation material are made of a two-photon absorption material represented by the following general formula (IV): ;

Ａｒ_４は置換若しくは無置換の、ベンゼン、チオフェン、ビフェニル、フルオレン又はアントラセンの二価基であり、
Ａｒ_５及びＡｒ_６はそれぞれ独立に置換又は無置換の芳香族炭化水素基であり、
ｖは１以上３以下の整数であり、ｗ、ｘ及びｙは１以上４以下の整数であり、
Ｒ_１、Ｒ_２、Ｒ_４、Ｒ_５、Ｒ_６及びＲ_７はそれぞれ独立に水素原子、ハロゲン基、置換若しくは無置換のアルキル基、置換若しくは無置換のアルコキシ基又は置換若しくは無置換のアルキルチオ基であり、かつ、前記ｖ、前記ｗ、前記ｘ及び前記ｙが２以上である場合、複数個の前記Ｒ_１、前記Ｒ_２、前記Ｒ_４及び前記Ｒ_５がそれぞれ独立している。」、
（１１）「光導電性材料及び電荷発生材料が、下記一般式（Ｖ）である二光子吸収材料からなる前記第（１）項乃至第（６）項の何れかに記載の有機フォトリフラクティブ材料；

Ar ₄ is a substituted or unsubstituted divalent group of benzene, thiophene, biphenyl, fluorene or anthracene,
Ar ₅ and Ar ₆ are each independently a substituted or unsubstituted aromatic hydrocarbon group,
v is an integer of 1 to 3, w, x and y are integers of 1 to 4.
R ₁ , R ₂ , R ₄ , R ₅ , R ₆ and R ₇ are each independently a hydrogen atom, a halogen group, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkoxy group, or a substituted or unsubstituted alkylthio group. And v, w, x and y are 2 or more, the plurality of R ₁ , R ₂ , R ₄ and R ₅ are independent of each other. "
(11) The organic photorefractive material according to any one of (1) to (6), wherein the photoconductive material and the charge generation material are made of a two-photon absorption material represented by the following general formula (V): ;

Ａｒ_４は置換若しくは無置換の、ベンゼン、チオフェン、ビフェニル、フルオレン又はアントラセンの二価基であり、
Ａｒ_５及びＡｒ_６はそれぞれ独立に置換又は無置換の芳香族炭化水素基であり、
ｖは１以上３以下の整数であり、ｗ、ｘ及びｙは１以上４以下の整数であり、
Ｒ_１、Ｒ_２、Ｒ_４及びＲ_５はそれぞれ独立に水素原子、ハロゲン基、置換若しくは無置換のアルキル基、置換若しくは無置換のアルコキシ基又は置換若しくは無置換のアルキルチオ基であり、かつ、前記ｖ、前記ｗ、前記ｘ及び前記ｙが２以上である場合、複数個の前記Ｒ_１、前記Ｒ_２、前記Ｒ_４ 及び前記Ｒ_５がそれぞれ独立している。」、
（１２）「光導電性材料及び電荷発生材料が、下記一般式（VI）で表される繰り返し単位を有する二光子吸収材料からなる前記第（１）項乃至第（６）項の何れかに記載の有機フォトリフラクティブ材料；

Ar ₄ is a substituted or unsubstituted divalent group of benzene, thiophene, biphenyl, fluorene or anthracene,
Ar ₅ and Ar ₆ are each independently a substituted or unsubstituted aromatic hydrocarbon group,
v is an integer of 1 to 3, w, x and y are integers of 1 to 4.
R ₁ , R ₂ , R ₄ and R ₅ are each independently a hydrogen atom, a halogen group, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkoxy group or a substituted or unsubstituted alkylthio group, and When v, w, x and y are 2 or more, a plurality of R ₁ , R ₂ , R ₄ and R ₅ are independent of each other. "
(12) In any one of the above items (1) to (6), wherein the photoconductive material and the charge generation material are made of a two-photon absorption material having a repeating unit represented by the following general formula (VI) Organic photorefractive materials as described;

Ａｒ_１は置換又は無置換の芳香族炭化水素基であり、
Ａｒ_２及びＡｒ_３はそれぞれ独立に置換又は無置換の芳香族炭化水素基の二価基でありかつ、Ａｒ_４は置換若しくは無置換の、ベンゼン、チオフェン、ビフェニル、フルオレン又はアントラセンの二価基である。」、
（１３）「光導電性材料及び電荷発生材料が、下記一般式（VII）で表される繰り返し単位を有する二光子吸収材料からなる前記第（１）項乃至第（６）項の何れかに記載の有機フォトリフラクティブ材料；

Ar ₁ is a substituted or unsubstituted aromatic hydrocarbon group,
Ar ₂ and Ar ₃ are each independently a divalent group of a substituted or unsubstituted aromatic hydrocarbon group, and Ar ₄ is a substituted or unsubstituted divalent group of benzene, thiophene, biphenyl, fluorene or anthracene. is there. "
(13) In any one of the above items (1) to (6), wherein the photoconductive material and the charge generation material are made of a two-photon absorption material having a repeating unit represented by the following general formula (VII): Organic photorefractive materials as described;

Ａｒ_１は置換又は無置換の芳香族炭化水素基であり、
Ａｒ_４は置換若しくは無置換の、ベンゼン、チオフェン、ビフェニル、フルオレン又はアントラセンの二価基であり、ｘ及びｙは１以上４以下の整数であり、
Ｒ_１及びＲ_２はそれぞれ独立に、水素原子、ハロゲン基、置換若しくは無置換のアルキル基、置換若しくは無置換のアルコキシ基又は置換若しくは無置換のアルキルチオ基であり、かつ、前記ｘ及び／又は前記ｙが２以上である場合、複数個の前記Ｒ_１及び前記Ｒ_２は、それぞれ独立している。」、
（１４）「光導電性材料及び電荷発生材料が、下記一般式（VIII）で表される繰り返し単位を有する二光子吸収材料からなる前記第（１）項乃至第（６）項の何れかに記載の有機フォトリフラクティブ材料；

Ar ₁ is a substituted or unsubstituted aromatic hydrocarbon group,
Ar ₄ is a substituted or unsubstituted divalent group of benzene, thiophene, biphenyl, fluorene or anthracene, x and y are integers of 1 or more and 4 or less,
R ₁ and R ₂ are each independently a hydrogen atom, a halogen group, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkoxy group, or a substituted or unsubstituted alkylthio group, and the above x and / or the above When y is 2 or more, the plurality of R ₁ and R ₂ are independent of each other. "
(14) In any one of the above items (1) to (6), wherein the photoconductive material and the charge generation material are made of a two-photon absorption material having a repeating unit represented by the following general formula (VIII): Organic photorefractive materials as described;

Ａｒ_４は置換若しくは無置換の、ベンゼン、チオフェン、ビフェニル、フルオレン又はアントラセンの二価基であり、
ｘ及びｙは１以上４以下の整数であり、ｚは１以上５以下の整数であり、
Ｒ_１及びＲ_２はそれぞれ独立に水素原子、ハロゲン基、置換若しくは無置換のアルキル基、置換若しくは無置換のアルコキシ基又は置換若しくは無置換のアルキルチオ基であり、
Ｒ_３は水素基、ハロゲン基、置換若しくは無置換のアルキル基、置換若しくは無置換のアルコキシ基、置換若しくは無置換のアルキルチオ基又は置換若しくは無置換のアリール基であり、かつ、前記ｘ、前記ｙ及び前記ｚが２以上である場合、複数個の前記Ｒ_１、前記Ｒ_２及び前記Ｒ_３はそれぞれ独立している。」、
（１５）「光導電性材料及び電荷発生材料が、下記一般式（IX）で表される繰り返し単位を有する二光子吸収材料からなる前記第（１）項乃至第（６）項の何れかに記載の有機フォトリフラクティブ材料；

Ar ₄ is a substituted or unsubstituted divalent group of benzene, thiophene, biphenyl, fluorene or anthracene,
x and y are integers of 1 or more and 4 or less, z is an integer of 1 or more and 5 or less,
R ₁ and R ₂ are each independently a hydrogen atom, a halogen group, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkoxy group, or a substituted or unsubstituted alkylthio group,
R ₃ is a hydrogen group, a halogen group, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkoxy group, a substituted or unsubstituted alkylthio group, or a substituted or unsubstituted aryl group, and the above x, y And when z is 2 or more, the plurality of R ₁ , R ₂ and R ₃ are independent of each other. "
(15) In any one of the above items (1) to (6), wherein the photoconductive material and the charge generation material are made of a two-photon absorption material having a repeating unit represented by the following general formula (IX) Organic photorefractive materials as described;

Ａｒ_４は置換若しくは無置換の、ベンゼン、チオフェン、ビフェニル、フルオレン又はアントラセンの二価基であり、
ｖは１以上３以下の整数であり、ｗ、ｘ及びｙは１以上４以下の整数であり、
Ｒ_１、Ｒ_２、Ｒ_４、Ｒ_５、Ｒ_６及びＲ_７はそれぞれ独立に水素原子、ハロゲン基、置換若しくは無置換のアルキル基、置換若しくは無置換のアルコキシ基又は置換若しくは無置換のアルキルチオ基であり、かつ、前記ｖ、前記ｗ、前記ｘ及び前記ｙが２以上である場合、複数個の前記Ｒ_１、前記Ｒ_２、前記Ｒ_４及び前記Ｒ_５がそれぞれ独立している。」、
（１６）「光導電性材料及び電荷発生材料が、下記一般式（Ｘ）で表される繰り返し単位を有する二光子吸収材料からなる前記第（１）項乃至第（６）項の何れかに記載の有機フォトリフラクティブ材料；

Ar ₄ is a substituted or unsubstituted divalent group of benzene, thiophene, biphenyl, fluorene or anthracene,
v is an integer of 1 to 3, w, x and y are integers of 1 to 4.
R ₁ , R ₂ , R ₄ , R ₅ , R ₆ and R ₇ are each independently a hydrogen atom, a halogen group, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkoxy group, or a substituted or unsubstituted alkylthio group. And v, w, x and y are 2 or more, the plurality of R ₁ , R ₂ , R ₄ and R ₅ are independent of each other. "
(16) In any one of the above items (1) to (6), wherein the photoconductive material and the charge generation material are made of a two-photon absorption material having a repeating unit represented by the following general formula (X) Organic photorefractive materials as described;

