JP2012137549A - Two-photon absorbing material and use thereof - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a two-photon absorbing material having an absorption band as short as possible and having an excellent two-photon absorbing property.SOLUTION: A two-photon absorbing material comprises a diphenylsulfone derivative represented by Chemical Formula (1), wherein m indicates 1 or 2; n indicates 1 or 2; and Rto Rand Rto Rmay be the same as or different from one another and indicate hydrogen, a halogen atom, a hydroxyl group, an alkyl group, an alkoxyl group, an amino group, a monoalkylamino group, a dialkylamino group, an alkylthio group, a phenyl group or -NHCOR(wherein R' indicates an alkyl group), or a combination of Rand R, a combination of Rand R, a combination of Rand Ror a combination of Rand Rmay form a 5- to 7-membered condensed ring, and a combination of Rand R, a combination of Rand R, a combination of Rand Ror a combination of Rand Rmay form a 5- to 7-membered condensed ring.

Description

  The present invention relates to a two-photon absorbing material containing a diphenylsulfone derivative, which is a novel organic nonlinear optical material. More specifically, the present invention can be used for applications such as three-dimensional optical recording materials, light-limiting materials, photocuring materials used for optical modeling applications, photochemotherapy materials, fluorescent dye materials for two-photon fluorescence microscopes, The present invention relates to a two-photon absorbing material containing a diphenylsulfone derivative, which is a novel organic nonlinear optical material.

  The nonlinear optical effect has an important role in information processing using light. The non-linear optical effect is a general term for effects generated from second-order, third-order, and higher-order terms in the polarization induced by the optical electric field strength. Of these, the effects of the fourth and higher order have a very low susceptibility and it is difficult to observe effective phenomena in application, so much research has been conducted mainly on the second and third order nonlinear optical effects. ing.

  As the second-order nonlinear optical effect, second harmonic generation (SHG), electro-optic effect (Pockels effect), photorefractive effect, and the like are known. For this reason, development of non-linear optical materials having a second-order nonlinear optical effect to optical communication using wavelength control, phase control, and the like has been studied. On the other hand, third-order nonlinear optical effects include optical third-harmonic generation (THG), electro-optical effect (Kerr effect), optical Kerr effect, photoinduced refractive index change, degenerate four-wave mixing, and optical bifurcation. Stability phenomena and two-photon absorption phenomena are known. Therefore, a nonlinear optical material having a three-dimensional nonlinear optical effect is expected to be applied to an optical switch using a change in refractive index and an absorption coefficient due to light.

  Conventionally, with regard to nonlinear optical materials, the above-described nonlinear optical characteristics of organic compound materials are excellent, but there is a problem that durability and reliability are inferior. Therefore, organic compound materials cannot surpass inorganic materials, and inorganic materials have been generally used. However, in recent years, the excellent characteristics and high-speed response of organic compound materials having a much larger nonlinear optical constant than inorganic materials are being reviewed. Therefore, development of an organic nonlinear optical material having these excellent characteristics and having excellent durability and reliability is demanded.

  As a general method for improving nonlinear optical characteristics in an organic compound material, there is a method of further expanding the conjugated system by selecting an appropriate electron donating / attracting substituent. However, since this method involves a deep color effect, there is a problem that the light resistance of the molecule (organic compound material) itself is reduced, and the light that induces nonlinear optical characteristics and the increase of the absorption coefficient for the generated harmonic region are promoted. It was.

  As an effort to improve such a problem, for example, in Patent Document 1, as a second-order nonlinear optical material, by introducing a substituent that induces a hypochromic effect in a molecular structure, excellent nonlinearity is shown and second order. We have proposed organic nonlinear optical materials that can generate harmonics efficiently.

  In a third-order nonlinear optical material that is expected to be applied to an optical switch or the like, a technique for enlarging a conjugate system is generally taken as a means for improving nonlinear optical characteristics. For example, in Patent Documents 2, 3, 4, and 5, improvements are made with respect to styryl, ketone, arylamine, and porphyrin compounds.

  Patent Document 6 discloses a two-photon absorption polymerizable composition containing (a) a polymerizable compound, (b) a dithiocarbamate group-containing polymer compound, and (c) a two-photon absorption compound. It is disclosed that this composition is highly sensitive, does not require a high-power laser light source, and can obtain a shaped article with high resolution and high accuracy.

JP-A-5-196976 US Pat. No. 6,267,913 JP 2003-183213 A JP 2007-241168 A Japanese Patent Laying-Open No. 2005-267338 JP 2010-065083 A

  In the above document, an organic compound having a structure in which a conjugated system is expanded in order to improve two-photon absorption characteristics is described. However, by enlarging the conjugated system, the two-photon absorption characteristics are improved, while the excitation wavelength region that induces two-photon absorption is also shifted to the long wavelength region. Therefore, in this method, there is a possibility that the selection range of the excitation light source that induces two-photon absorption may be narrowed, and there is room for improvement. Therefore, a two-photon absorbing material having an absorption band with a short wavelength as much as possible and having excellent two-photon absorption characteristics is desired.

  Patent Document 3 reports that a ketone derivative having a two-photon absorption characteristic is extended to improve the two-photon absorption characteristic by extending the conjugated system. However, this characteristic improvement has a drawback with a significant deep color effect. Accordingly, the present invention aims to solve these problems. More specifically, the present invention relates to a two-photon absorbing material containing a diphenylsulfone derivative that has improved two-photon absorption characteristics while suppressing deepening of the absorption wavelength, and a photocuring containing the two-photon absorbing material. It is in providing a conductive resin composition. This two-photon absorbing material can be applied to uses such as three-dimensional optical recording materials, light-limiting materials, photocuring materials used for optical modeling applications, photochemotherapy materials, and fluorescent dye materials for two-photon fluorescence microscopes. .

The present inventors have focused on sulfone derivatives as two-photon absorbing materials. And when the styryl group was added to the sulfone derivative and the conjugated system was expanded, it was found that the two-photon absorption characteristics can be improved by the effect of the substituent while suppressing the deep color effect of the absorption wavelength. The present invention has been completed.
Accordingly, the present invention provides the following two-photon absorbing material.

［式中、ｍは１または２を示し、ｎは１または２を示し、
Ｒ^１〜Ｒ^５、Ｒ^６〜Ｒ^１０はそれぞれ、同一または異なっていてもよく、水素、ハロゲン原子、ヒドロキシル基、アルキル基、アルコキシル基、アミノ基、モノアルキルアミノ基、ジアルキルアミノ基、アルキルチオ基、フェニル基、−ＮＨＣＯＲ^’（但しＲ’はアルキル基を示す）を示すか、或いは、Ｒ^１及びＲ^２、Ｒ^２及びＲ^３、Ｒ^３及びＲ^４、またはＲ^４及びＲ^５が一緒になって５〜７員環の縮合環を形成してよく、Ｒ^６及びＲ^７、Ｒ^７及びＲ^８、Ｒ^８及びＲ^９、またはＲ^９及びＲ^１０が一緒になって５〜７員環の縮合環を形成してよい。］
で表わされるジフェニルスルホン誘導体を含有する二光子吸性材料である。 Following formula (1)

[Wherein m represents 1 or 2, n represents 1 or 2,
R ^{1 to} R ⁵ and R ^{6 to} R ¹⁰ may be the same or different and each is a hydrogen atom, a halogen atom, a hydroxyl group, an alkyl group, an alkoxyl group, an amino group, a monoalkylamino group, a dialkylamino group, or an alkylthio group. , Phenyl group, —NHCOR ^′ (wherein R ′ represents an alkyl group), or R ¹ and R ² , R ² and R ³ , R ³ and R ⁴ , or R ⁴ and R ⁵ together May form a 5- to 7-membered condensed ring, and R ⁶ and R ⁷ , R ⁷ and R ⁸ , R ⁸ and R ⁹ , or R ⁹ and R ¹⁰ together form a 5- to 7-membered ring. The condensed ring may be formed. ]
Is a two-photon absorbing material containing a diphenylsulfone derivative represented by the formula:

At least one of the substituents R ³ and R ⁸ of the diphenylsulfone derivative represented by the above formula (1) is an alkyl group, an alkoxyl group, an amino group, a monoalkylamino group, a dialkylamino group, an alkylthio group, a phenyl group,- It is preferably an electron donating substituent selected from NHCOR ^′ (where R ′ represents an alkyl group), and it is more preferable that both R ³ and R ⁸ are the same electron donating substituent. Moreover, it is preferable that at least one of R ³ and R ⁸ is a dialkylamino group, and it is more preferable that both R ³ and R ⁸ are dialkylamino groups.

