JP5321941B2 - Two-photon absorption materials and their applications - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an organic material having a large two-photon absorption cross section, that is, a two-photon absorption organic material having high sensitivity, and to provide an optical recording material having at least the above two-photon absorption material having a large two-photon absorption cross section, in which recording is carried out through an unrewritable system. <P>SOLUTION: A two-photon absorption polymer is provided, having a repeating unit expressed by general formula (I). In the formula, Ar<SB>2</SB>and Ar<SB>3</SB>represent substituted or unsubstituted bivalent aromatic hydrocarbon groups; Ar<SB>1</SB>represents a substituted or unsubstituted aromatic hydrocarbon group; each of R<SP>1</SP>, R<SP>2</SP>and R<SP>3</SP>independently represents a group selected from substituted or unsubstituted alkyl groups, substituted or unsubstituted alkoxy groups and substituted or unsubstituted alkylthio groups, which may be identical or different from one another; each of x, y and z represents an integer from 0 to 2, which may be identical or different from one another; and n represents an integer of 1 or larger. <P>COPYRIGHT: (C)2009,JPO&amp;INPIT

Description

  The present invention relates to a novel two-photon absorption material, and more particularly to a poly (triarylamine) having a high two-photon absorption cross section. In addition, the present invention is applied to uses such as a three-dimensional optical recording medium containing the novel two-photon absorption material, an optical modeling device, a light limiting device, and a two-photon excitation fluorescence detection device.

As conventional examples of the two-photon absorption material, there are those disclosed in Patent Documents 1 to 5.
Further, as conventional examples relating to a three-dimensional (multilayer) optical recording medium (material), there are those disclosed in Patent Documents 6 to 11.
Moreover, there exists a thing of patent document 12 as a prior art example regarding an optical modeling technique.
Further, as conventional examples relating to optical functional elements, there are those disclosed in Patent Documents 13 to 16.
Further, as conventional examples of light detection using two-photon characteristics, there are those disclosed in Patent Documents 17 to 21.
In addition, we have developed and proposed a technology related to two-photon absorption materials (Patent Documents 22 to 30).

As a three-dimensional optical recording medium using a two-photon absorbing material, a method of reading with fluorescence using a fluorescent substance for recording and reproduction (Levic, Eugene, Polis et al., Patent Document 6: JP-T-2001-524245, Pavel, Eugene et al., Patent Document 7: JP-T 2000-512061), absorption or fluorescence reading using a photochromic compound (Korotif, Nikolai Eye et al., Patent Document 8: JP-T 2001-522119, Arsenoff, Vladimir In addition, Patent Document 9: JP-T-2001-508221) and the like have been proposed, but none of them presents a specific two-photon absorption material, and examples of two-photon absorption compounds presented abstractly. Also, a two-photon absorption compound having extremely small two-photon absorption efficiency is used. Further, since the photochromic compounds used in these patent documents are reversible materials, there are problems in non-destructive reading, long-term storage stability of recording, S / N ratio of reproduction, and the like, a method that is practical as an optical recording medium I can't say that. In particular, in terms of non-destructive readout, long-term storage stability of recording, etc., it is preferable to reproduce by changing the reflectance (refractive index or absorptivity) or emission intensity using an irreversible material. There was no example that specifically disclosed the absorbent material.
Further, in Kawada Jun, Kawada Yoshimasa, Patent Document 10: JP-A-6-28672, Kawada Kei, Kawada Yoshimasa et al., Patent Document 11: JP-A-6-118306, three-dimensional recording is performed by refractive index modulation. However, there is no description of a method using a two-photon absorption three-dimensional optical recording material.

JP-A-2005-213434 JP 2005-82507 A JP 2004-168690 A JP 2005-325087 A JP 2005-529913 A JP-T-2001-524245 Special table 2000-512061 gazette Special table 2001-522119 gazette Special table 2001-508221 gazette JP-A-6-28672 JP-A-6-118306 JP 2005-134873 A JP 2004-277416 A JP-A-11-167036 JP 2005-257741 A JP-A-8-320422 Japanese Patent Laid-Open No. 9-230246 JP 10-142507 A JP 2005-165212 A JP 2005-123513 A JP 2005-132663 A Japanese Patent Application No. 2006-73792 Japanese Patent Application No. 2006-67089 Japanese Patent Application No. 2006-67067 Japanese Patent Application No. 2006-70305 Specification Japanese Patent Application No. 2006-74156 Japanese Patent Application No. 2006-250292 Japanese Patent Application No. 2006-354063 Japanese Patent Application No. 2007-56886 Special table 2007-227353 Jean-Luc Bredas et al Science, 281,1653 (1998)

The use of the two-photon absorption phenomenon makes it possible to develop applications for various devices with excellent spatial resolution. However, the two-photon absorption materials available at this time have a very low two-photon transition efficiency. In order to induce absorption, it was necessary to use an excitation light source that outputs a very large electric field. For this reason, there has been a strong demand for the development of a two-photon absorption material with excellent two-photon transition efficiency that is practical.
That is, an object of the present invention is to provide an organic material having a large two-photon absorption cross section, that is, a highly sensitive two-photon absorption organic material.
It is another object of the present invention to provide an optical recording material that has at least the two-photon absorption material of the present invention having a large two-photon absorption cross-section and that performs recording in a manner in which recording cannot be rewritten.

As a result of intensive studies, the present inventors have found that the above problems can be solved by a specific arylamine derivative, and have reached the present invention.
That is, the said subject is solved by the following this invention.
(1) “A two-photon absorption polymer having a repeating unit represented by the following general formula (I);

（式中、Ａｒ_２およびＡｒ_３は、置換もしくは無置換の芳香族炭化水素基の２価基であり、Ａｒ_１は置換もしくは無置換の芳香族炭化水素基を表わす。Ｒ^１、Ｒ^２およびＲ^３は、アルキル基を表わし、ｘ、ｙおよびｚは、それぞれ０から２までの整数を表わし、同一でも別異でもよく、ｎは１以上の整数を表わす。）」、
（２）「前記第（１）項に記載の二光子吸収ポリマーが、特に下記一般式（II）で表わされることを特徴とする二光子吸収ポリマー；

(In the formula, Ar ₂ and Ar ₃ are a divalent group of a substituted or unsubstituted aromatic hydrocarbon group, and Ar ₁ represents a substituted or unsubstituted aromatic hydrocarbon group. R ¹ , R ² and R ³ represents an alkyl group, x, y and z each represents an integer of 0 to 2, which may be the same or different, and n represents an integer of 1 or more.
(2) “Two-photon absorption polymer according to the item (1), especially represented by the following general formula (II):

（式中、Ａｒ_１は置換もしくは無置換の芳香族炭化水素基の２価基であり、Ｒ^１、Ｒ^２、Ｒ^３ は、アルキル基を表わし、Ｒ^４およびＲ^５は、それぞれ独立に、置換もしくは無置換のアルキル基、置換もしくは無置換のアルコキシ基、または置換もしくは無置換のアルキルチオ基から選択された基を表わし、同一でも別異でもよく、ｘ、ｙおよびｚは、それぞれ０から２までの整数を表わし、同一でも別異でもよく、ｕおよびｖは、それぞれ０から４までの整数を表わし、同一でも別異でもよく、ｎは１以上の整数を表わす。）」、
（３）「前記第（２）項に記載の二光子吸収ポリマーが、特に下記一般式（III）で表わされることを特徴とする二光子吸収ポリマー；

(In the formula, Ar ₁ is a divalent group of a substituted or unsubstituted aromatic hydrocarbon group, R ¹ , R ² , and R ³ represent an alkyl group, and R ⁴ and R ⁵ are each independently, Represents a group selected from a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkoxy group, or a substituted or unsubstituted alkylthio group, and may be the same or different, and each of x, y, and z is 0 to 2 And may be the same or different, and u and v each represent an integer of 0 to 4, and may be the same or different, and n represents an integer of 1 or more.
(3) “Two-photon absorption polymer according to item (2), particularly represented by the following general formula (III):