Ａｒ_４は置換若しくは無置換の、ベンゼン、チオフェン、ビフェニル、フルオレン又はアントラセンの二価基であり、
ｖは１以上３以下の整数であり、ｗ、ｘ及びｙは１以上４以下の整数であり、
Ｒ_１、Ｒ_２、Ｒ_４及びＲ_５はそれぞれ独立に水素原子、ハロゲン基、置換若しくは無置換のアルキル基、置換若しくは無置換のアルコキシ基又は置換若しくは無置換のアルキルチオ基であり、かつ、前記ｖ、前記ｗ、前記ｘ及び前記ｙが２以上である場合、複数個の前記Ｒ_１、前記Ｒ_２、前記Ｒ_４及び前記Ｒ_５がそれぞれ独立している。」、
（１７）「前記第（１）項乃至第（１６）項の何れかに記載の有機フォトリフラクティブ材料に二光子吸収過程により電気光学効果を発現させる電気光学効果付与方法」、
（１８）「前記第（１）項乃至第（１６）項の何れかに記載の有機フォトリフラクティブ材料に二光子吸収過程によりホログラム記録する電気光学効果付与方法」によって達成される。

Ar ₄ is a substituted or unsubstituted divalent group of benzene, thiophene, biphenyl, fluorene or anthracene,
v is an integer of 1 to 3, w, x and y are integers of 1 to 4.
R ₁ , R ₂ , R ₄ and R ₅ are each independently a hydrogen atom, a halogen group, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkoxy group or a substituted or unsubstituted alkylthio group, and When v, w, x and y are 2 or more, a plurality of R ₁ , R ₂ , R ₄ and R ₅ are independent of each other. "
(17) "Electro-optical effect imparting method for causing the organic photorefractive material according to any one of (1) to (16) to exhibit an electro-optical effect by a two-photon absorption process",
(18) This is achieved by “an electro-optical effect imparting method for recording a hologram on an organic photorefractive material according to any one of items (1) to (16) by a two-photon absorption process”.

In here, the (1) to (6) shows the basic configuration of a two-photon response organic photorefractive material of the present invention, (7) - (16), two-photon response photoconductive material and the charge of the present invention The polymer structure of the generating material is shown, and (17) to (18) show the electro-optic effect imparting method of the two-photon responsive organic photorefractive material of the present invention and the most suitable application example thereof.

According to the present invention, the arylamine polymer compound represented by the above formulas (I) to (X) is used as a photoconductive material or charge generation material of an organic photorefractive material.
Thereby, a photoconductive material and a charge generation material that efficiently absorb two-photons can be obtained.
This compound has a large two-photon absorption cross section in the wavelength region almost twice the maximum absorption wavelength, and the organic photorefractive material composed of this compound has high sensitivity and electro-optic effect by the two-photon absorption process. It can be given.

As will be apparent from the following detailed and specific description, the present invention makes it possible to realize a two-photon responsive organic photorefractive material not found in the prior art.
In addition, by applying an electro-optic effect to the organic photorefractive material by a two-photon absorption process, application to an electro-optic element characterized by extremely high spatial resolution that cannot be achieved by the conventional one-photon process can be realized.
In addition, the two-photon hologram recording using the present organic photorefractive material has an extremely excellent effect of enabling volume holographic recording with high reliability, extremely high spatial resolution to the inside, and high modulation. Is.

As described above, as a result of intensive studies, the present inventors have found that a material system having a specific structure has a function as a photoconductive material and a charge generation material, and also has a large two-photon absorption cross section. As a result, they have reached the present invention.
That is, an organic photorefractive material is configured by coexisting a photoconductive material or charge generation material having two-photon absorption ability and a nonlinear optical material. In order to further enhance the electro-optic effect, an electron accepting compound, a charge trapping material, and a charge transport material are mixed as appropriate. In addition, it is composed of a polymer base material that supports these materials, a sensitizer to improve the efficiency of absorption of irradiation light, a plasticizer, a compatibilizer, etc. to change the physical properties of the base material. Is done. In addition, one component may play a plurality of roles such as a charge transfer material / polymer base material, an electron accepting material / charge trap material, and a charge trap material / polymer base material.
The organic photorefractive material configured as described above can impart an electro-optic effect not only by a normal one-photon process but also by a two-photon absorption process.

As the photoconductive material or charge generation material, an arylamine polymer compound having the following specific structure can be used, but a material having both the function as a photoconductive material or charge generation material and the two-photon absorption ability Any of them can be applied.
The organic photorefractive material of the present invention has a large two-photon absorption cross section in a wavelength region approximately twice the maximum absorption wavelength of the photoconductive material or charge generation material, and exhibits high sensitivity and electro-optic effect by the two-photon absorption process. It can be given.

By applying an electro-optic effect to organic photorefractive materials in a two-photon process, it can be pinpointed inside the space peculiar to two-photon absorption, and features extremely high spatial resolution that cannot be achieved with conventional one-photon processes. Application to an electro-optic element is possible.
Furthermore, by applying this phenomenon to hologram recording, there is no deterioration in the signal characteristics of the unrecorded part and recorded part due to the accumulation of photon mode reaction when left indoors (one-photon absorption is a light-shielding structure) with high reliability. In addition, since there is no attenuation of light due to absorption of the recording layer itself as in one-photon recording, volume holographic recording is possible with extremely high spatial resolution and high modulation degree.

(Organic photoconductive material)
The organic photoconductive material is a compound having a function of generating electrons and holes (carriers) by irradiating light, and generating a spatial electric field when the carriers move.
A feature of the organic photoconductive material of the present invention is that the above function can be expressed not only in a normal one-photon process but also in a two-photon process.
That is, according to the present invention, a two-photon absorption material made of a compound represented by the following general formulas (I) to (X) is used as the organic photoconductive material.

A two-photon absorption material comprising a compound represented by formula (I).

Ａｒ_１は置換又は無置換の芳香族炭化水素基であり、
Ａｒ_２及びＡｒ_３はそれぞれ独立に置換又は無置換の芳香族炭化水素基の二価基であり
かつ、Ａｒ_４は置換若しくは無置換の、チオフェン、ビフェニル、フルオレン又はアントラセンの二価基であり、
Ａｒ_５及びＡｒ_６はそれぞれ独立に置換又は無置換の芳香族炭化水素基である二光子吸収材料。
これにより、効率良く二光子を吸収する有機材料を得ることができる。

Ar ₁ is a substituted or unsubstituted aromatic hydrocarbon group,
Ar ₂ and Ar ₃ are each independently a divalent group of a substituted or unsubstituted aromatic hydrocarbon group, and Ar ₄ is a substituted or unsubstituted divalent group of thiophene, biphenyl, fluorene or anthracene,
Ar ₅ and Ar ₆ are each a two-photon absorption material in which each is independently a substituted or unsubstituted aromatic hydrocarbon group.
Thereby, the organic material which absorbs two photons efficiently can be obtained.

A two-photon absorption material comprising a compound represented by the general formula (II).

Ａｒ_１は置換又は無置換の芳香族炭化水素基であり、
Ａｒ_４は置換若しくは無置換の、チオフェン、ビフェニル、フルオレン又はアントラセンの二価基であり、ｘ及びｙは１以上４以下の整数であり、
Ａｒ_５及びＡｒ_６はそれぞれ独立に置換又は無置換の芳香族炭化水素基であり、
Ｒ_１及びＲ_２はそれぞれ独立に、水素原子、ハロゲン基、置換若しくは無置換のアルキル基、置換若しくは無置換のアルコキシ基又は置換若しくは無置換のアルキルチオ基であり、かつ、前記ｘ及び／又は前記ｙが２以上である場合、複数個の前記Ｒ_１及び前記Ｒ_２は、それぞれ独立している二光子吸収材料。
これにより、効率良く二光子を吸収する有機材料を得ることができる。

Ar ₁ is a substituted or unsubstituted aromatic hydrocarbon group,
Ar ₄ is a substituted or unsubstituted divalent group of thiophene, biphenyl, fluorene, or anthracene, x and y are integers of 1 or more and 4 or less,
Ar ₅ and Ar ₆ are each independently a substituted or unsubstituted aromatic hydrocarbon group,
R ₁ and R ₂ are each independently a hydrogen atom, a halogen group, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkoxy group, or a substituted or unsubstituted alkylthio group, and the above x and / or the above When y is 2 or more, the plurality of R ₁ and R ₂ are independent two-photon absorption materials.
Thereby, the organic material which absorbs two photons efficiently can be obtained.

A two-photon absorption material comprising a compound represented by the general formula (III).

Ａｒ_４は置換若しくは無置換の、チオフェン、ビフェニル、フルオレン又はアントラセンの二価基であり、
Ａｒ_５及びＡｒ_６はそれぞれ独立に置換又は無置換の芳香族炭化水素基であり、
ｘ及びｙは１以上４以下の整数であり、ｚは１以上５以下の整数であり、
Ｒ_１及びＲ_２はそれぞれ独立に水素原子、ハロゲン基、置換若しくは無置換のアルキル基、置換若しくは無置換のアルコキシ基又は置換若しくは無置換のアルキルチオ基であり、
Ｒ_３は水素基、ハロゲン基、置換若しくは無置換のアルキル基、置換若しくは無置換のアルコキシ基、置換若しくは無置換のアルキルチオ基又は置換若しくは無置換のアリール基であり、かつ、前記ｘ、前記ｙ及び前記ｚが２以上である場合、複数個の前記Ｒ_１、前記Ｒ_２及び前記Ｒ_３はそれぞれ独立している二光子吸収材料。
これにより、効率良く二光子を吸収する有機材料を得ることができる。

Ar ₄ is a substituted or unsubstituted divalent group of thiophene, biphenyl, fluorene or anthracene,
Ar ₅ and Ar ₆ are each independently a substituted or unsubstituted aromatic hydrocarbon group,
x and y are integers of 1 or more and 4 or less, z is an integer of 1 or more and 5 or less,
R ₁ and R ₂ are each independently a hydrogen atom, a halogen group, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkoxy group, or a substituted or unsubstituted alkylthio group,
R ₃ is a hydrogen group, a halogen group, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkoxy group, a substituted or unsubstituted alkylthio group, or a substituted or unsubstituted aryl group, and the above x, y And when z is 2 or more, the plurality of R ₁ , R ₂ and R ₃ are independent two-photon absorption materials.
Thereby, the organic material which absorbs two photons efficiently can be obtained.