In addition, a two-photon absorbing material in which the molar absorption coefficient of the maximum wavelength at 250 to 800 nm of the diphenylsulfone derivative represented by the above formula (1) is 55000 mol ⁻¹ dm ³ cm ⁻¹ or more is more preferable.

  And the photocurable resin composition of this invention is a photocurable resin composition containing the two-photon absorptive material containing the diphenyl sulfone derivative shown by Formula (1).

  The light-emitting material of the present invention is a light-emitting material containing a two-photon absorbing material containing a diphenylsulfone derivative represented by the formula (1).

  The optical recording material of the present invention is an optical recording material containing a two-photon absorbing material containing a diphenylsulfone derivative represented by the formula (1).

  The microscope fluorescent dye material of the present invention is a microscope fluorescent dye material containing a two-photon absorbing material containing a diphenylsulfone derivative represented by the formula (1).

  In addition, the light limiting material of the present invention is a light limiting material containing a two-photon absorbing material containing a diphenylsulfone derivative represented by the formula (1).

  The two-photon absorbing material of the present invention contains a genyl sulfone derivative having a styryl group. This two-photon absorptive material is colorless to yellow and has a characteristic of having a high efficiency two-photon absorptivity. Furthermore, this two-photon absorbing material has an excellent characteristic that two-photon absorption occurs in an absorption band of a short wavelength because deepening of the absorption wavelength is suppressed. The two-photon absorbing material of the present invention can be contained in, for example, a photocurable resin composition, a light emitting material, an optical recording material, a fluorescent dye material for a microscope, or a light limiting material. For example, by using the photocurable resin composition containing the two-photon absorbing material of the present invention, ultrahigh density optical recording, MEMS or photonic crystal creation by photocurable resin microfabrication, fluorescent probe, light limiting material It is possible to provide a photosensitive material that is useful in fields such as the above and has high spatial selectivity or controllability by light.

It is the schematic of the two-photon fluorescence measuring system used by this invention, and an excitation laser optical path. It is the schematic of the two-photon fluorescence measuring system used by this invention, and a fluorescence detection optical path. It is the schematic of the two-photon polymerization system used by this invention.

［式中、ｍは１または２を示し、ｎは１または２を示し、
Ｒ^１〜Ｒ^５、Ｒ^６〜Ｒ^１０はそれぞれ、同一または異なっていてもよく、水素、ハロゲン原子、ヒドロキシル基、アルキル基、アルコキシル基、アミノ基、モノアルキルアミノ基、ジアルキルアミノ基、アルキルチオ基、フェニル基、−ＮＨＣＯＲ^’（但しＲ’はアルキル基を示す）を示すか、或いは、Ｒ^１及びＲ^２、Ｒ^２及びＲ^３、Ｒ^３及びＲ^４、またはＲ^４及びＲ^５が一緒になって５〜７員環の縮合環を形成してよく、Ｒ^６及びＲ^７、Ｒ^７及びＲ^８、Ｒ^８及びＲ^９、またはＲ^９及びＲ^１０が一緒になって５〜７員環の縮合環を形成してよい。］
で表わされるジフェニルスルホン誘導体を含有する。 Two-photon absorbing material The two-photon absorbing material of the present invention has the following formula (1):

[Wherein m represents 1 or 2, n represents 1 or 2,
R ^{1 to} R ⁵ and R ^{6 to} R ¹⁰ may be the same or different and each is a hydrogen atom, a halogen atom, a hydroxyl group, an alkyl group, an alkoxyl group, an amino group, a monoalkylamino group, a dialkylamino group, or an alkylthio group. , Phenyl group, —NHCOR ^′ (wherein R ′ represents an alkyl group), or R ¹ and R ² , R ² and R ³ , R ³ and R ⁴ , or R ⁴ and R ⁵ together May form a 5- to 7-membered condensed ring, and R ⁶ and R ⁷ , R ⁷ and R ⁸ , R ⁸ and R ⁹ , or R ⁹ and R ¹⁰ together form a 5- to 7-membered ring. The condensed ring may be formed. ]
The diphenyl sulfone derivative represented by these is contained.

In the above formula (1), examples of the substituent represented by R ^{1 to} R ¹⁰ include the following substituents.

  Examples of the halogen atom include fluorine, chlorine, bromine and iodine.

  Examples of the alkyl group include a linear or branched alkyl group having 1 to 18 carbon atoms and an alicyclic alkyl group having 3 to 18 carbon atoms. The alkyl group is more preferably a linear or branched alkyl group having 1 to 10 carbon atoms. Specific examples of the alkyl group include, for example, methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, i-butyl group, sec-butyl group, t-butyl group, n-pentyl group, neo-pentyl, n-hexyl, n-heptyl, n-octyl, 2-ethylhexyl, n-decyl, lauryl, stearyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cyclo An octyl group etc. are mentioned.

  Examples of the alkoxyl group include alkoxyl groups having 1 to 18 carbon atoms. The alkoxyl group is more preferably an alkoxyl group having 1 to 10 carbon atoms. Specific examples of the alkoxyl group include, for example, methoxy group, ethoxy group, n-propoxy group, i-propoxy group, n-butoxy group, i-butoxy group, sec-butoxy group, t-butoxy group, and n-pentyloxy group. , Neo-pentyloxy group, n-hexyloxy group, n-heptyloxy group, n-octyloxy group and the like.

  Examples of the monoalkylamino group include an amino group having one linear or branched alkyl group having 1 to 18 carbon atoms or one alicyclic alkyl group having 3 to 18 carbon atoms. The alkyl group constituting the monoalkylamino group is more preferably a linear or branched alkyl group having 1 to 10 carbon atoms, and a linear or branched alkyl group having 2 to 8 carbon atoms. More preferably. Specific examples of the monoalkylamino group include, for example, a monomethylamino group, a monoethylamino group, a mono-n-propylamino group, a mono-i-propylamino group, a mono-n-butylamino group, and a mono-sec-butylamino group. Group, mono-t-butylamino group, mono-n-pentylamino group, mono-neo-pentylamino group, mono-n-hexylamino group, mono-n-heptylamino group, mono-n-octylamino group, etc. Is mentioned.

  Examples of the dialkylamino group include the above-described linear or branched alkyl groups having 1 to 18 carbon atoms, or amino groups having two alicyclic alkyl groups having 3 to 18 carbon atoms. The alkyl group constituting the dialkylamino group is more preferably a linear or branched alkyl group having 1 to 10 carbon atoms, and a linear or branched alkyl group having 2 to 8 carbon atoms. More preferably. Specific examples of the dialkylamino group include, for example, dimethylamino group, diethylamino group, di-n-propylamino group, di-i-propylamino group, di-n-butylamino group, di-sec-butylamino group, di- -T-butylamino group, di-n-pentylamino group, di-neo-pentylamino group, di-n-hexylamino group, di-n-heptylamino group, di-n-octylamino group and the like. .

  Examples of the alkylthio group include a thio group having a linear or branched alkyl group having 1 to 18 carbon atoms or an alicyclic alkyl group having 3 to 18 carbon atoms. The alkyl group constituting the alkylthio group is more preferably a linear or branched alkyl group having 1 to 10 carbon atoms, and is a linear or branched alkyl group having 2 to 8 carbon atoms. Is more preferable. Specific examples of the alkylthio group include, for example, methylthio group, ethylthio group, n-propylthio group, i-propylthio group, n-butylthio group, i-butylthio group, sec-butylthio group, t-butylthio group, n-pentylthio group, Examples include neo-pentylthio group, n-hexylthio group, n-heptylthio group, n-octylthio group, phenylthio group, naphthylthio group and the like.

In the —NHCOR ^′ group, R ′ represents an alkyl group. Examples of the alkyl group R ′ include the aforementioned linear or branched alkyl group having 1 to 18 carbon atoms, or an alicyclic alkyl group having 3 to 18 carbon atoms. Here, the alkyl group R ′ is more preferably a linear or branched alkyl group having 1 to 10 carbon atoms, and is a linear or branched alkyl group having 2 to 8 carbon atoms. Is more preferable.

Moreover, R < ¹ > -R < ⁵ >, R < ⁶ > -R < ¹⁰ > may form a 5-7 membered condensed ring by combining two adjacent groups. More specifically, R ¹ and R ² , R ² and R ³ , R ³ and R ⁴ , or R ⁴ and R ⁵ may be combined to form a 5- to 7-membered condensed ring, and R ⁶ and R ⁷ , R ⁷ and R ⁸ , R ⁸ and R ⁹ , or R ⁹ and R ¹⁰ may be combined to form a 5- to 7-membered condensed ring. Examples of the 5- to 7-membered condensed ring include condensed rings such as phenyl, pyrrolyl, oxazolyl, thiophenyl, pyridinyl, and pyrimidinyl.