（式中、Ｒ^１、Ｒ^２、Ｒ^３ は、アルキル基を表わし、Ｒ^４、Ｒ^５およびＲ^６は、それぞれ独立に、置換もしくは無置換のアルキル基、置換もしくは無置換のアルコキシ基、または置換もしくは無置換のアルキルチオ基から選択された基を表わし、同一でも別異でもよく、ｘ、ｙおよびｚは、それぞれ０から２までの整数を表わし、同一でも別異でもよく、ｕおよびｖは、それぞれ０から４までの整数を表わし、同一でも別異でもよく、ｗは０から５までの整数を表わし、ｎは１以上の整数を表わす。」、
（４）「下記一般式（IＶ）で表わされることを特徴とする二光子吸収材料；

(Wherein R ¹ , R ² and R ³ represent an alkyl group, and R ⁴ , R ⁵ and R ⁶ each independently represents a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkoxy group, or Represents a group selected from substituted or unsubstituted alkylthio groups, which may be the same or different; x, y and z each represent an integer of 0 to 2, and may be the same or different; u and v are Each represents an integer from 0 to 4, which may be the same or different, w represents an integer from 0 to 5, and n represents an integer of 1 or more.
(4) “two-photon absorption material characterized by being represented by the following general formula (IV);

（式中、Ａｒ_２およびＡｒ_３は、置換もしくは無置換の芳香族炭化水素基の２価基であり、Ａｒ_１は置換もしくは無置換の芳香族炭化水素基を表わす。Ｒ^１、Ｒ^２およびＲ^３は、アルキル基を表わし、同一でも別異でもよく、ｘ、ｙおよびｚは、それぞれ０から２までの整数を表わし、同一でも別異でもよく、ｎは１以上の整数を表わす。）」、
（５）「前記第（４）項に記載の二光子吸収材料が、特に下記一般式（Ｖ）で表わされることを特徴とする二光子吸収材料；

(In the formula, Ar ₂ and Ar ₃ are a divalent group of a substituted or unsubstituted aromatic hydrocarbon group, and Ar ₁ represents a substituted or unsubstituted aromatic hydrocarbon group. R ¹ , R ² and R ³ represents an alkyl group, which may be the same or different, and x, y and z each represents an integer of 0 to 2, and may be the same or different, and n represents an integer of 1 or more.) "
(5) “Two-photon absorbing material according to item (4), particularly represented by the following general formula (V):

（式中、Ａｒ_１は置換もしくは無置換の芳香族炭化水素基の２価基であり、Ｒ^１、Ｒ^２、Ｒ^３ は、アルキル基を表わし、Ｒ^４およびＲ^５は、それぞれ独立に、置換もしくは無置換のアルキル基、置換もしくは無置換のアルコキシ基、または置換もしくは無置換のアルキルチオ基から選択された基を表わし、同一でも別異でもよく、ｘ、ｙおよびｚは、それぞれ０から２までの整数を表わし、同一でも別異でもよく、ｕおよびｖは、それぞれ０から４までの整数を表わし、同一でも別異でもよく、ｎは１以上の整数を表わす。）」、
（６）「前記第（５）項に記載の二光子吸収材料が、特に下記一般式（ＶI）で表わされることを特徴とする二光子吸収材料；

(In the formula, Ar ₁ is a divalent group of a substituted or unsubstituted aromatic hydrocarbon group, R ¹ , R ² , and R ³ represent an alkyl group, and R ⁴ and R ⁵ are each independently, Represents a group selected from a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkoxy group, or a substituted or unsubstituted alkylthio group, and may be the same or different, and each of x, y, and z is 0 to 2 And may be the same or different, and u and v each represent an integer of 0 to 4, and may be the same or different, and n represents an integer of 1 or more.
(6) “Two-photon absorbing material according to item (5), especially represented by the following general formula (VI):

（式中、Ｒ^１、Ｒ^２、Ｒ^３ は、アルキル基を表わし、Ｒ^４、Ｒ^５およびＲ^６は、それぞれ独立に、置換もしくは無置換のアルキル基、置換もしくは無置換のアルコキシ基、または置換もしくは無置換のアルキルチオ基から選択された基を表わし、同一でも別異でもよく、ｘ、ｙおよびｚは、それぞれ０から２までの整数を表わし、同一でも別異でもよく、ｕおよびｖは、それぞれ０から４までの整数を表わし、同一でも別異でもよく、ｗは０から５までの整数を表わし、ｎは１以上の整数を表わす。）」、
（７）「前記第（１）項乃至第（６）項のいずれかに記載の二光子吸収材料を含むことを特徴とする光記録材料」、
（８）「前記第（１）項乃至第（６）項のいずれかに記載の二光子吸収材料を含むことを特徴とする光造形材料」、
（９）「前記第（１）項乃至第（６）項のいずれかに記載の二光子吸収材料を含むことを特徴とする光制限材料」、
（１０）「前記第（１）項乃至第（６）項のいずれかに記載の二光子吸収材料を含むことを特徴とする二光子励起蛍光材料」、
（１１）「平面上に形成され、該平面に対し水平、及び垂直方向に記録再生が可能な三次元光記録媒体において、前記第（１）項乃至第（６）項のいずれかに記載の二光子吸収材料が、光記録が行なわれる記録層の少なくとも一部として含まれていることを特徴とする三次元光記録媒体」、
（１２）「光硬化性樹脂に光を照射して造形を行なう光造形装置において、前記第（１）項乃至第（６）項のいずれかに記載の二光子吸収材料が、前記光硬化性樹脂の少なくとも一部として含まれていることを特徴とする光造形装置」、
（１３）「透過光強度を制限する素子を備えた光制限装置において、前記第（１）項乃至第（６）項のいずれかに記載の二光子吸収材料が、前記素子の少なくとも一部として含まれていることを特徴とする光制限装置」、
（１４）「光の進路を制限する素子を備えた光制限装置において、前記第（１）項乃至第（６）項のいずれかに記載の二光子吸収材料が、前記素子の少なくとも一部として含まれていることを特徴とする光制限装置」、
（１５）「試料中の被分析物に前記第（１）項乃至第（６）項のいずれかに記載の二光子吸収材料を選択的に担持させ、前記二光子吸収材料を検出することによって、被分析物を検出することを特徴とする二光子励起蛍光検出装置」。
これらにより、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。

(Wherein R ¹ , R ² and R ³ represent an alkyl group, and R ⁴ , R ⁵ and R ⁶ each independently represents a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkoxy group, or Represents a group selected from substituted or unsubstituted alkylthio groups, which may be the same or different; x, y and z each represent an integer of 0 to 2, and may be the same or different; u and v are Each represents an integer from 0 to 4, which may be the same or different, w represents an integer from 0 to 5, and n represents an integer of 1 or more.
(7) "Optical recording material comprising the two-photon absorption material according to any one of (1) to (6)",
(8) “Optical modeling material comprising the two-photon absorption material according to any one of (1) to (6)”,
(9) "Light limiting material comprising the two-photon absorption material according to any one of (1) to (6)",
(10) "Two-photon excited fluorescent material characterized by including the two-photon absorption material according to any one of (1) to (6)",
(11) In the three-dimensional optical recording medium formed on a plane and capable of recording / reproducing in a horizontal and vertical direction with respect to the plane, any one of (1) to (6) A three-dimensional optical recording medium comprising a two-photon absorbing material as at least a part of a recording layer on which optical recording is performed, "
(12) In the optical modeling apparatus that performs modeling by irradiating light to the photocurable resin, the two-photon absorbing material according to any one of the items (1) to (6) is the photocurable material. An optical modeling apparatus characterized by being included as at least a part of a resin ",
(13) In the light limiting device including an element for limiting transmitted light intensity, the two-photon absorption material according to any one of (1) to (6) is used as at least a part of the element. Light limiting device characterized in that it is included ",
(14) "In the light limiting device including an element that limits a light path, the two-photon absorption material according to any one of (1) to (6) is used as at least a part of the element. Light limiting device characterized in that it is included ",
(15) “By selectively supporting the two-photon absorption material according to any one of the items (1) to (6) on an analyte in a sample and detecting the two-photon absorption material” , A two-photon excitation fluorescence detection apparatus characterized by detecting an analyte ”.
By these, the organic material which absorbs two photons efficiently can be obtained.