A two-photon absorption material comprising a compound represented by the general formula (IV).

Ａｒ_４は置換若しくは無置換の、ベンゼン、チオフェン、ビフェニル、フルオレン又はアントラセンの二価基であり、
Ａｒ_５及びＡｒ_６はそれぞれ独立に置換又は無置換の芳香族炭化水素基であり、
ｖは１以上３以下の整数であり、ｗ、ｘ及びｙは１以上４以下の整数であり、
Ｒ_１、Ｒ_２、Ｒ_４、Ｒ_５、Ｒ_６及びＲ_７はそれぞれ独立に水素原子、ハロゲン基、置換若しくは無置換のアルキル基、置換若しくは無置換のアルコキシ基又は置換若しくは無置換のアルキルチオ基であり、かつ、前記ｖ、前記ｗ、前記ｘ及び前記ｙが２以上である場合、複数個の前記Ｒ_１、前記Ｒ_２、前記Ｒ_４及び前記Ｒ_５がそれぞれ独立している二光子吸収材料。
これにより、効率良く二光子を吸収する有機材料を得ることができる。

Ar ₄ is a substituted or unsubstituted divalent group of benzene, thiophene, biphenyl, fluorene or anthracene,
Ar ₅ and Ar ₆ are each independently a substituted or unsubstituted aromatic hydrocarbon group,
v is an integer of 1 to 3, w, x and y are integers of 1 to 4.
R ₁ , R ₂ , R ₄ , R ₅ , R ₆ and R ₇ are each independently a hydrogen atom, a halogen group, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkoxy group, or a substituted or unsubstituted alkylthio group. And when v, w, x and y are 2 or more, a plurality of R ₁ , R ₂ , R ₄ and R ₅ are independent from each other. material.
Thereby, the organic material which absorbs two photons efficiently can be obtained.

A two-photon absorption material comprising a compound represented by the general formula (V).

Ａｒ_４は置換若しくは無置換の、ベンゼン、チオフェン、ビフェニル、フルオレン又はアントラセンの二価基であり、
Ａｒ_５及びＡｒ_６はそれぞれ独立に置換又は無置換の芳香族炭化水素基であり、
ｖは１以上３以下の整数であり、ｗ、ｘ及びｙは１以上４以下の整数であり、
Ｒ_１、Ｒ_２、Ｒ_４及びＲ_５はそれぞれ独立に水素原子、ハロゲン基、置換若しくは無置換のアルキル基、置換若しくは無置換のアルコキシ基又は置換若しくは無置換のアルキルチオ基であり、かつ、前記ｖ、前記ｗ、前記ｘ及び前記ｙが２以上である場合、複数個の前記Ｒ_１、前記Ｒ_２、前記Ｒ_４及び前記Ｒ_５がそれぞれ独立している二光子吸収材料。
これにより、効率良く二光子を吸収する有機材料を得ることができる。

Ar ₄ is a substituted or unsubstituted divalent group of benzene, thiophene, biphenyl, fluorene or anthracene,
Ar ₅ and Ar ₆ are each independently a substituted or unsubstituted aromatic hydrocarbon group,
v is an integer of 1 to 3, w, x and y are integers of 1 to 4.
R ₁ , R ₂ , R ₄ and R ₅ are each independently a hydrogen atom, a halogen group, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkoxy group or a substituted or unsubstituted alkylthio group, and When v, the w, the x, and the y are 2 or more, a plurality of the R ₁ , R ₂ , R _4, and R ₅ are independent from each other.
Thereby, the organic material which absorbs two photons efficiently can be obtained.

A two-photon absorption material comprising a material having a repeating unit represented by the general formula (VI).

Ａｒ_１は置換又は無置換の芳香族炭化水素基であり、
Ａｒ_２及びＡｒ_３はそれぞれ独立に置換又は無置換の芳香族炭化水素基の二価基であり
かつ、Ａｒ_４は置換若しくは無置換の、ベンゼン、チオフェン、ビフェニル、フルオレン又はアントラセンの二価基である二光子吸収材料。
これにより、効率良く二光子を吸収する有機材料を得ることができる。

Ar ₁ is a substituted or unsubstituted aromatic hydrocarbon group,
Ar ₂ and Ar ₃ are each independently a divalent group of a substituted or unsubstituted aromatic hydrocarbon group, and Ar ₄ is a substituted or unsubstituted divalent group of benzene, thiophene, biphenyl, fluorene or anthracene. A two-photon absorbing material.
Thereby, the organic material which absorbs two photons efficiently can be obtained.

A two-photon absorption material comprising a material having a repeating unit represented by formula (VII).

Ａｒ_１は置換又は無置換の芳香族炭化水素基であり、
Ａｒ_４は置換若しくは無置換の、ベンゼン、チオフェン、ビフェニル、フルオレン又はアントラセンの二価基であり、ｘ及びｙは１以上４以下の整数であり、
Ｒ_１及びＲ_２はそれぞれ独立に、水素原子、ハロゲン基、置換若しくは無置換のアルキル基、置換若しくは無置換のアルコキシ基又は置換若しくは無置換のアルキルチオ基であり、かつ、前記ｘ 及び／又は前記ｙが２以上である場合、複数個の前記Ｒ_１及び前記Ｒ_２は、それぞれ独立している二光子吸収材料。
これにより、効率良く二光子を吸収する有機材料を得ることができる。

Ar ₁ is a substituted or unsubstituted aromatic hydrocarbon group,
Ar ₄ is a substituted or unsubstituted divalent group of benzene, thiophene, biphenyl, fluorene or anthracene, x and y are integers of 1 or more and 4 or less,
R ₁ and R ₂ are each independently a hydrogen atom, a halogen group, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkoxy group, or a substituted or unsubstituted alkylthio group, and x 1 and / or When y is 2 or more, the plurality of R ₁ and R ₂ are independent two-photon absorption materials.
Thereby, the organic material which absorbs two photons efficiently can be obtained.

A two-photon absorption material comprising a material having a repeating unit represented by formula (VIII).

Ａｒ_４は置換若しくは無置換の、ベンゼン、チオフェン、ビフェニル、フルオレン又はアントラセンの二価基であり、
ｘ及びｙは１以上４以下の整数であり、ｚは１以上５以下の整数であり、
Ｒ_１及びＲ_２はそれぞれ独立に水素原子、ハロゲン基、置換若しくは無置換のアルキル基、置換若しくは無置換のアルコキシ基又は置換若しくは無置換のアルキルチオ基であり、
Ｒ_３は水素基、ハロゲン基、置換若しくは無置換のアルキル基、置換若しくは無置換のアルコキシ基、置換若しくは無置換のアルキルチオ基又は置換若しくは無置換のアリール基であり、かつ、前記ｘ、前記ｙ及び前記ｚが２以上である場合、複数個の前記Ｒ_１、前記Ｒ_２及び前記Ｒ_３はそれぞれ独立している二光子吸収材料。
これにより、効率良く二光子を吸収する有機材料を得ることができる。

Ar ₄ is a substituted or unsubstituted divalent group of benzene, thiophene, biphenyl, fluorene or anthracene,
x and y are integers of 1 or more and 4 or less, z is an integer of 1 or more and 5 or less,
R ₁ and R ₂ are each independently a hydrogen atom, a halogen group, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkoxy group, or a substituted or unsubstituted alkylthio group,
R ₃ is a hydrogen group, a halogen group, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkoxy group, a substituted or unsubstituted alkylthio group, or a substituted or unsubstituted aryl group, and the above x, y And when z is 2 or more, the plurality of R ₁ , R ₂ and R ₃ are independent two-photon absorption materials.
Thereby, the organic material which absorbs two photons efficiently can be obtained.

A two-photon absorption material comprising a material having a repeating unit represented by the general formula (IX).

Ａｒ_４は置換若しくは無置換の、ベンゼン、チオフェン、ビフェニル、フルオレン又はアントラセンの二価基であり、
ｖは１以上３以下の整数であり、ｗ、ｘ及びｙは１以上４以下の整数であり、
Ｒ_１、Ｒ_２、Ｒ_４、Ｒ_５、Ｒ_６及びＲ_７はそれぞれ独立に水素原子、ハロゲン基、置換若しくは無置換のアルキル基、置換若しくは無置換のアルコキシ基又は置換若しくは無置換のアルキルチオ基であり、
かつ、前記ｖ、前記ｗ、前記ｘ及び前記ｙが２以上である場合、複数個の前記Ｒ_１、前記Ｒ_２、前記Ｒ_４及び前記Ｒ_５がそれぞれ独立している二光子吸収材料。
これにより、効率良く二光子を吸収する有機材料を得ることができる。

Ar ₄ is a substituted or unsubstituted divalent group of benzene, thiophene, biphenyl, fluorene or anthracene,
v is an integer of 1 to 3, w, x and y are integers of 1 to 4.
R ₁ , R ₂ , R ₄ , R ₅ , R ₆ and R ₇ are each independently a hydrogen atom, a halogen group, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkoxy group, or a substituted or unsubstituted alkylthio group. And
And wherein v, the w, the x and the case y is 2 or more, a plurality of said _{R 1,} said _{R 2,} wherein _{R 4} and wherein _{R 5} is two-photon absorption materials are independent.
Thereby, the organic material which absorbs two photons efficiently can be obtained.

A two-photon absorption material comprising a material having a repeating unit represented by the general formula (X).