These hydroxyl group, alkyl group, alkoxyl group, monoalkylamino group, dialkylamino group, alkylthio group, phenyl group, —NHCOR ^′ (wherein R ′ represents an alkyl group), and the condensed ring described above are optionally used. May have a substituent. Examples of the substituent include halogen groups such as F, Cl, Br, and I; nitro groups; cyano groups; hydroxyl groups; mercapto groups; methyl groups, ethyl groups, propyl groups, butyl groups, pentyl groups, hexyl groups, 2 -C1-C10 linear or branched alkyl group such as ethylhexyl group, n-octyl group; methoxy group, ethoxy group, propoxy group, butoxy group, pentyloxy group, hexyloxy group, 2-ethylhexyl An alkoxy group having 1 to 10 carbon atoms such as an oxy group and an n-octyloxy group; an aryl group such as a phenyl group, a naphthyl group and a phenethyl group; an aralkyl group such as a benzyl group and an α, α-dimethylbenzyl group; an amino group; A monoalkylamino group having a linear or branched alkyl group having 1 to 10 carbon atoms; a linear or branched alkyl group having 1 to 10 carbon atoms Examples thereof include a dialkylamino group having two groups.

In R ^{1 to} R ⁵ and R ^{6 to} R ¹⁰ of the diphenylsulfone derivative represented by the above formula (1), at least one of R ³ and R ⁸ is an alkyl group, an alkoxyl group, an amino group, or a monoalkylamino group. It is more preferably an electron donating substituent selected from a dialkylamino group, an alkylthio group, a phenyl group, and —NHCOR ^′ (wherein R ′ represents an alkyl group). When at least one of R ³ and R ⁸ is the electron donating substituent, there is an advantage that a better two-photon absorption characteristic effect can be obtained due to the electron donating effect at the para position. An embodiment in which R ³ and R ⁸ are both electron-donating substituents selected from the same alkyl group, alkoxyl group, dialkylamino group, alkylthio group, and phenyl group is more preferable. Specific examples of the alkyl group, alkoxyl group, amino group, monoalkylamino group, dialkylamino group, alkylthio group, phenyl group, and —NHCOR ^′ (where R ′ represents an alkyl group) are the same as described above.

Moreover, it is more preferable that at least one of R ³ and R ⁸ is a dialkylamino group, and it is still more preferable that both R ³ and R ⁸ are dialkylamino groups. Moreover, as a dialkylamino group, the dialkylamino group which has a C2-C6 alkyl group is more preferable.

More preferably, R ¹ , R ² , R ⁴ , R ⁵ and R ⁶ , R ⁷ , R ⁹ , R ¹⁰ are hydrogen. R ¹ , R ² , R ⁴ , R ⁵ and R ⁶ , R ⁷ , R ⁹ and R ¹⁰ correspond to the ortho position or the meta position. When these are hydrogen, a better two-photon absorption characteristic effect can be obtained.

  Examples of the diphenylsulfone derivative include compounds represented by the following formulas (2) to (5).

［式中、Ｒ^１１〜Ｒ^１５、Ｒ^１６〜Ｒ^２０はそれぞれ、同一または異なっていてもよく、水素、ハロゲン原子、ヒドロキシル基、アルキル基、アルコキシル基、アミノ基、モノアルキルアミノ基、ジアルキルアミノ基、アルキルチオ基、フェニル基、−ＮＨＣＯＲ^’（但しＲ’はアルキル基を示す）を示すか、或いはＲ^１１〜Ｒ^１５、Ｒ^１６〜Ｒ^２０は、隣接する２つの基が一緒になって５〜７員環の縮合環を形成してもよい。］

[Wherein, R ^{11 to} R ¹⁵ and R ^{16 to} R ²⁰ may be the same or different and each represents a hydrogen atom, a halogen atom, a hydroxyl group, an alkyl group, an alkoxyl group, an amino group, a monoalkylamino group, a dialkylamino group. A group, an alkylthio group, a phenyl group, —NHCOR ^′ (wherein R ′ represents an alkyl group), or R ^{11 to} R ¹⁵ and R ^{16 to} R ²⁰ are a group of two adjacent groups A condensed ring having ˜7 members may be formed. ]

［式中、Ｒ^２１〜Ｒ^２５、Ｒ^２６〜Ｒ^３０はそれぞれ、同一または異なっていてもよく、水素、ハロゲン原子、ヒドロキシル基、アルキル基、アルコキシル基、アミノ基、モノアルキルアミノ基、ジアルキルアミノ基、アルキルチオ基、フェニル基、−ＮＨＣＯＲ^’（但しＲ’はアルキル基を示す）を示すか、或いはＲ^２１〜Ｒ^２５、Ｒ^２６〜Ｒ^３０は、隣接する２つの基が一緒になって５〜７員環の縮合環を形成してもよい。］

[Wherein R ^{21 to} R ²⁵ , R ^{26 to} R ³⁰ may be the same or different, and each of hydrogen, halogen atom, hydroxyl group, alkyl group, alkoxyl group, amino group, monoalkylamino group, dialkylamino A group, an alkylthio group, a phenyl group, —NHCOR ^′ (wherein R ′ represents an alkyl group), or R ^{21 to} R ²⁵ and R ^{26 to} R ³⁰ are formed by combining two adjacent groups together. A condensed ring having ˜7 members may be formed. ]

［式中、Ｒ^３１〜Ｒ^３５、Ｒ^３６〜Ｒ^４０はそれぞれ、同一または異なっていてもよく、水素、ハロゲン原子、ヒドロキシル基、アルキル基、アルコキシル基、アミノ基、モノアルキルアミノ基、ジアルキルアミノ基、アルキルチオ基、フェニル基、−ＮＨＣＯＲ^’（但しＲ’はアルキル基を示す）を示すか、或いはＲ^３１〜Ｒ^３５、Ｒ^３６〜Ｒ^４０は、隣接する２つの基が一緒になって５〜７員環の縮合環を形成してもよい。］

[Wherein, R ^{31 to} R ³⁵ and R ^{36 to} R ⁴⁰ may be the same or different and each represents a hydrogen atom, a halogen atom, a hydroxyl group, an alkyl group, an alkoxyl group, an amino group, a monoalkylamino group, a dialkylamino group. A group, an alkylthio group, a phenyl group, —NHCOR ^′ (wherein R ′ represents an alkyl group), or R ^{31 to} R ³⁵ and R ^{36 to} R ⁴⁰ are formed by combining two adjacent groups together. A condensed ring having ˜7 members may be formed. ]

［式中、Ｒ^４１〜Ｒ^４５、Ｒ^４６〜Ｒ^５０はそれぞれ、同一または異なっていてもよく、水素、ハロゲン原子、ヒドロキシル基、アルキル基、アルコキシル基、アミノ基、モノアルキルアミノ基、ジアルキルアミノ基、アルキルチオ基、フェニル基、−ＮＨＣＯＲ^’（但しＲ’はアルキル基を示す）を示すか、或いはＲ^４１〜Ｒ^４５、Ｒ^４６〜Ｒ^５０は、隣接する２つの基が一緒になって５〜７員環の縮合環を形成してもよい。］

[Wherein, R ^{41 to} R ⁴⁵ and R ^{46 to} R ⁵⁰ may be the same or different and each represents a hydrogen atom, a halogen atom, a hydroxyl group, an alkyl group, an alkoxyl group, an amino group, a monoalkylamino group, a dialkylamino group. A group, an alkylthio group, a phenyl group, —NHCOR ^′ (wherein R ′ represents an alkyl group), or R ^{41 to} R ⁴⁵ and R ^{46 to} R ⁵⁰ are formed by combining two adjacent groups together. A condensed ring having ˜7 members may be formed. ]

In the above formulas (2) to (5), examples of the substituents represented by R ^{11 to} R ²⁰ , R ^{21 to} R ³⁰ , R ^{31 to} R ⁴⁰ , and R ^{41 to} R ⁵⁰ include the following substituents. Can do.

  Examples of the halogen atom include fluorine, chlorine, bromine and iodine.