  According to the present invention, an organic material having a large two-photon absorption cross section, that is, a highly sensitive two-photon absorption organic material can be provided. Moreover, if the novel two-photon absorption material of the present invention is used, the photosensitivity of various devices such as three-dimensional optical recording, optical modeling, and light detection can be dramatically improved.

Hereinafter, the present invention will be described in detail.
The two-photon absorption material of the present invention is a material capable of exciting a molecule at a wavelength in a non-resonant region, and an actual excited state exists at an energy level twice that of the photon used for excitation at this time. It is a material to do.
The two-photon absorption phenomenon is a kind of third-order nonlinear optical effect, and refers to a phenomenon in which a molecule absorbs two photons simultaneously and transitions from a ground state to an excited state.
The two-photon simultaneous absorption transition efficiency is extremely low compared to the one-photon absorption transition efficiency found in ordinary dye materials. Can not.
In order for two-photon absorption to occur, light with instantaneously high photon density, such as a mode-locked ultrashort (about femtosecond) pulse laser with extremely high peak light intensity (light intensity at the maximum emission wavelength) Must be used.
Such a phenomenon has been known for a long time, but since Jean-Luc Bredas et al. Recently clarified the relationship between molecular structure and mechanism in 1998 (Science, 281, 1653 (1998): Non-patent literature. 1) Two-photon absorption materials with high two-photon transition efficiency have been actively researched.

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, a two-photon absorption occurs only in a spot where the electric field strength is high, and a two-photon absorption does not occur in a spot peripheral portion where the electric field strength is low.
That is, in the three-dimensional space, two-photon absorption occurs only near the focal point where the electric field intensity collected by the lens is high, and no two-photon absorption occurs in a region outside the focal point where the electric field intensity is low. Compared with one-photon absorption in which absorption occurs in proportion to the first power of the field, the two-photon absorption material has a feature of having extremely high spatial resolution.

Until now, many inorganic materials have been found as highly efficient two-photon absorption materials.
However, inorganic materials have difficulty in practical use because so-called molecular design such as optimization of obtaining desired characteristics and optimization of structure and form is difficult. On the other hand, compared with inorganic materials, organic materials are excellent in practical use because they can be optimized by molecular design and can easily control other physical properties.
As conventional organic two-photon absorption materials, pigment compounds such as rhodamine and coumarin, compounds such as dithienothiophene derivatives and oligophenylene vinylene derivatives are known. However, the two-photon absorption cross section per molecule (which is an indicator of the two-photon transition efficiency, 1GM = 1 × 10 ^-50 cm ⁴ · s · photon ^-1 ) is obtained using a femtosecond pulse laser. Was as small as less than 200GM and was not practical.

  On the other hand, light that records data by causing spectral change, refractive index change, or polarization change due to two-photon absorption at a predetermined position of a recording medium that utilizes the extremely high spatial resolution that is characteristic of such a two-photon absorption material. Research on recording media has also been reported. Compared with the conventional optical recording method using the one-photon absorption phenomenon, the optical recording using the two-photon absorption phenomenon can theoretically reduce the recording / reproducing area, thereby realizing super-resolution recording. Is also possible. In addition, the use as an optical modeling material utilizing the characteristics of such a two-photon absorption material, the use as a light limiting material, and the application to a two-photon excited fluorescent material are also being studied.

  As an application of the two-photon excitation fluorescent material, when a short pulse laser in the near infrared region having a longer wavelength than the wavelength region where the linear absorption band of the two-photon absorbing material exists is used as the light source of the irradiation light, the irradiation is performed. Research can be applied to photodynamic therapy (PDT), such as performing two-photon image shadows in living tissue, because the loss of light being absorbed or scattered at locations other than the focal region can be minimized. Many examples have been reported.

<Characteristics of two-photon absorption material>
The method for producing the arylamine polymer of the present invention will be described below.
The method for producing an arylamine polymer of the present invention is, for example, Suzuki coupling (Synthetic Communications 11 (7), 513-519 (1981), Chem. Rev. 95 2457-2483 () using an aryl halide and an aryl boron compound. 1995), WO99 / 20675, and the method for polymer synthesis described in JP-A-2005-21434 of Patent Document 1), and cross-coupling reactions such as Still Coupling using arylhalogen and aryltin compounds are preferable.
The halogen atom of the aryl halide is preferably an iodide or bromide from the viewpoint of reactivity.
As the aryl boron compound, aryl boronic acid or aryl boronic acid ester is used. However, the aryl boronic acid ester does not form a dianhydride (boroxine) like aryl boronic acid, and has high crystallinity and purification. Is more preferable because it is easy.

As a synthesis method of the aryl boronic acid ester,
(I) A reaction of heating arylboronic acid and alkyldiol in an anhydrous organic solvent (Polymer 38 (5), 1221-1226 (1997), Chem. Mater. 13, 1540-1544 (2001)).
(Ii) Reaction in which an alkoxy boron ester is added after metallation of the halogen moiety of an aryl halide (Macromolecules 30,7686-7691 (1997), Macromolecules 32, 3306-3313 (1999), Macromolecules 37, 4087-4098 (2004) )reference.),
(Iii) a reaction in which an alkoxyboron ester is added after preparing a Grignard reagent of aryl halogen,
(Iv) Reaction in which aryl halide and bis (pinacolato) diboron or bis (neopentylglycolato) diboron are heated in the presence of a palladium catalyst (see J. Org. Chem. 60 (23), 7508-7519 (1995). ),
Obtained by.

As the palladium catalyst, various catalysts such as Pd (PPh ₃ ) ₄ , PdCl ₂ (PPh ₃ ) ₂ , Pd (OAc) ₂ , PdCl ₂ or separately adding triphenylphosphine as a ligand to palladium carbon are used. However, for the most general purpose, Pd (PPh ₃ ) ₄ is used. This reaction always requires a base, but relatively weak bases such as Na ₂ CO ₃ , NaHCO ₃ , K ₂ CO ₃ give good results. When affected by steric hindrance or the like, strong bases such as Ba (OH) ₂ and K ₃ PO ₄ are effective. Other caustic soda, caustic potash, metal alkoxide, etc., for example, 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 and the like can also be used. Further, a phase transfer catalyst may be used to make the reaction proceed more smoothly, preferably tetraalkylammonium halide, tetraalkylammonium hydrogensulfate, or tetraalkylammonium hydroxide. -N-butylammonium halide, benzyltriethylammonium halide, or tricaprylylmethylammonium chloride. Examples of the reaction solvent include alcohols such as methanol, ethanol, isopropanol, butanol, 2-methoxyethanol, 1,2-dimethoxyethane, and bis (2-methoxyethyl) ether, and ether ethers, and cyclic ethers such as dioxane and tetrahydrofuran. Benzene, toluene, xylene, dimethyl sulfoxide, N, N-dimethylformamide, N-methylpyrrolidone, 1,3-dimethyl-2-imidazolidinone and the like.