Ａｒ_４は置換若しくは無置換の、ベンゼン、チオフェン、ビフェニル、フルオレン又はアントラセンの二価基であり、
ｖは１以上３以下の整数であり、ｗ、ｘ及びｙは１以上４以下の整数であり、
Ｒ_１、Ｒ_２、Ｒ_４及びＲ_５はそれぞれ独立に水素原子、ハロゲン基、置換若しくは無置換のアルキル基、置換若しくは無置換のアルコキシ基又は置換若しくは無置換のアルキルチオ基であり、かつ、前記ｖ、前記ｗ、前記ｘ及び前記ｙが２以上である場合、複数個の前記Ｒ_１、前記Ｒ_２、前記Ｒ_４ 及び前記Ｒ_５ がそれぞれ独立している二光子吸収材料。

Ar ₄ is a substituted or unsubstituted divalent group of benzene, thiophene, biphenyl, fluorene or anthracene,
v is an integer of 1 to 3, w, x and y are integers of 1 to 4.
R ₁ , R ₂ , R ₄ and R ₅ are each independently a hydrogen atom, a halogen group, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkoxy group or a substituted or unsubstituted alkylthio group, and When v, the w, the x, and the y are 2 or more, a plurality of the R ₁ , R ₂ , R _4, and R ₅ are independent from each other.

A method for synthesizing these organic photorefractive materials and the like are described in the specification of Japanese Patent Application No. 2006-0667067, but will be described again below just in case.
The organic photorefractive material manufacturing method of the present invention includes, for example, Wittig-Horner reaction using aldehyde and phosphonate, Wittig reaction using aldehyde and phosphonium salt, Heck reaction using vinyl substituent and halide, amine and halide Ullmann reaction using can be used, and can be produced by a known method. In particular, the Wittig-Horner reaction and the Wittig reaction are effective because of the simplicity of the reaction operation.

As an example, a method for producing an organic photorefractive material (polymer) in the present invention using a Wittig-Horner reaction will be described.
As shown in the following reaction formula, the organic photorefractive material in the present invention is prepared by mixing a solution in which the phosphonate ester compound and the aldehyde compound are present stoichiometrically and a base more than twice the molar amount thereof. The polymerization reaction proceeds and can be obtained.
In the production of organic photorefractive material of the present invention, for example, an aryl amine moiety as A, or using a monomer combination of Ar ⁴ as B, or A as Ar ^{4, B} as a monomer of a combination of an aryl amine moiety Use it.

  The dialdehyde compound can be synthesized by various known reactions. For example, the following Vilsmeier reaction,

  Alternatively, a reaction of an aryllithium compound with a formylating agent such as DMF, N-formylmorpholine, N-formylpiperidine,

  Alternatively, the following Gatterman reaction,

  Alternatively, various oxidation reactions of hydroxymethyl compounds,

等を挙げることができ、これら反応を用いてジアルデヒド化合物を合成することができる。
また、上記ホスホン酸ジエステル化合物についても、公知の種々の反応により合成することが可能であるが、下記Ｍｉｃｈａｅｌｉｓ−Ａｒｂｕｚｏｖ 反応が特に容易である。

These reactions can be used to synthesize dialdehyde compounds.
The phosphonic acid diester compound can also be synthesized by various known reactions, but the following Michaelis-Arbuzov reaction is particularly easy.

  The base used in the above reaction is not particularly limited as long as a phosphonate carbanion is formed, and examples thereof include metal alkoxides, metal hydrides, and organic lithium compounds, such as potassium t-butoxide, sodium t-butoxide, lithium t. -Butoxide, potassium 2-methyl-2-butoxide, sodium 2-methyl-2-butoxide, sodium methoxide, sodium ethoxide, potassium ethoxide, potassium methoxide, sodium hydride, potassium hydride, methyllithium, ethyllithium Propyl lithium, n-butyl lithium, s-butyl lithium, t-butyl lithium, phenyl lithium, lithium naphthylide, lithium amide, lithium diisopropylamide and the like.

The amount of the base used in the reaction is usually only the same amount as the polymerization active point of the phosphonate ester compound, but an excessive amount can be used.
The above base may be added to the reaction system in a solid state or a suspension solution. However, it is particularly preferable to add the base as a homogeneous solution in order to improve the homogeneity of the resulting polymer. As the solvent for dissolving the base, a solvent that forms a stable solution with the base to be used must be selected, but as other factors, those having a high solubility of the base are preferable, and the high molecular weight product produced in the reaction system is also preferred. Those that do not impair the solubility in the reaction solvent are good. Further, the solvent in which the high molecular weight product to be formed dissolves well is good. Depending on the characteristics of the base used and the high molecular weight to be produced, generally known alcohols and ethers are used. It can be arbitrarily selected from a system, an amine system, a hydrocarbon solvent and the like.

  Examples of a combination of a base and a solvent for uniformly dissolving the base include, for example, a methanol solution of sodium methoxide, an ethanol solution of sodium ethoxide, a 2-propanol solution of potassium t-butoxide, and 2-methyl-2-methyl ester of potassium t-butoxide. Propanol solution, tetrahydrofuran solution of potassium t-butoxide, dioxane solution of potassium t-butoxide, hexane solution of n-butyllithium, ether solution of methyllithium, tetrahydrofuran solution of lithium t-butoxide, cyclohexane solution of lithium diisopropylamide, potassium bis There are various combinations of solutions including a toluene solution of trimethylsilylamide and the like, and some solutions are easily available as commercial products. From the viewpoint of mild reaction conditions and ease of handling, a metal alkoxide-based solution is preferably used, such as solubility of the polymer to be produced, ease of handling, efficiency of the reaction, solubility of the polymer to be produced, etc. From the viewpoint, an ether-based solution of metal t-butoxide is preferably used, and a tetrahydrofuran solution of potassium t-butoxide is more preferably used.

In the above polymerization reaction, a base solution may be added to the solution of the phosphonate ester compound and the aldehyde compound, a solution of the phosphonate ester compound and the aldehyde compound may be added to the base solution, and may be added to the reaction system at the same time. There is no restriction on the order of addition.
The polymerization time in the above polymerization reaction may be appropriately set according to the reactivity of the monomers used or the molecular weight of the desired polymer, but is preferably 0.2 hours to 30 hours.
The reaction temperature in the above polymerization reaction does not need to be controlled and the polymerization reaction proceeds favorably at room temperature. However, it is possible to heat or cool to raise the reaction efficiency to a milder condition.
Moreover, it is also possible to add a molecular weight regulator in order to adjust the molecular weight in the above polymerization operation, or a sealing agent for sealing the end of the polymer as a terminal modifying group to the reaction system during the reaction, It can also be added at the start of the reaction. Therefore, a substituent based on a terminator may be bonded to the terminal of the arylamine polymer in the present invention.
Examples of the molecular weight regulator and terminal blocking agent include compounds having one reactive group such as diethyl benzylphosphonate and benzaldehyde.

The preferred molecular weight of the organic photorefractive material (polymer) of the present invention is 1000 to 1000000 in terms of polystyrene-equivalent number average molecular weight, more preferably 2000 to 500000. When the molecular weight is too small, the film forming property such as the generation of cracks is deteriorated and the practicality becomes poor. On the other hand, when the molecular weight is too large, the solubility in a general organic solvent is deteriorated, the viscosity of the solution becomes high and the coating becomes difficult, which also causes a problem in practical use.
Also, a small amount of a branching agent can be added during the polymerization in order to improve the mechanical properties. The branching agent used is a compound having three or more polymerization reaction active groups (which may be the same or different). These branching agents may be used alone or in combination.

The arylamine polymer obtained as described above is used after removing impurities such as the base used in the polymerization, unreacted monomer, terminal terminator, and inorganic salts generated during the polymerization. For these purification operations, conventionally known methods such as reprecipitation, extraction, Soxhlet extraction, ultrafiltration, dialysis and the like can be used.
<Synthesis example>

[Synthesis Example 1; Synthesis of Polymer 1]

A 100 ml four-necked flask was charged with 0.852 g (2.70 mmol) of dialdehyde and 1.525 g (2.70 mmol) of diphosphonate shown in the above reaction formula, and purged with nitrogen, and 75 ml of tetrahydrofuran was added. To this solution, 6.75 ml (6.75 mmol) of a 1.0 moldm- ³ tetrahydrofuran solution of potassium t-butoxide was added dropwise and stirred at room temperature for 2 hours, and then diethyl benzylphosphonate and benzaldehyde were sequentially added, followed by further stirring for 2 hours. About 1 ml of acetic acid was added to terminate the reaction, and the solution was washed with water. After the solvent was distilled off under reduced pressure, purification by reprecipitation was performed using tetrahydrofuran and methanol to obtain 1.07 g of polymer 1. The yield was 73%, and the elemental analysis values were as follows.
Elemental analysis value (calculated value); C: 84.25% (84.02%), H: 8.20% (7.93%), N: 2.33% (2.45%).
The glass transition temperature determined from differential scanning calorimetry was 116.9 ° C.
The number average molecular weight in terms of polystyrene measured by gel filtration chromatography (GPC) was 8500, and the weight average molecular weight was 20000.

[Synthesis Example 2; Synthesis of Polymer 2]

The same operation as in Synthesis Example 1 was performed, and 518.3 mg of Polymer 2 was obtained from 419.5 mg (1.00 mmol) of the dialdehyde and 564.5 mg (1.00 mmol) of the diphosphonate. The yield was 62%, and the elemental analysis values were as follows.
Elemental analysis value (calculated value); C: 85.18% (85.55%), H: 8.03% (7.63%), N: 2.10% (2.08%).
The glass transition temperature determined from differential scanning calorimetry was 133 ° C.
The number average molecular weight in terms of polystyrene measured by GPC was 39200, and the weight average molecular weight was 116000.