  Examples of the alkyl group include a linear or branched alkyl group having 1 to 18 carbon atoms and an alicyclic alkyl group having 3 to 18 carbon atoms. The alkyl group is more preferably a linear or branched alkyl group having 1 to 10 carbon atoms. Specific examples of the alkyl group include, for example, methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, i-butyl group, sec-butyl group, t-butyl group, n-pentyl group, neo-pentyl, n-hexyl, n-heptyl, n-octyl, 2-ethylhexyl, n-decyl, lauryl, stearyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cyclo An octyl group etc. are mentioned.

  Examples of the alkoxyl group include alkoxyl groups having 1 to 18 carbon atoms. The alkoxyl group is more preferably an alkoxyl group having 1 to 10 carbon atoms. Specific examples of the alkoxyl group include, for example, methoxy group, ethoxy group, n-propoxy group, i-propoxy group, n-butoxy group, i-butoxy group, sec-butoxy group, t-butoxy group, and n-pentyloxy group. , Neo-pentyloxy group, n-hexyloxy group, n-heptyloxy group, n-octyloxy group and the like.

  Examples of the monoalkylamino group include an amino group having one linear or branched alkyl group having 1 to 18 carbon atoms or one alicyclic alkyl group having 3 to 18 carbon atoms. The alkyl group constituting the monoalkylamino group is more preferably a linear or branched alkyl group having 1 to 10 carbon atoms, and a linear or branched alkyl group having 2 to 8 carbon atoms. More preferably. Specific examples of the monoalkylamino group include, for example, a monomethylamino group, a monoethylamino group, a mono-n-propylamino group, a mono-i-propylamino group, a mono-n-butylamino group, and a mono-sec-butylamino group. Group, mono-t-butylamino group, mono-n-pentylamino group, mono-neo-pentylamino group, mono-n-hexylamino group, mono-n-heptylamino group, mono-n-octylamino group, etc. Is mentioned.

  Examples of the dialkylamino group include the above-described linear or branched alkyl groups having 1 to 18 carbon atoms, or amino groups having two alicyclic alkyl groups having 3 to 18 carbon atoms. The alkyl group constituting the dialkylamino group is more preferably a linear or branched alkyl group having 1 to 10 carbon atoms, and a linear or branched alkyl group having 2 to 8 carbon atoms. More preferably. Specific examples of the dialkylamino group include, for example, dimethylamino group, diethylamino group, di-n-propylamino group, di-i-propylamino group, di-n-butylamino group, di-sec-butylamino group, di- -T-butylamino group, di-n-pentylamino group, di-neo-pentylamino group, di-n-hexylamino group, di-n-heptylamino group, di-n-octylamino group and the like. .

  Examples of the alkylthio group include a thio group having a linear or branched alkyl group having 1 to 18 carbon atoms or an alicyclic alkyl group having 3 to 18 carbon atoms. The alkyl group constituting the alkylthio group is more preferably a linear or branched alkyl group having 1 to 10 carbon atoms, and is a linear or branched alkyl group having 2 to 8 carbon atoms. Is more preferable. Specific examples of the alkylthio group include, for example, methylthio group, ethylthio group, n-propylthio group, i-propylthio group, n-butylthio group, i-butylthio group, sec-butylthio group, t-butylthio group, n-pentylthio group, Examples include neo-pentylthio group, n-hexylthio group, n-heptylthio group, n-octylthio group, phenylthio group, naphthylthio group and the like.

In the —NHCOR ^′ group, R ′ represents an alkyl group. Examples of the alkyl group R ′ include the aforementioned linear or branched alkyl group having 1 to 18 carbon atoms, or an alicyclic alkyl group having 3 to 18 carbon atoms. Here, the alkyl group R ′ is more preferably a linear or branched alkyl group having 1 to 10 carbon atoms, and is a linear or branched alkyl group having 2 to 8 carbon atoms. Is more preferable.

In addition, R ^{11 to} R ¹⁵ and R ^{16 to} R ²⁰ may be formed by combining two adjacent groups to form a 5- to 7-membered condensed ring. R ^{21 to} R ²⁵ , R ^{26 to} R ³⁰ may form a 5- to 7-membered condensed ring by combining two adjacent groups, and R ^{31 to} R ³⁵ and R ^{36 to} R ⁴⁰ may be formed by combining two adjacent groups. 5 to 7-membered condensed rings may be formed. Examples of the 5- to 7-membered condensed ring include condensed rings such as phenyl, pyrrolyl, oxazolyl, thiophenyl, pyridinyl, and pyrimidinyl.

These hydroxyl group, alkyl group, alkoxyl group, monoalkylamino group, dialkylamino group, alkylthio group, phenyl group, —NHCOR ^′ (wherein R ′ represents an alkyl group), and the condensed ring described above are optionally used. May have a substituent. Examples of the substituent include halogen groups such as F, Cl, Br, and I; nitro groups; cyano groups; hydroxyl groups; mercapto groups; methyl groups, ethyl groups, propyl groups, butyl groups, pentyl groups, hexyl groups, 2 -C1-C10 linear or branched alkyl group such as ethylhexyl group, n-octyl group; methoxy group, ethoxy group, propoxy group, butoxy group, pentyloxy group, hexyloxy group, 2-ethylhexyl An alkoxy group having 1 to 10 carbon atoms such as an oxy group and an n-octyloxy group; an aryl group such as a phenyl group, a naphthyl group and a phenethyl group; an aralkyl group such as a benzyl group and an α, α-dimethylbenzyl group; an amino group; A monoalkylamino group having a linear or branched alkyl group having 1 to 10 carbon atoms; a linear or branched alkyl group having 1 to 10 carbon atoms Examples thereof include a dialkylamino group having two groups.

^A preferable embodiment of ^{R 11 ~R 20, R 21 ~R} 30, R 31 ~R 40 is the same as in the case of the ^R 1 ^{to R 10.}

  As one of the methods for synthesizing the diphenylsulfone derivative, for example, as shown by the following formula, synthesis is performed by a condensation reaction of di (p-tolyl) sulfone (6) and benzylideneaniline derivatives (7) and (8). Can do. This synthesis method is a more preferable method when the benzylidene aniline derivatives (7) and (8) have the same structure.

上記式中、Ｒ^１〜Ｒ^１０は上記と同様の基を示し、及びｎ、ｍは上記と同様の数を示し、及びｌ、ｐは０または１を示す。

In the above formula, R ^{1 to} R ¹⁰ represent the same groups as described above, and n and m represent the same numbers as described above, and l and p represent 0 or 1.

  To exemplify the above synthesis method, di (p-tolyl) sulfone (6) and benzylideneaniline derivatives (7) and (8) are dissolved or suspended and heated to synthesize a diphenylsulfone derivative. It is. In this heating, a base may be used as necessary. The benzylidene aniline derivatives (7) and (8) used in this method can be easily prepared by ordinary techniques in the art such as mixing aniline and benzaldehyde derivative and heating if necessary.

  The amount of each component used in the above synthesis method is preferably 0.8 to 1.2 mol of benzylideneaniline derivatives (7) and (8) with respect to 1 mol of di (p-tolyl) sulfone (6).

  As a solvent that can be used in the above synthesis method, di (p-tolyl) sulfone (6) and benzylideneaniline derivatives (7) and (8) can be dissolved or suspended, and the reaction with these substrates can be performed. There is no particular limitation as long as it does not occur. Examples of such solvents include alkylbenzenes such as benzene, toluene, xylene, mesitylene, ethylbenzene, n-propylbenzene and cumene; halogenated benzenes such as monochlorobenzene, dichlorobenzene, bromobenzene and dibromobenzene; N, N -Nitrogen-containing solvents such as dimethylformamide, N, N-dimethylacetamide, N-methylpyrrolidone, 1,3-dimethyl-2-imidazolidinone, 1,3-dimethylpropylene urea; tetrahydrofuran, diphenyl ether, anisole, Examples include ethers such as 1,4-dioxane, monoglyme, diglyme and triglyme.

  In this reaction, the reaction may be promoted using an appropriate base. The base is not particularly limited as long as it does not affect the groups of di (p-tolyl) sulfone (6) and benzylideneaniline derivatives (7) and (8). Examples of the base that can be used as necessary include alkali metal and alkaline earth metal hydroxides such as lithium hydroxide, sodium hydroxide, potassium hydroxide, and calcium hydroxide; sodium methoxide, sodium ethoxide, Examples thereof include alkali metal alkoxide compounds such as sodium propoxide, sodium t-butoxide, potassium methoxide, potassium ethoxide, potassium propoxide, potassium t-butoxide and the like.