  The reaction temperature of the polymerization reaction is appropriately set depending on the reactivity of the monomer used and the reaction solvent, but it is preferable to keep it below the boiling point of the solvent. The reaction time in the polymerization reaction can be appropriately set in terms of the reactivity of the monomer used or the molecular weight of the desired polymer, and is preferably 2 to 50 hours, and more preferably 4 to 24 hours. . It is also possible to add a molecular weight regulator in order to adjust the molecular weight in these polymerization operations, or a sealing agent for sealing the end of the polymer as a terminal modifying group, at the start of the reaction. It is also possible to add it. Therefore, a group based on a terminator may be bonded to the end of the polymer in the present invention. Examples of the molecular weight regulator and the end-capping agent include compounds having one reactive group such as phenylboronic acid, bromobenzene, and iodobenzene. The preferred molecular weight of the polymer of the present invention is 1,000 to 1,000,000, more preferably 2000 to 500,000 in terms of polystyrene-reduced number average molecular weight. When the molecular weight is too small, the film formability 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 is also a practical problem.

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 polymer of the present invention obtained as described above is used after removing impurities such as the base, unreacted monomer, terminal terminator used in the polymerization, 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.

Specific examples of the general formulas (I) to (III) thus obtained are shown below. These are similarly applied to the arylamine monomers (IV) to (VI) of the present invention.
The substituted or unsubstituted aromatic hydrocarbon group Ar _{1 in the} general formulas (I) and (VI) may be a monocyclic group or a polycyclic group (a condensed polycyclic group or a non-condensed polycyclic group). Examples include phenyl, naphthyl, pyrenyl, fluorenyl, azulenyl, anthryl, triphenylenyl, chrycenyl, biphenyl, and terphenyl groups.
Examples of the divalent groups Ar ₂ and Ar ₃ of the substituted or unsubstituted aromatic hydrocarbon group in the general formulas (I) and (IV) include, as an example, the divalent group of the above substituted or unsubstituted aromatic hydrocarbon group. Groups. Further, these groups having a cyclic structure (Ar ₁ , Ar ₂ and Ar ₃ ) may have various substituents as shown in the following (a) to (f).

(A) A halogen atom, a trifluoromethyl group, a cyano group, or a nitro group.
(B) A linear or branched alkyl group or alkoxy group having 1 to 25 carbon atoms. These may be further substituted with a halogen atom, a cyano group, a phenyl group, a hydroxyl group, a carboxyl group, an alkoxy group, or an alkylthio group.
(C) Aryloxy group. Examples of the aryl group include an aryloxy group having a phenyl group and a naphthyl group. These may contain a halogen atom as a substituent, and may contain a linear or branched alkyl group, alkoxy group, or alkylthio group having 1 to 25 carbon atoms. Specific examples include phenoxy group, 1-naphthyloxy group, 2-naphthyloxy group, 4-methylphenoxy group, 4-methoxyphenoxy group, 4-chlorophenoxy group, 6-methyl-2-naphthyloxy group and the like. It is done.
(D) an alkylthio group or an arylthio group. Specific examples of the alkylthio group or arylthio group include a methylthio group, an ethylthio group, a phenylthio group, and a p-methylphenylthio group.
(E) an alkyl-substituted amino group. Specifically, diethylamino group, N-methyl-N-phenylamino group, N, N-diphenylamino group, N, N-di (p-tolyl) amino group, dibenzylamino group, piperidino group, morpholino group, Examples include a yurolidyl group.
(F) Acyl group. Specific examples of the acyl group include an acetyl group, a propionyl group, a butyryl group, a malonyl group, and a benzoyl group.

  These substituents can increase the solubility of the arylamine of the present invention in a solvent by increasing the number of carbon atoms constituting the substituent. Increasing the solubility can expand, for example, the choice of coating solvent, the temperature range during solution preparation, and the temperature range and pressure range during solvent drying. It is possible to obtain a high-quality thin film or bulk with high purity and high uniformity. In this case, a known film forming method such as spin coating method, casting method, dipping method, ink jet method, doctor blade method, screen printing method, dispensing method, spray coating, etc. can be used. A good thin film or bulk excellent in strength, toughness, durability and the like can be produced. On the other hand, since the two-photon absorption efficiency is lowered even if the number of carbon atoms is too large, it is necessary to appropriately select a substituent within a range that does not impair the solubility. In this case, preferable examples include an alkyl group having 1 to 25 carbon atoms, an alkoxy group, and an alkylthio group, and these may be used in the same manner or in a different manner. These alkyl groups, alkoxy groups and alkylthio groups are further halogen atoms, cyano groups, aryl groups, hydroxyl groups, carboxyl groups, linear, branched or cyclic alkyl groups having 1 to 12 carbon atoms, alkoxy groups or alkylthio groups. An aryl group substituted with a group may be contained. Specific examples of the alkyl group include methyl group, ethyl group, n-propyl group, i-propyl group, t-butyl group, s-butyl group, n-butyl group, i-butyl group, pentyl group, hexyl group, Heptyl group, octyl group, nonyl group, decyl group, dodecyl group, 3,7-dimethyloctyl group, 2-ethylhexyl group, trifluoromethyl group, 2-cyanoethyl group, benzyl group, 4-chlorobenzyl group, 4-methyl Examples thereof include a benzyl group, a cyclopentyl group, and a cyclohexyl group, and examples of the alkoxy group and the alkylthio group include those in which an oxygen atom or a sulfur atom is inserted into the bonding position of the alkyl group to form an alkoxy group or an alkylthio group, respectively.

In addition, the monomers according to claims 4 to 6 have the merit that, when mixed with other resins, compared with the corresponding polymers according to claims 1 to 3, it is not necessary to consider much compatibility. Therefore, there is an advantage that it is easy to mix with other resins and is excellent in processability. Moreover, since the solubility in a solvent is larger than that of a polymer, a high concentration solution can be prepared.
The arylamine of the present invention according to any one of claims 1 to 6 which efficiently absorbs two-photons is formed on (i) a plane, and can be recorded and reproduced horizontally and vertically with respect to the plane. Possible three-dimensional optical recording medium, or (ii) an optical modeling device that performs modeling by irradiating light to a photocurable resin, or (iii) an optical limiting device that changes the transmitted light intensity or path of incident light, or ( iv) A novel device having high sensitivity and three-dimensional high resolution can be provided by using in each of the light detection methods for detecting an analyte in a sample by light irradiation. These are matters of claims 7 to 15 of the present invention, and details thereof will be described below.

<Application to three-dimensional optical recording media>
Today, with the expansion of networks such as the Internet and Intranet, the widespread use of high-definition TV with 1920 x 1080 (vertical x horizontal) dot image information volume, and HDTV (HighDefinition Television) broadcasts in the near future, today's consumer data archiving applications Therefore, a recording medium of 50 GB or more, preferably 100 GB or more is required. Further, as a backup application for computers and broadcast videos, a recording medium capable of recording large-capacity information of about 1 TB or more at high speed and at low cost is required.
Under such circumstances, a three-dimensional optical recording medium that is attracting attention as an ultimate high-density, large-capacity recording medium is a recording medium that can record / reproduce in the vertical and horizontal directions with respect to incident light. By stacking dozens or hundreds of recording layers in the direction, or by using a thick film, it is possible to record and play back multiple times in the light incident direction, so conventional two-dimensional recording such as CD and DVD It is said to be a recording medium having the possibility of ultra-high density and ultra-high capacity recording that is tens or hundreds of times higher than that of the medium.
As described above, as a three-dimensional optical recording medium using a two-photon absorption material, a method of reading with fluorescence using a fluorescent substance for recording and reproduction (Levich, Eugene, Polis et al., Patent Document 6: Special Table 2001-524245). Publication, Pavel, Eugene et al., Patent Document 7: Japanese Translation of PCT International Publication No. 2000-512061), a method of reading by absorption or fluorescence using a photochromic compound (Corotif, Nikolai Eye et al., Patent Document 8: Japanese Patent Application Publication No. 2001-522119). Patent Literature 9: JP-A-2001-508221) and the like have been proposed, but none of them presents a specific two-photon absorption material and is presented abstractly. An example of the photon absorption compound also uses a two-photon absorption compound having extremely small two-photon absorption efficiency. Further, since the photochromic compounds used in these patent documents are reversible materials, there are problems in non-destructive reading, long-term storage stability of recording, S / N ratio of reproduction, and the like, a method that is practical as an optical recording medium I can't say that. In particular, in terms of non-destructive readout, long-term storage stability of recording, etc., it is preferable to reproduce by changing the reflectance (refractive index or absorptivity) or emission intensity using an irreversible material. There was no example that specifically disclosed the absorbent material.
Further, in Kawada Jun, Kawada Yoshimasa, Patent Document 10: JP-A-6-28672, Kawada Kei, Kawada Yoshimasa et al., Patent Document 11: JP-A-6-118306, three-dimensional recording is performed by refractive index modulation. However, there is no description of a method using a two-photon absorption three-dimensional optical recording material.