[Synthesis Example 3; Synthesis of Polymer 3]

The same operation as in Synthesis Example 1 was performed to obtain 1.32 g of the polymer 3 from 1.00 g (2.40 mmol) of the dialdehyde and 1.35 g (2.40 mmol) of the diphosphonate. The yield was 82%, and the elemental analysis values were as follows.
Elemental analysis value (calculated value); C: 85.33% (85.55%), H: 7.86% (7.63%), N: 2.30% (2.08%).
The glass transition temperature determined from differential scanning calorimetry was 151.9 ° C.
The number average molecular weight in terms of polystyrene measured by GPC was 44400, and the weight average molecular weight was 118,000.

[Synthesis Example 4; Synthesis of Polymer 4]

In a 200 ml four-necked flask, 0.872 g (2.648 mmol) of the above dialdehyde and 1.495 g (2.648 mmol) of diphosphonate were placed, and the atmosphere was purged with nitrogen to 80 ml of tetrahydrofuran and 14.1 mg (0.132 mmol) of benzaldehyde. Was added. To this solution, 8.00 ml (8.00 mmol) of a 1.0 moldm- ³ tetrahydrofuran solution of potassium t-butoxide was added dropwise and stirred at room temperature for 2 hours, and then 60.5 mg (0.265 mmol) of diethyl benzylphosphonate was added. Stir for 1 hour. About 1 ml of acetic acid was added to complete the reaction, and the reaction solution was washed with water. After the solvent was distilled off under reduced pressure, purification by reprecipitation was performed using tetrahydrofuran and methanol to obtain 1.328 g of polymer 5. The yield was 86%, and the elemental analysis values were as follows.
Elemental analysis value (calculated value); C: 83.80% (84.06%), H: 8.60% (8.90%), N: 2.15% (2.39%).
The glass transition temperature determined from differential scanning calorimetry was 122.1 ° C.
The number average molecular weight in terms of polystyrene measured by GPC was 13200, and the weight average molecular weight was 32500.

[Synthesis Example 5; Synthesis of Polymer 5]

The same operation as in Synthesis Example 4 was performed to obtain 0.74 g of the polymer 7 from 1.00 g (2.48 mmol) of the dialdehyde and 1.40 g (2.48 mmol) of the diphosphonate. The yield was 45%, and the elemental analysis values were as follows.
Elemental analysis value (calculated value); C: 85.56 (85.27%), H: 8.02% (7.78%), N: 2.01% (2.12%).
The number average molecular weight in terms of polystyrene measured by GPC was 22700, and the weight average molecular weight was 51900.

[Synthesis Example 6; Synthesis of Polymer 6]

The same operation as in Synthesis Example 4 was performed to obtain 1.473 g of the polymer 8 from 0.872 g (2.648 mmol) of the dialdehyde and 1.495 g (2.648 mmol) of the diphosphonate. The yield was 95%, and the elemental analysis values were as follows.
Elemental analysis value (calculated value); C: 84.25% (84.06%), H: 8.75% (8.90%), N: 2.23% (2.39%).
The glass transition temperature determined from differential scanning calorimetry was 135.8 ° C.
The number average molecular weight in terms of polystyrene measured by GPC was 15400, and the weight average molecular weight was 39900.

[Synthesis Example 7; Synthesis of Polymer 7]

The same operation as in Synthesis Example 4 was performed to obtain 2.72 g of the polymer 11 from 2.12 g (5.50 mmol) of the dialdehyde and 2.63 g (5.50 mmol) of the diphosphonate. The yield was 89%, and the elemental analysis values were as follows.
Elemental analysis value (calculated value); C: 90.89% (90.77%), H: 6.50% (6.71%), N: 2.22% (2.52%).
The number average molecular weight in terms of polystyrene measured by GPC was 3700, and the weight average molecular weight was 8,000.

[Synthesis Example 8; Synthesis of Polymer 8]

The same operation as in Synthesis Example 4 was performed to obtain 2.34 g of the polymer 12 from 2.12 g (5.50 mmol) of the dialdehyde and 2.50 g (5.50 mmol) of the diphosphonate. The yield was 80%, and the elemental analysis values were as follows.
Elemental analysis value (calculated value); C: 90.64% (90.35%), H: 6.82% (7.01%), N: 2.55% (2.63%).
The number average molecular weight in terms of polystyrene measured by GPC was 5,500, and the weight average molecular weight was 13,300.

[Synthesis Example 9: Synthesis of Polymer 9]

A 200 ml four-necked flask was charged with 0.835 g (2.648 mmol) of the dialdehyde and 1.241 g (2.648 mmol) of diphosphonate, and purged with nitrogen to 80 ml of tetrahydrofuran and 14.1 mg (0.132 mmol) of benzaldehyde. Was added. To this solution, 8.00 ml (8.00 mmol) of a 1.0 moldm-3 tetrahydrofuran solution of potassium t-butoxide was added dropwise, followed by stirring at room temperature for 0.5 hours and then refluxing for 3 hours. 60.5 mg (0.265 mmol) of diethyl benzylphosphonate was added, and the mixture was further refluxed for 1 hour. After allowing to cool, about a few drops of acetic acid were added to terminate the reaction, and the reaction solution was added dropwise to water. The precipitated solid was filtered off and purified by reprecipitation using tetrahydrofuran and methanol to obtain 0.83 g of polymer 13. The yield was 66%, and the elemental analysis values were as follows.
Elemental analysis value (calculated value); C: 83.01% (83.32%), H: 7.01% (6.99%), N: 2.89% (2.94%), S: 6 80% (6.76%).
The glass transition temperature determined from differential scanning calorimetry was 163.4 ° C.
The number average molecular weight in terms of polystyrene measured by GPC was 7900, and the weight average molecular weight was 17,200.

[Synthesis Example 10; Synthesis of Polymer 10]

The same operation as in Synthesis Example 9 was performed to obtain 0.918 g of the polymer 14 from 1.021 g (2.648 mmol) of the dialdehyde and 1.241 g (2.648 mmol) of the diphosphonate. The yield was 62%, and the elemental analysis values were as follows.
Elemental analysis value (calculated value); C: 83.55% (83.62%), H: 7.74% (7.94%), N: 2.63% (2.57%), S: 6 0.02% (5.87%).
The glass transition temperature determined from differential scanning calorimetry was 125.9 ° C.
The number average molecular weight in terms of polystyrene measured by GPC was 15500, and the weight average molecular weight was 48700.

[Synthesis Example 11; Synthesis of Polymer 11]

The same operation as in Synthesis Example 9 was performed to obtain 0.817 g of polymer 15 from 1.106 g (2.648 mmol) of the dialdehyde and 1.241 g (2.648 mmol) of diphosphonate. The yield was 53%, and the elemental analysis values were as follows.
Elemental analysis value (calculated value); C: 85.52% (85.22%), H: 7.00% (6.80%), N: 2.15% (2.42%), S: 5 .50% (5.55%).
The glass transition temperature determined from differential scanning calorimetry was 186.9 ° C.
The number average molecular weight in terms of polystyrene measured by GPC was 11800, and the weight average molecular weight was 28400.

[Synthesis Example 12; Synthesis of Polymer 12]

The same operation as in Synthesis Example 4 was performed, and 1.386 g of the polymer 12 was obtained from 0.837 g (2.655 mmol) of the dialdehyde and 1.485 g (2.655 mmol) of the diphosphonate. The yield was 81%, and the elemental analysis values were as follows.
Elemental analysis value (calculated value); C: 90.11 (89.81%), H: 7.92% (8.01%), N: 2.01% (2.18%).
The glass transition temperature determined from differential scanning calorimetry was 182.9 ° C.
The number average molecular weight in terms of polystyrene measured by GPC was 14400, and the weight average molecular weight was 42600.
1.682 g of polymer 18 was obtained from 1.681 g (2.648 mmol) of diphosphonate. Yield 85%.
Thereby, a photoconductive material and a charge generation material that efficiently absorb two-photons can be obtained.

  In the material of the present invention, the content of the photoconductive material is preferably 10 to 90% by weight, and more preferably 40 to 80% by weight. When the content of the photoconductive material is 10% by weight or less, the photorefractive effect is lowered because the photocharge generation efficiency and the charge transport ability are lowered. On the other hand, when the content is 90% by weight or more, the photorefractive characteristics are exhibited. The concentration of other necessary components is lowered, and the photorefractive effect is also lowered.

(Non-linear optical material)
A nonlinear optical material refers to a material whose refractive index changes according to the strength of a spatial electric field. Such a phenomenon in which the refractive index changes is presumed to be caused by the molecular orientation of molecules having large birefringence being changed by an electric field or by the Pockels effect or the Kerr effect. It is preferable to have a large electro-optic constant, and it is preferable that a change in refractive index can be maintained.

Specific examples of such compounds include N- (4-nitrophenyl) -L-prolinol, [[4- (hexahydro-1H-azepin-1-yl) phenyl] methylene] propanedinitrile or 4- ( N-ethyl-N- (5-hydroxyheptyl) aminodicyanostyrene, or N- (5-nitro-2-pyridyl) prolinol, 2-methyl-4-nitroaniline, 4- (2,2-dicyanovinyl ) -N, N-bis (2-methoxyethyl) aniline or Disperse Red 1 (DR1), Disperse Red 19, 2,5-dimethyl-4- (p-nitrophenylazo) anisole (DMNPAA), 2, Azo compounds such as 6-dimethyl-4-(-4′nitrophenylazo) anisole, 2-cyano-3- (4-dimethylamino-phenyl) Cyanoethylenes such as Nyl) -but-2-ene-dinitrile, oxaborins such as 1- (1- (difluoroboryl) oxy-3H-benzo [F] chromen-2-yl) -ethanone complex, 2-methyl Nitroanilines such as -4-nitroaniline and N-methyl-4-nitro-o-toluidine, 2,5-dimethyl-4- (p-nitrophenylazo) anisole (DMNPAA), 4-amino-4'- Nitroazobenzene (ANAB), s-(−)-1- (4-nitrophenyl) -2-pyrrolidine-methanol (NPP), 4- (diethylamino)-(E) -β-nitrostyrene (DEANST), (diethylamino ) Benzaldehyde diphenylhydrazone (DEH), N- (4-nitrophenyl) -L-prolinol, 4-dimethylamino-4 Nitrostilbene (DANS), 3-fluoro-4-N, N-diethylamino- (Z) -β-nitrostyrene (DEAMNST), 3-fluoro-4-N, N-diethylamino- (E) -β-nitrostyrene (FDEANST), 3-fluoro-4-N, N-diethylamino- (Z) -β-methyl- (E) -β-nitrostyrene (FDEAMNST), N-2-butyl-2,6-dimethyl-4H- Compounds exhibiting a second-order nonlinear response such as pyridone-4-ylidenecyanomethyl acetate (2BNCM), 4-cyano-4′-pentyl-biphenyl, 4-cyano-4′-heptyloxy-biphenyl, (4-cyano Liquid crystal compounds such as phenyl) -4-pentylbenzoate and (4-cyanophenyl) -4-pentylcyclohexanoate are preferred.
Of these, in particular, N- (4-nitrophenyl) -L-prolinol, [[4- (hexahydro-1H-azepin-1-yl) phenyl] methylene] propanedinitrile 4- (N-ethyl-N- (5-hydroxypentyl) aminodicyanostyrene, N- (5-nitro-2-pyridyl) prolinol, 2-methyl-4-nitroaniline, 4- (2,2-dicyanovinyl) -N, N-bis ( 2-Methoxyethyl) aniline is a nonlinear optical material having a large birefringence, and is also preferable from the viewpoint of compatibility with other components.