  The reaction temperature of this reaction is preferably room temperature such as 10 to 40 ° C. Moreover, as reaction time of this reaction, it is preferable that it is 0.5 to 12 hours, for example.

  After the condensation reaction is completed, the obtained reaction mixture is preferably dropped into water, preferably ice water, and then the pH is adjusted to 4 or less with hydrochloric acid or the like to obtain a diphenylsulfone derivative. The diphenylsulfone derivative thus obtained may be purified by a technique commonly used by those skilled in the art. For example, the product diphenylsulfone derivative can be purified using a purification means such as column chromatography or a usual method in the art such as recrystallization. The purification means is not limited to these.

  As another method for synthesizing a diphenylsulfone derivative contained in the two-photon absorbing material of the present invention, for example, as shown by the following formula, first, di (p-tolyl) sulfone (6) and a benzylideneaniline derivative ( 7) can be subjected to a condensation reaction, and then the product obtained and a benzylideneaniline derivative (8) can be subjected to a condensation reaction.

In the above formula, R ^{1 to} R ¹⁰ represent the same groups as described above, and n and m represent the same numbers as described above, and l and p represent 0 or 1.

  As a specific example of the above synthesis method, di (p-tolyl) sulfone (6) and benzylideneaniline derivative (7) are dissolved or suspended and heated to synthesize intermediate A. Next, the obtained intermediate A and the benzylidene aniline derivative (8) are dissolved or suspended and heated to synthesize a diphenyl sulfone derivative. This synthesis method is more preferable when the benzylidene aniline derivatives (7) and (8) have different structures.

  The amount of each component used in the synthesis method is preferably 1 to 1.05 mol of the benzylideneaniline derivative (7) with respect to 1 mol of di (p-tolyl) sulfone (6). Moreover, it is preferable to use 1.0-1.2 mol of benzylidene aniline derivative (8) with respect to 1 mol of reaction products of di (p-tolyl) sulfone (6) and benzylidene aniline derivative (7).

  Solvents that can be used in the above synthesis method, benzylideneaniline derivatives (7) and (8), bases that can be used as necessary, reaction time, purification means, and the like are the same as described above. About reaction temperature, it may be room temperature similarly to the above, but when reaction does not advance, you may carry out by heating to 50-100 degreeC, for example.

  If necessary, the intermediate A obtained by reacting di (p-tolyl) sulfone (6) and the benzylidene aniline derivative (7) may be purified before the reaction with the benzylidene aniline derivative (8). It may be purified by means.

  A diphenylsulfone derivative can be synthesized by the above synthesis method. Moreover, you may substitute the substituent which the diphenyl sulfone derivative obtained by the said method has with another substituent using the normal method known to those skilled in the art as needed. Examples of such a substitution method include a method of introducing an alkyl group by reacting an alkyl halide with a hydroxyl group.

  Specific examples of diphenylsulfone derivatives that can be used in the two-photon absorbing material of the present invention are shown below. In addition, the diphenyl sulfone derivative which can be used for the two-photon absorbing material of the present invention is not limited to these. In the following table, Me represents a methyl group, Et represents an ethyl group, Bu represents an n-butyl group, t-Bu and Bu-t represent a t-butyl group, Oc represents an octyl group, Ph represents a phenyl group.

  The diphenyl sulfone derivative, which is a two-photon absorbing material in the present invention, has a basic structure of 4,4′-bisstyryl diphenyl sulfone derivative. The above-mentioned 4,4′-bisstyryldiphenylsulfone derivative has a characteristic of having excellent two-photon absorption characteristics without deepening the absorption wavelength. In the conventional two-photon absorbing material, with the expansion of the conjugated system, the deepening of the color has occurred in which the excitation wavelength region that induces two-photon absorption is also shifted to the long wavelength region. Such deepening of color may cause one-photon absorption of the two-photon absorbing material with respect to the laser light source. Laser light sources used for two-photon absorption applications generally have very high power. Therefore, when such a two-photon absorbing material causes one-photon absorption with respect to the laser light source, the two-photon absorbing material may be destroyed.

  Since the two-photon absorbing material of the present invention has a 4,4′-bisstyryldiphenylsulfone derivative as a basic structure, the deepening of the absorption wavelength in two-photon absorption is effectively suppressed. The two-photon absorbing material of the present invention is characterized in that it has a good two-photon absorption characteristic even though the deep color is suppressed as described above.

  The two-photon absorbing material of the present invention preferably has a one-photon absorption wavelength of 500 nm or less. The two-photon absorbing material of the present invention is sufficiently separated from the wavelength region 660 to 1100 nm of the femtosecond titanium sapphire laser used for inducing two-photon absorption because the one-photon absorption wavelength is 500 nm or less, Unwanted one-photon absorption can be prevented.

In the two-photon absorbing material of the present invention, a 4-position substituted derivative in which R ³ and / or R ⁸ in the above formula (1) is an electron donating substituent is more preferable. These have an advantage that a better two-photon absorption characteristic effect can be achieved by the electron donating effect at the 4-position (para-position).

In R ^{1 to} R ⁵ and R ^{6 to} R ¹⁰ of the diphenylsulfone derivative represented by the above formula (1), at least one of R ³ and R ⁸ is an alkyl group, an alkoxyl group, an amino group, or a monoalkylamino group. It is more preferably an electron donating substituent selected from a dialkylamino group, an alkylthio group, a phenyl group, and —NHCOR ^′ (wherein R ′ represents an alkyl group). Moreover, it is more preferable that at least one of R ³ and R ⁸ is a dialkylamino group, and it is still more preferable that both R ³ and R ⁸ are dialkylamino groups. Moreover, as a dialkylamino group, the dialkylamino group which has a C2-C6 alkyl group is more preferable.

Moreover, it is preferable that the diphenylsulfone derivative contained in the two-photon absorbing material of the present invention has a molar extinction coefficient of a maximum wavelength at 250 to 800 nm of 55000 mol ⁻¹ dm ³ cm ⁻¹ or more. This molar extinction coefficient corresponds to a proportional coefficient of absorbance normalized by unit molar concentration and unit optical path length with respect to the maximum wavelength at which one-photon absorption is highest in a wavelength range of 250 to 800 nm.

  The two-photon absorbing material of the present invention can be contained in, for example, a photocurable resin composition, a light emitting material, an optical recording material, a fluorescent dye material for a microscope, or a light limiting material. For example, by using a photocurable resin composition containing the two-photon absorbing material of the present invention, a photosensitive material having high spatial selectivity or controllability by light can be provided. This photosensitive material is useful in fields such as ultra-high density optical recording, MEMS (Micro Electro Mechanical Systems) or photonic crystal production by photo-curable resin microfabrication, fluorescent probes, and light limiting materials.

Photocurable resin composition containing a two-photon absorbing material The two-photon absorbing material can be used by being included in a photocurable resin composition. The photocurable resin composition containing a two-photon absorbing material generally contains (A) a two-photon absorbing material, (B) a photopolymerizable component, and (C) a photopolymerization initiator. The photocurable resin composition may further contain (D) a binder resin and other additive components.

As the two-photon absorbing material (A), the above-described two-photon absorbing material is used. Examples of the photopolymerizable component (B) include polymerizable components such as a monofunctional monomer, a polyfunctional monomer, a monofunctional oligomer, and a polyfunctional oligomer having an ethylenically unsaturated group capable of radical polymerization.
Specific examples of monofunctional oligomers and polyfunctional oligomers include, for example, di-, tri-, tetra- or poly-alkylene glycol di (meth) acrylate, polyol (meth) acrylate, polyol alkylene oxide (meth) acrylate, polyester (meta ) Acrylate, urethane (meth) acrylate, epoxy (meth) acrylate, silicone (meth) acrylate, polybutadiene (meth) acrylate, melamine (meth) acrylate, and acrylate resin such as phosphazene (meth) acrylate.

These monofunctional oligomers and polyfunctional oligomers can be prepared by ordinary techniques in the art. For example, polyester (meth) acrylate is obtained by esterifying the hydroxyl group of a polyester oligomer having hydroxyl groups at both ends obtained by condensation of a polyvalent carboxylic acid and a polyhydric alcohol with (meth) acrylic acid, or a polyvalent carboxylic acid. It can be obtained by esterifying the terminal hydroxyl group of an oligomer obtained by adding alkylene oxide to (meth) acrylic acid.
The epoxy (meth) acrylate can be obtained, for example, by reacting (meth) acrylic acid with an oxirane ring of a relatively low molecular weight bisphenol type epoxy resin or novolak type epoxy resin and esterifying it. Further, a carboxyl-modified epoxy (meth) acrylate oligomer obtained by partially modifying this epoxy (meth) acrylate oligomer with a dibasic carboxylic acid anhydride can also be used.
The urethane (meth) acrylate oligomer can be obtained, for example, by esterifying a polyurethane oligomer obtained by a reaction between a polyether polyol or a polyester polyol and a polyisocyanate with (meth) acrylic acid.
The polyol (meth) acrylate oligomer can be obtained by esterifying the hydroxyl group of the polyether polyol with (meth) acrylic acid.