  If non-resonant two-photon absorption is used and the laser focus (recording) part and non-focus (non-recording) part can be modulated by a method that cannot be rewritten, recording can be performed at any place in a three-dimensional space with extremely high spatial resolution. It is possible to realize a three-dimensional optical recording medium that is an ultimate high-density recording medium. In addition, non-destructive readout is possible by using an irreversible material, and good storage characteristics can be maintained, which is more practical. However, currently available two-photon absorption materials have a low two-photon transition efficiency, so a very high-power light source is required as a light source used for recording, and furthermore, the sensitivity is low, so that the recording time is increased accordingly. There was a drawback that it took a long time. High-speed recording is indispensable for realizing a practical three-dimensional optical recording medium, and a highly sensitive optical recording material capable of high-speed recording has been strongly desired.

  The optical recording material of the present invention can be applied directly on a substrate by using a spin coater, roll coater, bar coater or the like, or cast as a film and then laminated on the substrate by a usual method. “Substrate” here means any natural or synthetic support, preferably one that can exist in the form of a flexible or rigid film, sheet or plate. The solvent used during solution preparation and coating can be removed by evaporation during drying, and heating or reduced pressure may be used for evaporation removal. Preferred substrates include polyethylene terephthalate, resin-primed polyethylene terephthalate, polyethylene terephthalate treated with flame or electrostatic discharge, cellulose acetate, polycarbonate, polymethyl methacrylate, polyester, polyvinyl alcohol, glass and the like. The substrate may be provided with a guide groove for tracking and address information in advance.

Further, a protective layer (intermediate layer) for blocking oxygen and preventing interlayer crosstalk may be formed on the two-photon absorption optical recording material. The protective layer (intermediate layer) is made of a plastic film or plate such as polypropylene, polyethylene, polyolefins such as polypropylene, polyvinyl chloride, polyvinylidene chloride, polyvinyl alcohol, polyethylene terephthalate or cellophane film. Alternatively, the layers may be laminated together or the polymer solution may be applied. Further, a glass plate may be bonded. However, even if such a protective layer (intermediate layer) is not provided, three-dimensional recording is possible due to the characteristics of the two-photon absorption material.
Furthermore, an adhesive or a liquid substance for enhancing airtightness may be present between the protective layer and the recording material and / or between the substrate and the recording material. Further, a guide groove for tracking and address information may be provided in advance in a protective layer (intermediate layer) between recording materials.

FIG. 1 shows an example (a) of a three-dimensional optical recording medium using the two-photon absorption material of the present invention as an optical recording material, and an example of a recording apparatus (b) thereof. However, the present invention is not limited in any way by these embodiments, and any other structure may be used as long as it can perform three-dimensional recording (recording in a plane and a film thickness direction).
FIG. 1A shows a flat support (substrate: 11a) having a recording layer (13a) made of the two-photon absorption material of the present invention and an intermediate layer (14a) (protective layer) for preventing crosstalk alternately. This is an example of a three-dimensional optical recording medium in which 50 layers are stacked. The thickness of the recording layer is preferably 0.01 to 0.5 μm, and the thickness of the intermediate layer is preferably 0.1 to 5 μm. With this structure, the recording layer has the same size as a CD or DVD that is widely used today, and has a large size of terabyte. An optical recording medium having a capacity can be realized.

In the three-dimensional recording of information, the light (15a) generated from the light source (11b) is focused on a desired location in the recording layer (13a) containing the two-photon absorption material comprising the arylamine of the present invention. Is done. A single beam is used as the light source, and in this case, ultrashort pulsed light of femtosecond order can be used. In addition to the bit-unit and depth-unit recording methods, a parallel recording method using a surface light source is preferable because it achieves a high transfer rate.
Although not shown here, a bulk-type recording medium having no intermediate layer is produced on the recording medium (FIG. 1a), and the page data is collectively recorded like hologram recording, thereby realizing a high transfer rate. It is also possible.

Reproduction is performed by irradiating the recording part and the non-recording part with laser light having a lower intensity than that at the time of recording, and detecting the change in the light emission intensity or the reflectance with the detector (13b). As the reproduction light, a light having a wavelength different from that of the beam used for data recording or the same wavelength with a low output can be used. Similar to recording, reproduction in bit units / page units is possible, and parallel recording / reproduction using a surface light source, a two-dimensional detector, or the like is effective in increasing the transfer rate.
In addition, as a form of the optical recording medium similarly formed according to the present invention, a card form, a plate form, a tape form, a drum form, and the like are also conceivable.

<Application as stereolithography material and stereolithography equipment>
The two-photon photocurable resin for stereolithography is a resin having a characteristic of causing a two-photon polymerization reaction when irradiated with light and changing from a liquid to a solid. The main components are a resin component consisting of an oligomer and a reactive diluent and a photopolymerization initiator (including a photosensitizing material as required). An oligomer is a polymer having a degree of polymerization of about 2 to 20, and has a large number of reactive groups at its ends. Further, a reactive diluent is added to adjust the viscosity, curability and the like. When irradiated with light, the polymerization initiator or photosensitizing material absorbs two photons, and reactive species are generated directly from the polymerization initiator or through the photosensitizing material, and react with the reactive groups of the oligomer and reactive diluent. Polymerization is started. Thereafter, a chain polymerization reaction is caused between them to form a three-dimensional cross-link, and in a short time, a solid resin having a three-dimensional network structure is formed.
Photocurable resins are used in fields such as photocurable inks, photoadhesives, and layered three-dimensional modeling, and resins having various characteristics have been developed. In particular, in layered three-dimensional modeling, it is important that the reactivity is good, the deposition shrinkage during curing is small, and the mechanical properties after curing are excellent.
The two-photon absorption material of the present invention can be used as a two-photon absorption polymerization initiator or a two-photon absorption photosensitizing material that satisfies such requirements. Since the two-photon absorption material of the present invention has a higher two-photon absorption sensitivity than before, high-speed modeling is possible, and since the two-photon absorption phenomenon is used, a fine and three-dimensional modeling can be realized.

In the present invention, the two-photon absorption material of the present invention used as a photosensitizing material is dispersed in an ultraviolet curable resin or the like to form a photosensitive material solid, and light irradiation is performed on a desired portion of the photosensitive material solid. The curing reaction is caused only in the vicinity of the focal point of the irradiation light to form an ultra-precise three-dimensional structure.
FIG. 2 is an example of an optical modeling apparatus when performing optical modeling using the two-photon absorption material of the present invention.
When the pulsed laser light from the light source (21) is condensed on the two-photon absorption material (24) of the present invention through the movable mirror (22) and the condenser lens (23), the photon density is only in the vicinity of the condensing point. A high region is formed. At this time, since the total number of photons passing through each cross section of the beam is constant, when the beam is scanned two-dimensionally within the focal plane, the total light intensity in each cross section is constant. However, since the probability of occurrence of two-photon absorption is proportional to the square of the light intensity, a region where the generation of two-photon absorption is high is formed only near the condensing point where the light intensity is high. The condensing point can be freely changed in the photocurable resin liquid by controlling the movable mirror (22) and the movable stage (25) (galvano mirror and Z stage). The resin can be locally cured with order accuracy, and a desired three-dimensional workpiece can be easily formed.