In addition, spirobenzofuran-based molecules, fulgide molecules, cyclophene molecules, diarylethene-based molecules, azobenzene-based molecules, polyacrylates or polysiloxanes with cyanobiphenyl groups containing photochromic molecules in polymer liquid crystals, polysiloxanes containing spirobenzofuran groups, etc. Molecules exhibiting photochromism; and materials exhibiting liquid crystals such as ethyl p-azoxybenzoate, ammonium oleate, and p-azoxy anneal; and urea and derivatives thereof; thiourea and derivatives thereof; nitrobenzenes; carbonylbenzenes; Π-conjugated benzene derivatives such as phonates; pyridine N oxides; pyridine derivatives such as nitropyridines; polyacetylene, polypyrrole, polythiophene, and poly Π-conjugated polymers and oligomers such as niline; σ-conjugated polymers and oligomers such as polysilane and polygerman; polycyclic aromatic compounds such as anthracene, pyrene, phenanthrene, and coronene; indole, carbazole, oxazole, isoxazole , Thiazole, imidazole, pyrazole, oxadiazole, pyrazoline, thiathiazole, and compounds having nitrogen-containing cyclic compounds such as triazole, or compounds having these in the main chain or side chain; hydrazone compounds, triphenylamines, Derivatives such as phenylmethanes, benzeneamines, butadienes, stilbenes, orphenes, imines, piperonal, TCNQ, anthraquinone, diphenoquinone, etc .; fullerenes such as C60 and C70 and their derivatives Etc., and the like.
The nonlinear optical dyes may be used alone or in combination of two or more.

  In the material of the present invention, the content of the nonlinear optical material is preferably 5.0 to 60% by weight, and more preferably 10 to 50% by weight. When the content of the nonlinear optical material is 5.0% by weight or less, the nonlinear electro-optic effect necessary for inducing refractive index modulation cannot be obtained. On the other hand, when the content is 60% by weight or more, the nonlinear optical material is generally a compound having high crystallinity, and if mixed in a large amount, it causes a decrease in phase stability due to crystal precipitation.

(Electron-accepting material)
In order to generate carriers, the photoconductive material or the charge generation material needs to absorb the irradiation light. In general, a photoconductive material or a charge generation material alone generates carriers efficiently only for light having a wavelength of 500 nm or less. Therefore, an electron-accepting material is required to improve the absorption of the photorefractive material for long-wavelength light having a visible wavelength (400 to 800 nm) or longer. The electron-accepting material is known to form a charge transfer complex with a photoconductive material or a charge generation material, and can absorb long-wavelength light of a visible wavelength or longer to generate carriers.

As the electron-accepting material used in the present invention, a material that forms a charge transfer complex with a photoconductive material or a charge generation material is preferable, and 2,4,7-trinitro-9-fluorenone shown below, 2,4 , 7-trinitro-9-fluorenylidenemalonitrile, dimethyl terephthalate, p-dicyanobenzene, C60, C70 and the like are known.
In addition, fluorene derivatives such as 2,4-dinitrofluorene, 9-oxo-9H-thioxanthene-3-carboxylic acid-10,10 dioxide and 9-oxo-9H-thioxanthene-3-carboxamide-10,10 dioxide And cyanoethylenes such as tetracyanoethylene and 7,7,8,8-tetracyanoquinodimethane are also used.
Of these, 2,4,7-trinitro-9-fluorenone is most preferable in consideration of compatibility with other coexisting materials.

  In the material of the present invention, the content of the electron-accepting material is preferably 0.1 to 40% by weight, and more preferably 1.0 to 25% by weight. When the content of the electron-accepting material is 0.1% by weight or less, the absorption ability of long-wavelength light longer than the visible wavelength is small and the generation efficiency of carriers is low. On the other hand, when the content is 40% by weight or more, the charge generation amount increases, but light absorption by the formed charge transfer complex becomes strong, which causes a decrease in signal light intensity as a light modulation element.

(Charge trapping material)
The photogenerated carrier is trapped by the charge trapping material present in the vicinity. The pair of carriers is diffused by the charge transport material, resulting in charge separation, and the electric field generated by this space charge causes a photorefractive phenomenon.

As a charge trapping material, for example, a molecule containing a —C═C— bond such as stilbene or a derivative thereof and exhibiting a cis-trans type isomerization or photocyclization reaction; a —N═N— bond such as azobenzene or a derivative thereof; A molecule showing cis-trans isomerization; a molecule showing a hydrogen transfer reaction containing a —C═N— bond such as salicylidene aniline; a molecule showing an ion pair formation reaction such as spiropyran; spirooxazines, fulgides , Molecules having an electrocyclic reaction such as diarylethenes, spirooxazines and cancon derivatives; cyclophanes such as anthracene-containing cyclophane and metacyclophane; Examples of the fans include molecules that exhibit stereoisomerization between a syn isomer and an anti isomer. In particular, when a cyclophane in which groups having charge transporting ability are cross-linked is used, it is preferable to use a group that easily performs charge transfer with the group having charge transporting ability of the charge transporting agent. Therefore, it is desirable to crosslink groups having charge transporting ability of molecules contained as charge transporting agents.
In addition, trinitrofluorenone, tetrachlorobenzoquinone, tetracyanobenzene, diazonaphthaquinone, azide, allyl ketone, alkanone, allyl aldehyde and the like can also be used.

  In the material of the present invention, the content of the charge trapping material is preferably 0.1 to 20% by weight, and more preferably 1.0 to 10% by weight. When the content of the electron-accepting material is 1.0% by weight or less, the efficiency with which the photogenerated carrier is trapped by the charge trapping material is low, and the photorefractive effect cannot be exhibited efficiently. On the other hand, when the content is 20.0% by weight or more, when the photogenerated carrier is transported, it is inhibited by the charge trapping material, so that the charge transport property cannot be sufficiently modulated and the photorefractive effect can be efficiently exhibited. Cannot be done.

(Charge generation material)
The charge generation material is a compound having a function of generating electrons and holes (carriers) when irradiated with light. A spatial electric field is generated by the movement of the carriers in the adjacent charge transport material.
A feature of the charge generating material of the present invention is that the above function can be expressed not only in a normal one-photon process but also in a two-photon process.
That is, according to the present invention, a two-photon absorption material composed of the compounds represented by the above formulas (I) to (X) can be used as a charge generation material.

For the purpose of increasing the charge generation efficiency, a known charge generation material can be added.
Polyvinylcarbazole, triphenylamine, phthalocyanine, porphyrin, porphyrazine, metallocene, squalene, azo dye, naphthalene, naphthacene, pyrene, perylene dye, styrylanthracene, anthrylethylene, anthracenophene, anthraceno crown ether, triphenylmethane dye , Rhodamine, perinone, picene, acene, thiapyrylium salt, cyanine dye, pyrarizone, phenylhydrazone, dithione, fullerene, dihaloanthrangeone, epindridione, trihalopyransrangeone, quinacridone, tetrahalothioindigo, azurenium dye, anthracene dye , Anthraquinone, chlorodiene blue, benzothiazole, oxazole, hydrazone, quinoline, stilbene, azobenze There benzylidene, acridine, fluorene, compounds such as indole.
In addition, spherical carbon molecules called fullerenes typified by C70 and C60, carbon clusters such as carbon nanotubes, and the like can also be used.

  In the material of the present invention, the content of the charge generating material is preferably 1.0 to 50% by weight, and more preferably 5.0 to 40% by weight. When the content of the charge generation material is 1.0% by weight or less, the photocharge generation efficiency is lowered, so that the photorefractive effect is lowered. On the other hand, when the content is 50% by weight or more, the photorefractive characteristics are required. As a result, the concentration of these components decreases and the photorefractive effect also decreases.

(Charge transport material)
Examples of the charge transport material include a hole transport material and an electron transport material.
Low molecular hole transport materials include (tri) arylamine derivatives, polyarylalkane derivatives, 4-diarylamino-substituted chalcones, nonionic cycloheptenyl derivatives, hydrazine derivatives, 3,3′-bisaryl-2-pyrazoline derivatives, carbazole N-ethylcarbazole, N-isopropylcarbazole, N-phenylcarbazole, halogenated carbazole and bis (carbazolylalkane), tetra-p-tolylbenzidine, N, N′-bis (3-methylphenyl)-[1 , 1′-biphenyl] -4,4′-diamine, tetraarylbenzidine, alkylhydrazone, arylhydrazone, diphenylhydrazone, organometallic compound having an aminoaryl substituent, diethylaminophenyloxadiazole, biscarba Rirupuropan and the like.