As the monofunctional monomer and polyfunctional monomer, various monofunctional (meth) acrylic monomers, bifunctional (meth) acrylic monomers, and trifunctional or higher (meth) acrylate monomers can be used.
Monofunctional (meth) acrylic monomers include, for example, cyclohexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, lauryl (meth) acrylate, stearyl (meth) acrylate, isobornyl (meth) acrylate, phenoxypolyethylene glycol acrylate, (Meth) acrylates such as phenoxyethylene glycol acrylate, phenoxydiethylene glycol acrylate, phenoxytriethylene glycol acrylate, tetrahydrofurfuryl monoacrylate, isooctyl monoacrylate, and dimethylacrylamide, dimethylaminoethyl acrylate, acryloylmorpholine, dimethylaminopropylacrylamide, Isopropylacrylamide, diethylacrylamido , Acrylamides, such as hydroxyethyl acrylamide.
Examples of the bifunctional (meth) acrylic monomer include 1,4-butanediol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, neopentyl glycol di (meth) acrylate, polyethylene glycol di ( (Meth) acrylate, polypropylene glycol di (meth) acrylate, neopentyl glycol adipate di (meth) acrylate, hydroxypivalate neopentyl glycol di (meth) acrylate, dicyclopentanyl di (meth) acrylate, caprolactone modified dicyclopentenyl di (Meth) acrylate, isocyanuric acid EO-modified diacrylate, ethylene oxide-modified phosphoric acid di (meth) acrylate, allylated cyclohexyl di (meth) acrylate, isocyanurate di (meth) Acrylate, dipropylene glycol diacrylate, tripropylene glycol di (meth) acrylate, tricyclodecane dimethanol (meth) acrylate.
Examples of tri- or higher functional (meth) acrylic monomers include trimethylolpropane tri (meth) acrylate, dipentaerythritol tri (meth) acrylate, propionic acid-modified dipentaerythritol tri (meth) acrylate, and pentaerythritol tri (meth). Acrylate, propylene oxide modified trimethylolpropane tri (meth) acrylate, tris (acryloxyethyl) isocyanurate, propionic acid modified dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, isocyanuric acid EO modified triacrylate , Caprolactone-modified dipentaerythritol hexa (meth) acrylate, pentaerythritol polyethoxy acrylate, pentaerythritol Li propoxy acrylate, dipentaerythritol polyacrylate, pentaerythritol polyacrylate, and the like.
In the present specification, the term “(meth) acryl” means a generic term for “acryl” and “methacryl”, and similarly, the term “(meth) acrylate” means a generic term for “acrylate” and “methacrylate”. To do.

  As the photopolymerization initiator (C), an initiator usually used by those skilled in the art can be used as necessary. Examples of such photopolymerization initiators include camphorquinone, benzoin, benzoin methyl ether, benzoin-n-propyl ether, benzoin-n-butyl ether, benzyl, benzophenone, p-methylbenzophenone, diacetyl, eosin, thionine, Michler's ketone, Acetophenone, 2-chlorothioxanthone, anthraquinone, chloroanthraquinone, 2-methylanthraquinone, α-hydroxyisobutylphenone, p-isopropyl-α-hydroxyisobutylphenone, α, α'-dichloro-4-phenoxyacetophenone, 1- Hydroxy-1-cyclohexylacetophenone, 2,2-dimethoxy-2-phenylacetophenone, methylbenzoinformate, 2-methyl-1- [4- (methylthio) phenyl] -2-methyl Rufolinoproben, dichlorothioxanthone, diisopropylthioxanthone, phenyl disulfide-2-nitrosofluorene, butyroin, anisoin ethyl ether, azobisisobutyronitrile, tetramethylthiuram disulfide, and JP-A-6-95378, JP-A Examples of known photopolymerization initiators described in JP-A-8-36261 include ammonium persulfate, 2,2′-azobis (N, N′-dimethyleneisobutylamine) hydrochloride, 2,2′-azobis ( 2-aminodipropane) hydrochloride, 4,4′-azobis (4-cyanopentanoic acid), 2,2′-azobis {2-methyl-N [1,1-bis (hydroxymethyl) -2-hydroxyethyl ] Propionamide}, 2,2′-azobis (2-mercaptopropiona Gin) and other radical polymerization initiators, and cationic polymerization of onium salts such as sulfur-based initiators such as triphenylsulfonium hexafluoroantimonate and iodine-based initiators such as diphenyliodonium hexafluoroantimonate Initiators are included, but not limited to these. These photopolymerization initiators (C) can be used alone or in combination of two or more. Further, the photopolymerization initiator (C) may not be used.

  The amount of the two-photon absorbing material (A) contained in the photocurable resin composition can be set to a concentration according to the use of the composition. For example, the two-photon absorbing material (A) is preferably 0.001 to 5 parts by mass, and 0.01 to 4 parts by mass with respect to 100 parts by mass of the photopolymerizable component (B). More preferably, it is 0.01-3 mass parts.

  When using a photoinitiator (C), it is preferable that it is 0.1-5 mass parts with respect to 100 mass parts of said photopolymerizable components (B), and it is 0.2-4 mass parts. More preferably, it is 0.5-3 mass parts. When the content of the photopolymerization initiator (C) exceeds 5 parts by mass, economical disadvantages occur, and the remaining photopolymerization initiator (C) may deteriorate the physical properties of the cured resin.

  The photocurable resin composition may contain a binder resin (D) as necessary. By using the binder resin (D), the film formability of the composition before polymerization, the uniformity of the film thickness, the stability during storage, and the like can be improved. As the binder resin (D), components usually used by those skilled in the art can be used. Specific examples of the binder resin (D) include, for example, (meth) acrylic resin, (meth) acrylic copolymer, polyvinyl ester, ethylene / vinyl acetate copolymer, epoxy resin, polyamide resin, cellulose resin, polyvinyl acetal, polyvinyl Examples include pyrrolidone, polyvinyl alcohol, fluororesin, and polystyrene resin.

  When the photocurable resin composition is used for producing a recording layer of an optical recording material described in detail below, the photocurable resin composition contains a binder resin (D), and the refraction of the binder resin (D). An aspect in which the value of the refractive index and the value of the refractive index of the polymerized photopolymerizable component (B) are different is preferable. When light irradiation (exposure) is performed on the recording layer of the optical recording material, photopolymerization that occurs due to two-photon absorption is started, and accordingly, a concentration gradient of the photopolymerizable component (B) is generated, and a portion where light is weak to a strong portion It is considered that diffusion transfer of the photopolymerizable component (B) occurs. As a result of this diffusion movement, a region where the photopolymerizable component (B) is present densely and a region where the binder resin (D) is present as a main component are formed according to the intensity of the recording light, and the refraction of these regions is formed. This is thought to be due to the difference in rate. This makes the composition ratio of the polymer of the photopolymerizable component (B) and the binder resin (D) nonuniform in the portion irradiated with the laser beam (laser focal portion) and the non-irradiated portion (non-focal portion). Occurs, and a large refractive index modulation can be caused, and the recording sensitivity can be increased. The refractive index modulation formed is preferably greater than 0.005, more preferably greater than 0.01, and even more preferably greater than 0.05. The difference in refractive index between the polymer of the photopolymerizable component (B) and the binder resin (D) is that the refractive index of the polymer of the photopolymerizable component (B) is larger than the refractive index of the binder resin (D). Moreover, the refractive index of the binder resin (D) may be larger than the refractive index of the polymer of the photopolymerizable component (B). From the viewpoint of recording sensitivity, an embodiment in which the refractive index of the polymer of the photopolymerizable component (B) is larger than the refractive index of the binder resin (D) is more preferable.

  When using a photocurable resin composition for preparation of the recording layer of an optical recording material, the quantity of binder resin (D) contained in a photocurable resin composition is 100 mass parts of photopolymerizable components (B). The amount is preferably 80 to 500 parts by mass.