In addition, as an example of the modeled object thus manufactured, FIG. 3 shows an optical waveguide.
In recent years, while a recording medium for large-capacity archives is demanded, an increase in information transmission speed and capacity is also demanded by development of optical fiber communication for realizing a ubiquitous network. One of them is known as WDM (Wavelength Multiplexing Communication), which is a large-capacity transmission technology that uses the incoherence of light of different wavelengths. In WDM, optical signals of specific wavelengths are combined or An element for demultiplexing is indispensable, and an optical waveguide is used as an element for that purpose. In the optical waveguide, by forming a specific refractive index distribution or the like inside the element, an optical signal can be guided along the distribution so that electrons flow in the electric circuit. An optical waveguide structure using such a refractive index change due to wavelength uses the optical modeling apparatus shown in FIG. 2, and a thin film containing the two-photon absorption material of the present invention or the two-photon absorption material of the present invention is used as a photocurable resin. It can be formed by stereolithography of a solid object dispersed in the same.

Japanese Patent Application Laid-Open No. 2005-134873 is a known document useful for understanding the optical modeling in the present invention. According to this, pulsed laser light is subjected to interference exposure on the surface of the photosensitive polymer film without using a mask. The laser beam consists of light having a wavelength component that exerts the photosensitive function of the photosensitive polymer film, and is selected according to the type of photosensitive polymer or the group or site having the photosensitive function of the photosensitive polymer. Has been.
Also, as publicly known documents concerning optical waveguides, Japanese Patent Application Laid-Open No. 08-320422 discloses an optical waveguide formed by irradiating light on a photorefractive index material, Japanese Patent Application Laid-Open No. 2004-277416, and Japanese Patent Application Laid-Open No. 11-167036. JP, 2005-257741, A, etc.

Compared to such a conventional technique, the features of the optically shaped object using the two-photon absorption material of the present invention are as follows. That is,
(1) Processing resolution beyond the diffraction limit Due to the non-linearity of the two-photon absorption with respect to the light intensity, the photocurable resin is not cured in a region other than the focal point. For this reason, processing resolution exceeding the diffraction limit of irradiation light is realizable.
(2) Ultra-high-speed modeling Since the two-photon absorption sensitivity is higher in the modeled object processed using the two-photon absorption material of the present invention, the beam scanning speed can be increased.
(3) Three-dimensional processability The photocurable resin is transparent to near-infrared light that induces two-photon absorption. Therefore, even when the focused light is condensed deeply into the resin, internal curing is possible. In the conventional SIH, when the beam is condensed deeply, the light intensity at the condensing point becomes small due to light absorption, and the internal curing becomes difficult. In the present invention, these problems can be solved reliably. .
(4) High Yield In the conventional method, there is a problem that the modeled object is damaged or deformed due to the viscosity or surface tension of the resin, but in this method, such a problem is solved because modeling is performed inside the resin.
(5) Application to mass production By using ultra-high-speed modeling, it is possible to manufacture a large number of parts or movable mechanisms continuously in a short time.

<Application as light limiting material and light limiting device>
In optical communication and optical information processing, optical control such as modulation and switching is required to carry signals such as information with light. For this type of light control, an electro-light control method using an electric signal has been conventionally employed. However, in the electro-optical control method, the processing speed (> 10 ps) is limited due to the band limitation due to the CR time constant as in an electric circuit, the response speed of the element itself, and the mismatch between the speed between the electric signal and the optical signal. In order to make full use of the broadband and high speed, which are the advantages of light, the light-light control technology for controlling the optical signal by the optical signal becomes very important. An optical element manufactured by processing the two-photon absorption material of the present invention in response to this requirement utilizes an optical change such as transmittance, refractive index, absorption coefficient, etc. caused by irradiating light, and an electronic circuit. By directly modulating light intensity and frequency with light without using technology, it can be applied to high-speed optical switches in optical communication, optical exchange, optical computer, optical interconnection, and the like.
The optical limiting element of the present invention that utilizes the change in optical characteristics due to two-photon absorption is an optically limiting element that is formed of a normal semiconductor material, or an element that has a much higher response speed (<1 ps) than those based on one-photon excitation. ), And because of its high sensitivity, it is possible to provide an optical limiting element excellent in signal characteristics with a high S / N ratio.

Examples of conventional optical limiting elements using single-photon absorption or supersaturated absorption include spectral hole burning, exciton absorption, intersubband transition, quantum confinement chattalc effect, etc. There are problems in that it is difficult to obtain an ultrafast response, device fabrication (composition and structure) is complicated, the corresponding wavelength range is narrow, and there are many systems with large polarization dependence.
On the other hand, an optical limiting element using nonlinearity of two-photon absorption has excellent ultrafast response, easy element fabrication (composition, structure), wide wavelength range and wide wavelength selection, polarization dependence There is an advantage that there is no.

FIG. 4 shows an element that switches signal light of a wavelength that can be excited by one photon by two-photon excitation of the two-photon absorption material of the present invention with control light of a specific wavelength.
The laser light incident from the control light (41) and the signal light (42) is collected by the light condensing device (43) (lens, concave mirror, etc.), and the protective layer only when the intensity of the control light (41) is extremely strong. Is absorbed in the optical filter (44) made of the two-photon absorption material of the present invention sandwiched between and the transmittance of the one-photon excitation wavelength is changed. If the intensity of the control light (42) is not strong or weak, it passes through as it is, and a photodetector (45) on the light exit side through a color filter (46) etc. that removes stray light by a collimator (45) (lens, concave mirror, etc.) 47). That is, by utilizing the change in transmittance due to the nonlinearity of two-photon absorption in this way, it is possible to perform high-speed optical switching that processes signal light with the intensity of control light.

FIG. 5 shows an operation example of a light control element that performs two-photon excitation of the two-photon absorption material of the present invention with signal light and control light and performs all-optical switching.
The control light and the signal light are collected by a light collecting device on a light limiting element having a two-photon absorption material as a main component. When the control light is off, the signal light is output as it is. When the control light is on, Two-photon is absorbed together with the signal light, and the output is lost. By turning on / off the control light, an optical switch of signal light is possible.

Further, FIG. 5 shows an example of a light control element that switches the optical path of output light by two-photon excitation of the two-photon absorption material of the present invention with control light having a wavelength capable of two-photon excitation.
The laser light incident from the control light and the signal light is focused on the branch path portion of the optical waveguide whose main component is the two-photon absorption material by the condensing device, and is branched only when the intensity of the control light is extremely strong. It is absorbed by the road part and the refractive index of the part changes. The optical path of the output light can be switched by adjusting the refractive index change of the branch path portion of the optical waveguide due to two-photon absorption, the refractive index of the optical waveguide of the signal light, and the refractive index of the optical waveguide of the output light. By utilizing the change in the refractive index accompanying the nonlinearity of two-photon absorption, it becomes possible to switch the optical path in, for example, an optical waveguide.

  Known documents useful for understanding the light limiting element in the present invention include an optical waveguide (Japanese Patent Laid-Open No. 8-320422) formed by irradiating light to a photorefractive index material, and Japanese Patent Laid-Open No. 2004-277416. The optical functional element using the two-photon absorption material of the present invention is an element formed of a normal semiconductor material, although disclosed in Japanese Laid-Open Patent Publication No. 11-167036 and Japanese Unexamined Patent Publication No. 2005-257741. Compared to a device that uses one-photon excitation of a material, it has excellent signal characteristics such as a far superior response speed, high sensitivity, and a high S / N ratio.