  As the electron transport material, 2,4,7-trinitro-9-fluorenone, phthalic anhydride, tetrachlorophthalic anhydride, benzyl, merit anhydride, S-tricyanobenzene, picryl chloride, 2,4-dinitrochlorobenzene, 2,4-dinitrobromobenzene, 4-nitrobiphenyl, 4,4′-dinitrobiphenyl, 2,4,6-trinitroanisole, trichlorotrinitrobenzene, p-dinitrobenzene, chloranyl, bromanyl, 9-fluorenylidenemethane 10-anthronylidenemethane, bisanthraquinodimethane, 4H-thiopyran-1,1-dioxide, dibenzo derivatives of benzophenone substituted by 4-dimesityl boron, naphthoquinone and anthraquinone derivatives, 7-nitro-2-aza-9- Fluorenylidene-Marono Tolyl, tetracyanoethylene, tetracyanoquinodimethane, 2,4,5,7-tetranitro-9-tetrafluorone, 2,4,7-trinitro-9-dicyanomethylenefluorenone, 2,4,5,7-tetranitro -Xanthone, 2,4,9-trinitrothioxanthone, N, N-bis (3,5-dimethylphenyl) -3,4,9,10-perylenetetracarboximide, diphenone, stilbenzoquinone.

  Polymer charge transport materials include π-conjugated polymers such as polyvinyl carbazole, polyvinyl ferrocene, polyvinyl pyrazoline, polyparaphenylene vinylene, polyparaphenylene, polythiophene, polyacetylene, polypyrrole, polythiophene, polyaniline, polysilane, and polygermane. And a polymer having the above-described low molecular charge transport material in the main chain or side chain of the polymer can be used.

  In the material of the present invention, the content of the charge transport material is preferably 1.0 to 60% by weight, and more preferably 5.0 to 50.0% by weight. When the content of the charge transport material is 1.0% by weight or less, the photocharge transport efficiency is lowered, so that the photorefractive effect is lowered. On the other hand, when the content is 60% by weight or more, the photocharge trapping efficiency is lowered. In addition, the photorefractive effect is reduced.

(Polymer compound)
As the polymer material, an organic polymer compound having high transparency and excellent heat resistance and weather resistance is preferable.
From this point, acrylic esters such as polymethyl methacrylate, poly t-butyl methacrylate, polypropyl methacrylate, poly (vinyl butyral), poly (vinyl acetate), poly (4-vinylbiphenyl), poly (2-vinylnaphthalene) Vinyl compounds such as polyacenaphthylene, polycarbonate, cyanoresins such as cyanoethyl hydroxyethyl cellulose and cyanoethyl pullulan, and polyolefin are preferable because of high transparency.
Polyimides, polyether ketones, polyether sulfones and the like are also preferable as the high transparency and high heat resistance polymer compound.

  The content of the polymer material is preferably 0.0 to 50% by weight. If the content is small, the compatibility is lowered. If the content is too large, the concentration of other components necessary for the expression of photorefractive characteristics is lowered, and the photorefractive effect is also lowered.

(Plasticizer)
The plasticizer preferably has the same characteristics as the organic polymer compound, and the photorefractive compatibility is improved.
As the plasticizer, 2- (1,2-cyclohexanedicarboximido) ethyl propionate, 2- (1,2-cyclohexanedicarboximido) ethyl butyrate, 2- (1,2-cyclohexanedicarboximide) Examples include ethyl benzoate, 2- (1,2-cyclohexanedicarboximide) ethyl acrylate, and 2- (phthalimido) ethyl propionate. Moreover, common plasticizers, such as tricresyl phosphate, dioctyl phthalate, butyl benzyl phthalate, and dibutyltin dilaurate, may be used.

  The content of the plasticizer is preferably 0.0 to 20% by weight. If the content is small, the compatibility is lowered. If the content is too large, the concentration of other components necessary for the expression of photorefractive characteristics is lowered, and the photorefractive effect is also lowered.

(Preparation method of photorefractive molding)
Photoconductive materials, nonlinear optical materials, electron accepting materials, charge trapping materials, charge generating agents, charge transporting agents, etc. as described above, and matrix materials (polymer base materials), sensitizers, plasticizers as necessary Is dissolved in an organic solvent at a predetermined ratio to prepare a solution.
Examples of the organic solvent include toluene, methyl ethyl ketone, tetrahydrofuran, ethyl lactate, ethyl acetate, chloroform, polyethylene glycol methacrylate (PEGMEA), fluorine alcohol, dimethylacetamide, dimethylformamide, dimethyl sulfoxide, dimethylimidazolinone, sulfolane, and N-methylpyrrolidone. Etc. These may be used alone or as a mixed solvent of two or more kinds, and the solvent may be heated when preparing the solution.
A practical photorefractive material is produced by preparing a film from the mixed solution thus obtained on a suitable transparent substrate by a spin coating method, a dip coating method or the like. In addition, the form of the photorefractive material of this invention is not limited to a film, It can change suitably according to the intended purpose. The thickness of the photorefractive material is also appropriately determined according to the purpose of use, and is controlled by the concentration of the mixed solution and application conditions.

  EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples. However, the present invention is not limited by these examples unless it exceeds the gist.

Example 1
A toluene / pyridine (parts by weight 75/25) solution having a composition of a weight part of 75:25 and a solid content of 10% was prepared for the photoconductive material (OP-1) and the nonlinear optical material (NL-1).
Using this solution, a film was formed between two glass substrates through a 100 μm spacer by a casting method to obtain a photorefractive molded sample.
Diffraction efficiency was determined for this photorefractive molded sample using the evaluation method shown in FIG. 1 ((9): sample) as described in the evaluation of the photorefractive effect below.

(Example 2)
In Example 1, the composition of the weight part 75:25 of the photoconductive material (OP-1) and the nonlinear optical material (NL-1) of the photorefractive material is changed to the photoconductive material (OP-2) and the nonlinear optical material. (NL-1) and the electron-accepting material (A-1) have a composition of parts by weight of 75: 20: 5, and a photorefractive molding sample was provided in the same manner to obtain diffraction efficiency.

(Example 3)
In Example 1, the composition of the weight part 75:25 of the photoconductive material (OP-1) and the nonlinear optical material (NL-1) of the photorefractive material is changed to the photoconductive material (OP-3), the nonlinear optical material. (NL-1) and the electron accepting material (A-2) have a weight part composition of 75: 20: 5, a photorefractive molded sample was similarly provided, and diffraction efficiency was obtained.

Example 4
In Example 1, the composition of the photoconductive material (OP-1) and the nonlinear optical material (NL-1) in the weight part 75:25 is changed to the photoconductive material (OP-4), the nonlinear optical material. (NL-1), electron-accepting material (A-1) and charge transporting material (CT-1) by weight 50: 20: 5: 25, followed by photorefractive molding sample, diffraction efficiency Asked.

(Example 5)
In Example 1, the composition of the weight part 75:25 of the photoconductive material (OP-1) and the nonlinear optical material (NL-1) of the photorefractive material is changed to the photoconductive material (OP-5), the nonlinear optical material. The composition of (NL-2) and charge trapping material (T-1) by weight part 75: 20: 5 was used, and a photorefractive molded sample was provided in the same manner to obtain diffraction efficiency.

(Example 6)
In Example 1, the composition of the weight part 75:25 of the photoconductive material (OP-1) and the nonlinear optical material (NL-1) of the photorefractive material is changed into the charge generation material (CG-1), the nonlinear optical material ( NL-1), electron-accepting material (A-1) and charge transporting material (CT-2) by weight 35: 20: 5: 40, and photorefractive molding samples are provided in the same manner to improve diffraction efficiency. Asked.

(Example 7)
In Example 1, the composition of the weight part 75:25 of the photoconductive material (OP-1) and the nonlinear optical material (NL-1) of the photorefractive material is changed into the charge generation material (CG-2), the nonlinear optical material ( NL-1), charge transport material (CT-3), charge trapping material (T-1), polystyrene weight parts 15: 15: 32: 3: 35, and photorefractive molding sample is provided in the same manner. The diffraction efficiency was determined.

(Example 8)
In Example 1, the composition of the weight part 75:25 of the photoconductive material (OP-1) and the nonlinear optical material (NL-1) of the photorefractive material was changed to charge generation material (CG-3), nonlinear optical material ( NL-2) and charge transport material (CT-1) in weight parts 35:20:45, and a photorefractive molded sample was provided in the same manner to obtain diffraction efficiency.

[Evaluation of photorefractive effect]
As evaluation characteristics of the photorefractive molded article, diffraction efficiency was evaluated by the following method.

(Diffraction efficiency)
The diffraction efficiency indicates the ratio of the intensity of transmitted light and diffracted light when a light beam is incident on a diffraction grating formed by the photorefractive effect. The diffraction efficiency was measured by P-polarization writing and S-polarization reading using a femtosecond titanium sapphire laser as a light source by the four-wave mixing method shown in FIG. At this time, the writing light is made incident at 40 ° and 60 ° (crossing angle 20 °) with respect to the normal of the sample plane, and the point where the diffracted light intensity is maximized is obtained. Efficiency (%) was calculated from the following formula.

（評価結果）

(Evaluation results)

It is explanatory drawing of the evaluation method of the photorefractive effect in this invention.