The photocurable resin composition may contain a photopolymerization accelerator as necessary. By containing the photopolymerization accelerator, the curing reaction by the photopolymerization initiator can be promoted. Specific examples of the photopolymerization accelerator include, for example, tertiary amines such as triethylamine, triethanolamine, 2-dimethylaminoethanol, alkylphosphine typified by triphenylphosphine, and β-thioglycol. Thiols and the like.
When a photopolymerization accelerator is included, it is preferably 0.1 to 5 parts by mass, more preferably 0.2 to 4 parts by mass with respect to 100 parts by mass of the photopolymerizable component (B). More preferably, it is 0.5-3 mass parts.

  The photocurable resin composition may contain additives or additive components usually used by those skilled in the art, such as a chain transfer agent, a heat stabilizer, a plasticizer, and an organic solvent, as necessary.

Luminescent Material Containing Two-Photon Absorbing Material A luminescent material using the two-photon absorbing material of the present invention is a material that utilizes light emitted from excited molecules generated by two-photon absorption in the radiation deactivation process of the excited state. Means. Such a light emission phenomenon can be used for, for example, information recording materials, fluorescent microscope dyes, light limiting agents, and the like.

  As described above, the two-photon absorption phenomenon is a kind of third-order nonlinear optical effect, and is a phenomenon in which a molecule absorbs two photons simultaneously and transitions from a ground state to an excited state. A two-photon absorbing material is a material that can excite molecules at a wavelength in the non-resonant region, and absorbs two photons, thereby exciting at an energy level about twice that of the photons used for excitation. It is a material that becomes a state. The transition efficiency of such two-photon simultaneous absorption is extremely lower than that of one-photon absorption, and a photon having an extremely large power density is required. Therefore, two-photon absorption hardly occurs at a general laser light intensity. For example, two-photon absorption can be observed by using an ultra-short pulse laser of about femtosecond such as a mode-locked laser having a high peak light intensity (light intensity at the maximum emission wavelength).

  Moreover, the transition efficiency of two-photon absorption is proportional to the square of the applied photoelectric field (square characteristic of two-photon absorption). Therefore, when a laser such as an ultra-short pulse 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. On the other hand, two-photon absorption does not occur at all in the peripheral portion where the electric field strength is weak. For example, in a three-dimensional space, two-photon absorption occurs only in the region where the electric field intensity at the focal point where laser light is collected by a lens is large. On the other hand, in a region out of focus, two-photon absorption does not occur because the electric field strength is weak.

  On the other hand, in one-photon linear absorption, excitation occurs at all positions in proportion to the intensity of the applied photoelectric field. Therefore, the two-photon absorption has a three-dimensional space selection performance that is not in the one-photon linear absorption, in which excitation occurs only at a pinpoint inside the space due to the square characteristic. Two-photon absorption has a feature that the spatial resolution is remarkably improved by this performance. For example, in a recording material using two-photon absorption, the spot size can be made smaller than that of a recording material using one-photon absorption. Therefore, super-resolution recording is possible by using the two-photon absorption performance in the information recording material.

  Two-photon absorptive materials can be used for applications such as light-limiting materials, photo-curing materials used for stereolithography, and fluorescent dye materials for two-photon fluorescence microscopes by taking advantage of the characteristics of high spatial resolution derived from the square characteristics. Can do.

  Two-photon absorbing materials can also be used in photochemotherapy such as two-photon imaging of biological tissue and two-photon photodynamic therapy (PDT). In the induction of two-photon absorption, the wavelength is longer than the wavelength region in which the linear absorption band of the compound exists, and absorption by living tissue does not occur, that is, the linear absorption band of living tissue does not exist. A short pulse laser can be used. Thereby, even if it is a use in a biological tissue, excitation light can be made to reach the inside of a sample, without receiving absorption and scattering by a biological tissue. In addition, the three-dimensional spatial selection performance based on the above-mentioned two-photon absorption square characteristic also has an advantage that the pinpoint inside the sample can be excited with high spatial resolution.

  Further, in two-photon absorption and two-photon emission, photons having an energy higher than that of incident photons can be extracted, and therefore can be used for upconversion lasing from the viewpoint of a wavelength conversion device.

  As such a light emitting material containing a two-photon absorbing material, for example, the two-photon absorbing material or a photocurable resin composition containing the two-photon absorbing material can be used.

Application to optical recording materials using two-photon absorbing materials In accordance with the spread of network environments such as the Internet and high-definition TV, image information of, for example, 50 GB or more, preferably 100 GB or more is inexpensive and simple in consumer use. There is an increasing demand for a large-capacity recording medium that can be recorded on the recording medium. Further, in business applications such as computer backup applications and broadcast backup applications, optical recording materials capable of recording large-capacity information of about 1 TB or more at high speed and at low cost are required.

  In conventional two-dimensional optical recording materials such as CD and DVD, the recording capacity can be increased by shortening the recording / reproducing wavelength. However, in such a conventional two-dimensional optical recording material, even if such a wavelength shortening technique is used, the recording capacity can be improved only up to about 25 GB on the physical principle. For this reason, the conventional two-dimensional optical recording material cannot ensure a sufficient recording capacity that can meet future requirements.

  As a next-generation high-density / high-capacity recording medium, a three-dimensional optical recording material using a two-photon absorbing material as in the present invention is attracting attention. In three-dimensional optical recording materials, tens or hundreds of layers are stacked in the three-dimensional (film thickness) direction, resulting in ultra-high density tens or hundreds of times higher than conventional two-dimensional recording media.・ It is thought that ultra-high capacity recording is possible. In such a three-dimensional optical recording material, it is required that an arbitrary place can be accessed and written in the three-dimensional (film thickness) direction. The two-photon absorbing material of the present invention can be used as a means for such a three-dimensional (film thickness) direction.

  In this way, in the three-dimensional optical recording material using the two-photon absorbing material, based on the physical principle described above, it is equivalent to tens or hundreds of times higher than the conventional two-dimensional optical recording material. Capacitance recording can be made possible. Therefore, a three-dimensional optical recording material using a two-photon absorbing material is considered as an effective means for achieving the next generation high density / high capacity optical recording material.

  In a three-dimensional optical recording material using a two-photon absorbing material, for example, a mode in which a curing reaction is generated using excitation energy obtained by non-resonant two-photon absorption is considered. As a result, if it is possible to modulate light emission, reflection intensity, etc. when irradiating light at the laser focus (recording) part and non-focus (non-recording) part, it is extremely high in any place in the three-dimensional space. Light emission and reflection intensity can be modulated with spatial resolution. Thereby, three-dimensional optical recording capable of extremely high density and high capacity recording can be achieved. Such a three-dimensional optical recording material can also be read nondestructively and is an irreversible material, so that good recording storability can be expected. Therefore, it has extremely high practicality.

  The optical recording material containing the two-photon absorption compound of the present invention has at least a two-photon absorption compound having a large two-photon absorption cross-section, and recording was performed by a method that cannot be rewritten using the two-photon absorption of the two-photon absorption compound. Thereafter, the recording material is reproduced by irradiating the recording material with light and detecting differences in light emission, reflection intensity, etc., and is a two-photon absorption optical recording material capable of recording / reproducing.

  The two-photon absorption optical recording material has a three-dimensional multilayer optical recording layer. In optical recording / reproduction, the recording / reproduction is performed by focusing on an arbitrary layer of the three-dimensional multilayer optical recording layer, thereby functioning as a three-dimensional recording medium. Further, there is an advantage that three-dimensional recording in an arbitrary depth direction is possible based on the characteristics of the two-photon absorbing material even if the layers are not separated by a protective layer (intermediate layer).

  The two-photon absorption optical recording material of the present invention, for example, by laminating about 50 layers of recording layers and intermediate layer protective layers made of the two-photon absorption material of the present invention alternately on a flat support substrate, Can be prepared. The thickness of the recording layer is preferably 0.01 to 0.5 μm, for example. Further, the thickness of the intermediate layer is preferably 0.1 to 5 μm, for example. With this structure, the two-photon absorption optical recording material of the present invention realizes a terabyte-class high-capacity optical recording material even if it is the same size as a conventional two-dimensional optical recording material such as a CD or DVD. be able to.

  Three-dimensional recording of information is performed by focusing light generated from a light source at a desired location in the recording layer. A single beam can generally be used as the light source. In this case, a femtosecond order ultrashort pulse light, a general-purpose laser excitation device, or the like can be used as the light source. In addition to the recording method in units of bits and in the depth direction, a parallel recording method using a surface light source is preferable because a high transfer rate is realized. It is also possible to realize a high transfer rate by producing a bulk-shaped recording medium having no intermediate layer in the recording medium and recording the page data collectively as in hologram recording.