<Application to two-photon excitation fluorescence detection method>
The two-photon excitation fluorescence detection method is a two-photon excited material that is scanned by focusing a near-infrared pulse laser on a sample containing an analyte labeled with a two-photon fluorescent material. It is a detection method that obtains an image three-dimensionally by detecting fluorescence that is sometimes generated. FIG. 7 shows a two-photon excitation fluorescence microscope as an example of such a light detection device.
The apparatus in FIG. 7 generates laser light from a light source (71) that generates sub-picosecond monochromatic coherent pulses in the near-infrared region, passes through a dichroic mirror (72), and is collected by a condenser (73). Two-photon fluorescence is generated by focusing in a sample (74) containing an analyte to which the two-photon absorbing material of the present invention is bound. A three-dimensional fluorescence image is obtained by manipulating the laser beam on the sample, detecting the fluorescence intensity at each location with a photodetector (76), and plotting the fluorescence intensity and the obtained position information on a computer. Can do. In this case, the microscope is provided with a scanning mechanism for scanning a desired condensing position with a laser beam. For example, a sample placed on a stage (75) may be moved, or a movable mirror ( A laser beam may be scanned using a galvanometer mirror or the like.
A two-photon excitation fluorescence microscope having such a configuration can obtain a high-resolution image in the optical axis direction. However, by using a confocal pinhole plate, the resolution can be further improved in both the in-plane and optical axis directions. it can.

  The two-photon fluorescent material used in this way can be used by staining an analyte or by dispersing it in the analyte, and is used not only for industrial use but also for three-dimensional image microimaging of living cells and the like. be able to. It can also be used as a photosensitive material in photodynamic therapy (PDT) by mixing with a biocompatible polymer.

Japanese Patent Laid-Open No. 9-230246 is a known document useful for understanding the two-photon excitation fluorescence microscope of the present invention. For example, a scanning fluorescent microscope includes a laser irradiation optical system that emits collimated light expanded to a desired size, and a substrate on which a plurality of condensing elements are formed. A beam splitter that transmits a long wavelength and reflects a short wavelength is disposed between the substrate on which the light condensing element is formed and the objective lens system, so as to coincide with the image position of the system. The surface is characterized by generating fluorescence by multiphoton absorption.
With such a configuration, it is possible to obtain high resolution in the optical axis direction by utilizing the nonlinear effect of multiphoton absorption itself. In addition, if a confocal pinhole plate is used, higher resolution (both in-plane and in the optical axis direction) can be obtained.

  The two-photon excitation fluorescent material including the two-photon absorption material of the present invention has a large two-photon absorption cross-sectional area as compared with the conventional two-photon excitation fluorescent material. Demonstrate the characteristics. Therefore, according to the present invention, since it is not necessary to increase the intensity of light applied to the material, deterioration and destruction of the material can be suppressed, and adverse effects on the characteristics of other components in the material can be reduced. In particular, when applied to a living body, the intensity of light to be irradiated can be lowered, so that damage to the living body can be reduced.

  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
The poly (triarylamine) derivative of the present invention was synthesized according to the following synthesis method.
In a 50 ml three-necked flask, 0.938 g (1.5 mmol) of a diboron ester having the following structure, 0.861 g (1.5 mmol) of a dibromo having the following structure, Aliquat 336 (manufactured by Aldrich) as a phase transfer catalyst 12. 8 mg (0.032 mmol), tetrakistriphenylphosphinepalladium 10.0 mg (0.0087 mmol), and toluene 9 ml were added. After replacing with argon gas, 2 M-sodium carbonate aqueous solution 3.5 ml was added and refluxed for 6 hours. As a reaction, first, 80 mg (0.66 mmol) of phenylboronic acid was added and refluxed for 4 hours, and then 150 mg (0.96 mmol) of bromobenzene was added and refluxed for 4 hours. Thereafter, the reaction solution was returned to room temperature, and then the organic layer was dropped into a mixed solvent of methanol / water and reprecipitated to obtain a crude polymer. The obtained polymer was used as a chloroform solution, and washing with ion-exchanged water was repeated until the conductivity of the washing liquid became equivalent to that of ion-exchanged water. After washing, the polymer was made into a tetrahydrofuran solution, and the polymer was purified by dropwise addition to methanol and reprecipitation.
The yield at this time was 0.925 g, the yield was 79%, the number average molecular weight in terms of polystyrene measured by GPC (gel permeation chromatography) was 35,000, and the weight average molecular weight was 94,000.
Elemental analysis values (calculated values) were C: 76.244% (76.39%), H: 7.73% (7.56%), N: 1.92% (1.78%), S : 11.95% (12.23%). FIG. 8 shows an infrared absorption spectrum (NaCl cast film).
A tetrahydrofuran solution of the two-photon absorption material (the following formula) synthesized in this way was prepared, and the prepared solution was evaluated according to a method for measuring a two-photon absorption cross section (σ ₂ ′) described later. The measured two-photon absorption spectrum and σ ₂ ′ evaluation results are shown in FIG. 11 and Table 1, respectively.

(Example 2)
The poly (triarylamine) derivative of the present invention was synthesized according to the following synthesis method.
In a 50 ml three-necked flask, 0.938 g (1.5 mmol) of a diboron ester having the following structure, 1.237 g (1.5 mmol) of a dibromo having the following structure, Aliquat 336 (manufactured by Aldrich) as a phase transfer catalyst. 5 mg (0.031 mmol), 10.0 mg (0.0087 mmol) of tetrakistriphenylphosphine palladium and 9 ml of toluene were added. After replacing with argon gas, 3.5 ml of 2M sodium carbonate aqueous solution was added and refluxed for 4 hours. As a reaction, first, 80 mg (0.66 mmol) of phenylboronic acid was added and refluxed for 4 hours, and then 150 mg (0.96 mmol) of bromobenzene was added and refluxed for 4 hours. Thereafter, the reaction solution was returned to room temperature, and then the organic layer was dropped into a mixed solvent of methanol / water and reprecipitated to obtain a crude polymer. The obtained polymer was used as a chloroform solution, and washing with ion-exchanged water was repeated until the conductivity of the washing liquid became equivalent to that of ion-exchanged water. After washing, the polymer was made into a tetrahydrofuran solution, and the polymer was purified by dropwise addition to methanol and reprecipitation.
The yield at this time was 1.10 g, and the yield was 71%. The number average molecular weight in terms of polystyrene measured by GPC (gel permeation chromatography) was 41400, and the weight average molecular weight was 116400.
Elemental analysis values (calculated values) were C: 76.43% (76.47%), H: 8.46% (8.26%), N: 1.51% (1.35%), S : 12.3% (12.37%). FIG. 9 shows an infrared absorption spectrum (NaCl cast film).
A tetrahydrofuran solution of the two-photon absorption material (the following formula) synthesized in this way was prepared, and the prepared solution was evaluated according to a method for measuring a two-photon absorption cross section (σ ₂ ′) described later. The measured two-photon absorption spectrum and the evaluation result of σ ₂ ′ are shown in FIG. 12 and Table 1, respectively.

(Example 3)
According to the following synthesis method, a tetrahydrofuran solution of a triarylamine derivative represented by the following formula was prepared. The prepared solution was evaluated according to a method for measuring a two-photon absorption cross-sectional area described later, and the evaluation results are shown in Table 1.

Example 4
In the same manner as in Example 1, a triarylamine derivative represented by the following formula was synthesized according to the following synthesis method, and a tetrahydrofuran solution (0.0025% concentration) was prepared. The prepared solution was evaluated according to a method for measuring a two-photon absorption cross-sectional area described later, and the evaluation results are shown in Table 1.

(Comparative Example 1)
As an example of a conventional material, a tetrahydrofuran solution of the following diallylethene derivative was prepared, and the two-photon absorption cross section was measured in the same manner. The evaluation results are shown in Table 1.

(Comparative Example 2)
As examples of materials having a large two-photon absorption cross section, the following styryl derivatives were evaluated in the same manner.