Explanation of symbols

1: Laser light source (measurement light source: femtosecond titanium sapphire laser
Wavelength: 800nm, pulse width: 100fs
(Repetition: 80 MHz, optical power: 800 mW)
2, 14: Polarizing plate,
4, 6: Beam splitters 3, 5, 10, 12, 15: Mirror 7: Polarizing beam splitter 8: First writing beam 9: Sample 11: Second writing beam 13: 1/2 wavelength plate 16: Reading beam 17: Diffracted beam 18: Photodiode

Claims (18)

An organic photorefractive material composed of a photoconductive material having two-photon absorption ability and a nonlinear optical material, wherein the photoconductive material is
An organic photorefractive material comprising a two-photon absorption material represented by the following general formula (III):

Ar ₄ is a substituted or unsubstituted divalent group of thiophene, biphenyl, fluorene or anthracene,
Ar ₅ and Ar ₆ are each independently a substituted or unsubstituted aromatic hydrocarbon group,
x and y are integers of 1 or more and 4 or less, z is an integer of 1 or more and 5 or less,
R ₁ and R ₂ are each independently a hydrogen atom, a halogen group, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkoxy group, or a substituted or unsubstituted alkylthio group,
R ₃ is a hydrogen group, a halogen group, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkoxy group, a substituted or unsubstituted alkylthio group, or a substituted or unsubstituted aryl group, and the above x, y And when z is 2 or more, the plurality of R ₁ , R ₂ and R ₃ are independent of each other. An organic photorefractive material comprising a light conductive material and a non-linear optical material is configured to coexist with two-photon absorption ability, the photoconductive material is,
An organic photorefractive material comprising a two-photon absorption material represented by the following general formula (IV):

Ar ₄ is a substituted or unsubstituted divalent group of benzene, thiophene, biphenyl, fluorene or anthracene,
Ar ₅ and Ar ₆ are each independently a substituted or unsubstituted aromatic hydrocarbon group,
v is an integer of 1 to 3, w, x and y are integers of 1 to 4.
R ₁ , R ₂ , R ₄ , R ₅ , R ₆ and R ₇ are each independently a hydrogen atom, a halogen group, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkoxy group, or a substituted or unsubstituted alkylthio group. And v, w, x and y are 2 or more, the plurality of R ₁ , R ₂ , R ₄ and R ₅ are independent of each other. An organic photorefractive material comprising a light conductive material and a non-linear optical material is configured to coexist with two-photon absorption ability, the photoconductive material is,
An organic photorefractive material made of a two-photon absorption material represented by the following general formula (V).

Ar ₄ is a substituted or unsubstituted divalent group of benzene, thiophene, biphenyl, fluorene or anthracene,
Ar ₅ and Ar ₆ are each independently a substituted or unsubstituted aromatic hydrocarbon group,
v is an integer of 1 to 3, w, x and y are integers of 1 to 4.
R ₁ , R ₂ , R ₄ and R ₅ are each independently a hydrogen atom, a halogen group, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkoxy group or a substituted or unsubstituted alkylthio group, and When v, w, x and y are 2 or more, a plurality of R ₁ , R ₂ , R ₄ and R ₅ are independent of each other. An organic photorefractive material comprising a photoconductive material having two-photon absorption ability and a nonlinear optical material, wherein the photoconductive material has a repeating unit represented by the following general formula (VIII): An organic photorefractive material comprising a two-photon absorbing material.

Ar ₄ is a substituted or unsubstituted divalent group of benzene, thiophene, biphenyl, fluorene or anthracene,
x and y are integers of 1 or more and 4 or less, z is an integer of 1 or more and 5 or less,
R ₁ and R ₂ are each independently a hydrogen atom, a halogen group, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkoxy group, or a substituted or unsubstituted alkylthio group,
R ₃ is a hydrogen group, a halogen group, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkoxy group, a substituted or unsubstituted alkylthio group, or a substituted or unsubstituted aryl group, and the above x, y And when z is 2 or more, the plurality of R ₁ , R ₂ and R ₃ are independent of each other. An organic photorefractive material comprising a photoconductive material having two-photon absorption ability and a nonlinear optical material, wherein the photoconductive material has a repeating unit represented by the following general formula (IX): An organic photorefractive material comprising a two-photon absorbing material.

Ar ₄ is a substituted or unsubstituted divalent group of benzene, thiophene, biphenyl, fluorene or anthracene,
v is an integer of 1 to 3, w, x and y are integers of 1 to 4.
R ₁ , R ₂ , R ₄ , R ₅ , R ₆ and R ₇ are each independently a hydrogen atom, a halogen group, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkoxy group, or a substituted or unsubstituted alkylthio group. And v, w, x and y are 2 or more, the plurality of R ₁ , R ₂ , R ₄ and R ₅ are independent of each other. An organic photorefractive material configured by coexistence of a photoconductive material having two-photon absorption ability and a nonlinear optical material , wherein the photoconductive material is
An organic photorefractive material comprising a two-photon absorption material having a repeating unit represented by the following general formula (X).

Ar ₄ is a substituted or unsubstituted divalent group of benzene, thiophene, biphenyl, fluorene or anthracene,
v is an integer of 1 to 3, w, x and y are integers of 1 to 4.
R ₁ , R ₂ , R ₄ and R ₅ are each independently a hydrogen atom, a halogen group, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkoxy group or a substituted or unsubstituted alkylthio group, and When v, w, x and y are 2 or more, a plurality of R ₁ , R ₂ , R ₄ and R ₅ are independent of each other. Furthermore, the organic photorefractive material according to claim 1, wherein an electron accepting material coexists. The organic photorefractive material according to claim 7, further comprising a charge trapping material. A charge generation material having a two-photon absorption ability, an organic photorefractive material configured by coexistence of a charge transport material and a nonlinear optical material, wherein the charge generation material comprises:
Following general formula (III) organic photorefractive material ing from the two-photon absorption material is.

Ar ₄ is a substituted or unsubstituted divalent group of thiophene, biphenyl, fluorene or anthracene,
Ar ₅ and Ar ₆ are each independently a substituted or unsubstituted aromatic hydrocarbon group,
x and y are integers of 1 or more and 4 or less, z is an integer of 1 or more and 5 or less,
R ₁ and R ₂ are each independently a hydrogen atom, a halogen group, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkoxy group, or a substituted or unsubstituted alkylthio group,
R ₃ is a hydrogen group, a halogen group, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkoxy group, a substituted or unsubstituted alkylthio group, or a substituted or unsubstituted aryl group, and the above x, y And when z is 2 or more, the plurality of R ₁ , R ₂ and R ₃ are independent of each other. Charge generation material having two-photon absorption ability, organic photorefractive material constituted by coexistence of charge transport material and nonlinear optical material, wherein the charge generation material is represented by the following general formula (IV) organic photorefractive material Ru Tona.

Ar ₄ is a substituted or unsubstituted divalent group of benzene, thiophene, biphenyl, fluorene or anthracene,
Ar ₅ and Ar ₆ are each independently a substituted or unsubstituted aromatic hydrocarbon group,
v is an integer of 1 to 3, w, x and y are integers of 1 to 4.
R ₁ , R ₂ , R ₄ , R ₅ , R ₆ and R ₇ are each independently a hydrogen atom, a halogen group, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkoxy group, or a substituted or unsubstituted alkylthio group. And v, w, x and y are 2 or more, the plurality of R ₁ , R ₂ , R ₄ and R ₅ are independent of each other. A charge generation material having a two-photon absorption ability, an organic photorefractive material configured by coexistence of a charge transport material and a nonlinear optical material, wherein the charge generation material comprises:
Following general formula (V) organic photorefractive material ing from the two-photon absorption material is.

Ar ₄ is a substituted or unsubstituted divalent group of benzene, thiophene, biphenyl, fluorene or anthracene,
Ar ₅ and Ar ₆ are each independently a substituted or unsubstituted aromatic hydrocarbon group,
v is an integer of 1 to 3, w, x and y are integers of 1 to 4.
R ₁ , R ₂ , R ₄ and R ₅ are each independently a hydrogen atom, a halogen group, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkoxy group or a substituted or unsubstituted alkylthio group, and When v, w, x and y are 2 or more, a plurality of R ₁ , R ₂ , R ₄ and R ₅ are independent of each other. An organic photorefractive material composed of a charge generation material having a two-photon absorption capability, a charge transport material and a nonlinear optical material, wherein the charge generation material is represented by the following general formula ( VIII ) organic photorefractive material ing from the two-photon absorption material having the units.

Ar ₄ is a substituted or unsubstituted divalent group of benzene, thiophene, biphenyl, fluorene or anthracene,
x and y are integers of 1 or more and 4 or less, z is an integer of 1 or more and 5 or less,
R ₁ and R ₂ are each independently a hydrogen atom, a halogen group, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkoxy group, or a substituted or unsubstituted alkylthio group,
R ₃ is a hydrogen group, a halogen group, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkoxy group, a substituted or unsubstituted alkylthio group, or a substituted or unsubstituted aryl group, and the above x, y And when z is 2 or more, the plurality of R ₁ , R ₂ and R ₃ are independent of each other. An organic photorefractive material composed of a charge generation material having a two-photon absorption ability, a charge transport material and a nonlinear optical material, wherein the charge generation material is represented by the following general formula ( IX ) organic photorefractive material ing from the two-photon absorption material having the units.

Ar ₄ is a substituted or unsubstituted divalent group of benzene, thiophene, biphenyl, fluorene or anthracene,
v is an integer of 1 to 3, w, x and y are integers of 1 to 4.
R ₁ , R ₂ , R ₄ , R ₅ , R ₆ and R ₇ are each independently a hydrogen atom, a halogen group, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkoxy group, or a substituted or unsubstituted alkylthio group. And v, w, x and y are 2 or more, the plurality of R ₁ , R ₂ , R ₄ and R ₅ are independent of each other. A charge generation material having a two-photon absorption ability, an organic photorefractive material configured by coexistence of a charge transport material and a nonlinear optical material, wherein the charge generation material is represented by the following general formula ( X ) organic photorefractive material ing from the two-photon absorption material having the units.

Ar ₄ is a substituted or unsubstituted divalent group of benzene, thiophene, biphenyl, fluorene or anthracene,
v is an integer of 1 to 3, w, x and y are integers of 1 to 4.
R ₁ , R ₂ , R ₄ and R ₅ are each independently a hydrogen atom, a halogen group, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkoxy group or a substituted or unsubstituted alkylthio group, and When v, w, x and y are 2 or more, a plurality of R ₁ , R ₂ , R ₄ and R ₅ are independent of each other. The organic photorefractive material according to claim 9, further comprising an electron accepting material. The organic photorefractive material according to claim 15, further comprising a charge trapping material. An electro-optical effect imparting method for causing the organic photorefractive material according to any one of claims 1 to 16 to exhibit an electro-optical effect by a two-photon absorption process. An electro-optical effect imparting method for recording a hologram on the organic photorefractive material according to claim 1 by a two-photon absorption process.

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