[Evaluation method of two-photon absorption cross section]
A schematic diagram of the measurement system is shown in FIG.
Measurement light source: femtosecond titanium sapphire laser Wavelength: 720-920 nm
Pulse width: 100 fs
Repetition frequency: 80 MHz
Measurement optical power: 500 mW
Measuring method: Z-scan method Cuvette inner diameter: 1mm
Condenser lens: f = 75 mm
Condensing diameter: 40 μm
A quartz cell filled with the sample solution was placed in the collected optical path portion, and Z-scan measurement was performed by moving the position along the optical path.
The transmittance was measured, and the nonlinear absorption coefficient was determined from the result by the theoretical formula (1).
T = [ln (1 + I ₀ L ₀ β)] / I ₀ L ₀ β (1)
(In the above formula, T represents transmittance (%), I ₀ represents excitation light density [GW / cm ² ], L ₀ represents sample cell length [cm], and β represents nonlinear absorption coefficient [cm / GW].)
From this nonlinear absorption coefficient β, a two-photon absorption cross-sectional area σ was obtained by the following equation (2).
(The unit of σ is 1GM = 1 × 10 ⁻⁵⁰ cm ⁴ · s · photon ⁻¹ .)
_{σ = 1000 × hνβ / N A} Cβ ···· (2)
(In the formula, h is Planck's constant [J · s], ν is the frequency of the incident laser light ^[s -1], _{N A} is Avogadro's number, C is concentration of solution [mol / L].)

<Evaluation results>
In any of the examples, it was found that the material is a high-efficiency two-photon absorption material having a larger two-photon absorption cross-sectional area than the conventional material shown in the comparative example.

It is a figure which shows an example of the three-dimensional optical recording medium (a) using the two-photon absorption material of this invention as an optical recording material, and its recording device (b). It is a figure which shows an example of the optical modeling apparatus in the case of performing optical modeling using the two-photon absorption material of this invention. It is a figure which shows the optical waveguide as an example of the molded article produced with an optical modeling apparatus. It is a figure which shows an example of the light control element which optically switches the signal light of the wavelength which can carry out one-photon excitation by carrying out the two-photon excitation of the two-photon absorption material of this invention with the control light of the wavelength which can carry out two-photon excitation. It is a figure which shows the operation example of the light control element which carries out the all-optical switching which excites the two-photon absorption material of this invention by signal light and control light. It is a figure which shows an example of the light control element which optically switches the optical path of output light by carrying out the two-photon excitation of the two-photon absorption material of this invention with the control light of the wavelength which can carry out a two-photon excitation. It is a figure which shows an example of a two-photon excitation fluorescence microscope. It is a figure which shows the infrared absorption spectrum (NaCl cast film | membrane) of Example 1. FIG. It is a figure which shows the infrared absorption spectrum (NaCl cast film) of Example 2. It is the schematic of the measurement system used by this invention. 2 is a diagram showing a two-photon absorption spectrum of Example 1. FIG. 6 is a diagram showing a two-photon absorption spectrum of Example 2. FIG.

Explanation of symbols

(About Figure 1)
11a Substrate (support)
11b Light source 12a Substrate (support)
12b Light source 13a Recording layer 13b Detector 14a Intermediate layer (protective layer)
14b Pinhole 15a Light (About Figure 2)
21 Light source 22 Movable mirror 23 Condensing lens 24 Two-photon absorbing material 25 Movable stage (about FIG. 4)
41 control light 42 signal light 43 condensing device 44 optical filter 45 collimating device 46 color filter 47 detector (about FIG. 7)
71 Light source 72 Dichroic mirror 73 Condensing device 74 Sample 75 Stage 76 Photodetector

Claims (15)

A two-photon absorption polymer comprising a repeating unit represented by the following general formula (I):

(In the formula, Ar ₂ and Ar ₃ are a divalent group of a substituted or unsubstituted aromatic hydrocarbon group, and Ar ₁ represents a substituted or unsubstituted aromatic hydrocarbon group. R ¹ , R ² and R ³ represents an alkyl group, x, y and z each represents an integer of 0 to 2, which may be the same or different, and n represents an integer of 1 or more.) The two-photon absorption polymer according to claim 1 is represented by the following general formula (II).

(In the formula, Ar ₁ is a divalent group of a substituted or unsubstituted aromatic hydrocarbon group, R ¹ , R ² , and R ³ represent an alkyl group, and R ⁴ and R ⁵ are each independently, Represents a group selected from a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkoxy group, or a substituted or unsubstituted alkylthio group, and may be the same or different, and each of x, y, and z is 0 to 2 And may be the same or different, and u and v each represent an integer of 0 to 4, may be the same or different, and n represents an integer of 1 or more.) The two-photon absorption polymer according to claim 2, wherein the two-photon absorption polymer is represented by the following general formula (III).

(Wherein R ¹ , R ² and R ³ represent an alkyl group, and R ⁴ , R ⁵ and R ⁶ each independently represents a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkoxy group, or Represents a group selected from substituted or unsubstituted alkylthio groups, which may be the same or different; x, y and z each represent an integer of 0 to 2, and may be the same or different; u and v are And each represents an integer of 0 to 4, which may be the same or different, w represents an integer of 0 to 5, and n represents an integer of 1 or more.) A two-photon absorption material represented by the following general formula (IV):

(In the formula, Ar ₂ and Ar ₃ are a divalent group of a substituted or unsubstituted aromatic hydrocarbon group, and Ar ₁ represents a substituted or unsubstituted aromatic hydrocarbon group. R ¹ , R ² and R ³ represents an alkyl group, which may be the same or different, and x, y and z each represents an integer of 0 to 2, and may be the same or different, and n represents an integer of 1 or more.) The two-photon absorbing material according to claim 4 is represented by the following general formula (V).

(In the formula, Ar ₁ is a divalent group of a substituted or unsubstituted aromatic hydrocarbon group, R ¹ , R ² , and R ³ represent an alkyl group, and R ⁴ and R ⁵ are each independently, Represents a group selected from a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkoxy group, or a substituted or unsubstituted alkylthio group, and may be the same or different, and each of x, y, and z is 0 to 2 And may be the same or different, and u and v each represent an integer of 0 to 4, may be the same or different, and n represents an integer of 1 or more.) The two-photon absorption material according to claim 5 is represented by the following general formula (VI).

(Wherein R ¹ , R ² and R ³ represent an alkyl group, and R ⁴ , R ⁵ and R ⁶ each independently represents a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkoxy group, or Represents a group selected from substituted or unsubstituted alkylthio groups, which may be the same or different; x, y and z each represent an integer of 0 to 2, and may be the same or different; u and v are And each represents an integer of 0 to 4, which may be the same or different, w represents an integer of 0 to 5, and n represents an integer of 1 or more.) An optical recording material comprising the two-photon absorption material according to claim 1. An optical modeling material comprising the two-photon absorption material according to claim 1. An optical limiting material comprising the two-photon absorption material according to claim 1. A two-photon excitation fluorescent material comprising the two-photon absorption material according to claim 1. 7. A three-dimensional optical recording medium formed on a plane and capable of recording and reproducing in a horizontal and vertical direction with respect to the plane, the two-photon absorbing material according to claim 1 performs optical recording. A three-dimensional optical recording medium comprising at least a part of a recording layer. The optical modeling apparatus which models by irradiating light to photocurable resin, The two-photon absorption material in any one of Claims 1 thru | or 6 is contained as at least one part of the said photocurable resin. Stereolithography apparatus characterized by A light limiting device comprising an element for limiting transmitted light intensity, wherein the two-photon absorption material according to any one of claims 1 to 6 is included as at least a part of the element. apparatus. An optical limiting device comprising an element for limiting the path of light, wherein the two-photon absorption material according to any one of claims 1 to 6 is included as at least a part of the optical element. apparatus. An analyte in a sample is detected by selectively supporting the two-photon absorbing material according to any one of claims 1 to 6 and detecting the two-photon absorbing material. Two-photon excitation fluorescence detection device.

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