  As the substrate, any natural or synthetic support having the shape of a flexible or rigid film, sheet or plate can be used. Specific examples include polyethylene terephthalate, resin-undercoated polyethylene terephthalate, or polyethylene terephthalate that has been subjected to electrostatic discharge treatment, cellulose acetate, polycarbonate, polymethyl methacrylate, polyester, polyvinyl alcohol, and glass. These substrates may be provided with tracking guide grooves or address information in advance.

  The recording layer can be formed, for example, by directly applying the photocurable resin composition onto a substrate using a spin coater, a roll coater, a bar coater or the like. The solvent used as necessary at the time of application can be removed by evaporation at the time of drying. Heating or reduced pressure may be used as the evaporation removing means. Thereby, a recording layer can be formed more satisfactorily.

  By forming the intermediate layer, the oxygen barrier property can be improved, and the interlayer crosstalk prevention performance can be improved. Examples of the intermediate layer include polyolefin films such as polypropylene and polyethylene, plastic films or plates such as polyvinyl chloride, polyvinylidene chloride, polyvinyl alcohol, polyethylene terephthalate, and cellophane films. The intermediate layer can be provided by being laminated with the recording layer by a method such as electrostatic adhesion or lamination using an extruder. Or you may apply | coat the photocurable resin composition which forms a recording layer to an intermediate | middle layer. Further, if necessary, an air-tightness may be improved by providing an adhesive layer or a liquid material layer between the protective layer and the recording layer and / or between the substrate and the recording layer. Further, a guide groove for tracking or address information may be provided in advance in the protective layer (intermediate layer) between the photosensitive films.

  Recording reproduction on the optical recording material is performed by irradiating the recording layer with laser light having a lower intensity than that at the time of recording, and detecting the difference in light emission and / or reflection intensity with a detector. The laser beam used for recording / reproduction may have a wavelength different from that of the beam used during recording, or may be light having the same wavelength with low output.

  The form of the optical recording material similarly formed according to the present invention is not limited to the form of the existing two-dimensional optical recording material, and may be, for example, a card shape, a plate shape, a tape shape, a drum shape, or the like. May be.

Fluorescent dye material for microscopes containing a two-photon absorbing material The two-photon absorbing material of the present invention can be suitably used as a fluorescent dye material for a microscope for a two-photon excitation laser scanning microscope. Here, the two-photon excitation laser scanning microscope is a microscope that obtains an image by condensing and scanning a near-infrared pulse laser on the sample surface and detecting fluorescence generated by excitation by two-photon absorption there. is there.

  The two-photon excitation laser scanning microscope uses a laser light source that emits sub-picosecond monochromatic coherent light pulses in the near-infrared region, a light beam conversion optical system that converts the light beam from the laser light source to a desired size, and a light beam conversion optical system for conversion. A scanning optical system for condensing the scanned light beam on the image plane of the objective lens and scanning; an objective lens system for projecting the collected converted light beam on the sample surface; and a photodetector.

  The pulsed laser light is focused by the light beam conversion optical system and the objective lens system through the dichroic mirror and focused on the specimen surface, and is induced by two-photon absorption in the fluorescent dye material in the specimen. Give rise to fluorescence. The sample surface is scanned with a laser beam, and the fluorescence intensity at each location is detected by a light detection device such as a light detector. Based on the obtained positional information, a computer plots the three-dimensional fluorescence image. can get. As the scanning mechanism, for example, a laser beam may be scanned using a movable mirror such as a galvanometer mirror, or a specimen containing a two-photon absorbing material placed on a stage may be moved.

  With such a configuration, it is possible to obtain high resolution in the optical axis direction by utilizing the nonlinear effect of two-photon absorption itself. In addition, by using a confocal pinhole plate, higher resolution (both in-plane and in the optical axis direction) can be obtained.

  The two-photon absorbing material of the present invention can be suitably used as a fluorescent dye material for a microscope for a two-photon excitation laser scanning microscope. The two-photon absorbing material of the present invention has a larger two-photon absorption cross-sectional area than conventional fluorescent dye materials for microscopes, so that it exhibits high two-photon absorption characteristics even at low concentrations. be able to. Therefore, according to the present invention, a highly sensitive fluorescent dye material for a microscope can be obtained. Furthermore, it is not necessary to increase the intensity of light applied to the material, so that deterioration and destruction of the material can be suppressed, and adverse effects on the characteristics of other components in the material can be reduced.

Light-limiting material containing a two-photon absorbing material In the fields of 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 used. However, in this electro-optical control method, the bandwidth is limited by the CR time constant as in an electric circuit, or the processing speed is limited by the response speed of the element itself or the mismatch of the speed between the electric signal and the optical signal. There are restrictions. Therefore, in order to make full use of the broadband property or high-speed property that is the advantage of light, a light-light control technique that performs light control with an optical signal becomes very important.

  The two-photon absorbing material of the present invention can be used as a light limiting material. The light-limiting material containing the two-photon absorbing material of the present invention can change optical properties such as transmittance, refractive index, and absorption coefficient by irradiating light. This makes it possible to modulate the intensity or frequency of light without using electronic circuit technology. Such an optical limiting material can be applied to an optical switch in optical communication, optical exchange, optical computer, optical interconnection, and the like. As such a light limiting material, the above-mentioned two-photon absorbing material may be used as it is, or the above-mentioned photocurable resin composition may be used.

  The light limiting material in the present invention has an advantage that it has an excellent response speed as compared with a light limiting element formed of a normal semiconductor material or a light limiting element based on one-photon excitation. Furthermore, since the light limiting material in the present invention has high sensitivity, it is possible to provide a light limiting element excellent in signal characteristics with a high S / N ratio.

  EXAMPLES Next, the present invention will be described more specifically with reference to examples. However, the present invention is not limited to these specific examples. In the examples, “parts” and “%” are based on mass unless otherwise specified.

The synthesis of benzylidene aniline is described in the published L.L. A. Bigelow, H .; Eatour, Org. Synth. , I, 80 (1941), and was synthesized by procedures commonly used by those skilled in the art.
The synthesis of bisstyryl diphenyl sulfone has been reported in the published H-. D. Becker, J. et al. Org. Chem. , 29, 2891 (1964) according to procedures usually used by those skilled in the art.

Production of homodisubstituted diphenylsulfone derivative (Production Example 1) Production of Compound Example A1 53 g (0.5 mol) of benzaldehyde and 46.5 g (0.5 mol) of aniline were mixed and reacted for 15 minutes to give 47.9 g of benzylideneaniline ( 52.8%).

  Under nitrogen atmosphere, 10.0 g (40.6 mmol) of p-tolylsulfone (manufactured by Tokyo Chemical Industry Co., Ltd.) and 14.72 g (81.2 mmol) of benzylidene aniline in 200 ml of dimethylformamide, 4.87 g (89.32 mmol) of potassium t-butoxide. ) In the presence for 3 hours to obtain 15.8 g (83.2%) of 4,4′-bisstyryldiphenylsulfone crude product.

1.0 g of the resulting 4,4′-bisstyryldiphenylsulfone crude purified product was purified by silica gel thin layer chromatography using chloroform as a developing solvent, and 4,4′-bisstyryldiphenylsulfone represented by the following formula: 0.1 g was obtained. Elemental analysis values are as follows.
Elemental analysis value (calculated value); C: 79.27% (79.59%), H: 5.39% (5.25%)

(Production Example 2) Production of Compound Example A2 4-t-butylbenzaldehyde 10.0 g (61.6 mmol) and aniline 6.03 g (64.7 mmol) were mixed and heated to reflux for 3 hours to give 4-t-butylbenzylideneaniline. Of 13.6 g (92.8%).

  Under a nitrogen atmosphere, 2.0 g (8.12 mmol) of p-tolylsulfone (manufactured by Tokyo Chemical Industry Co., Ltd.) and 4.06 g (17.05 mmol) of 4-t-butylbenzylideneaniline in 60 ml of dimethylformamide, 1. The mixture was stirred at room temperature for 3 hours in the presence of 82 g (17.05 mmol). The reaction solution was added dropwise to 300 ml of ice water, hydrochloric acid was added to adjust to pH <4, and the precipitate was collected by filtration, washed and dried to obtain 3.41 g of a yellow powder. The obtained yellow powder was subjected to silica gel column chromatography using chloroform as a developing solvent, and 1.9 g (43.8%) of 4,4′-bis (4-t-butylstyryl) diphenylsulfone crude purified product was obtained. Obtained.

0.1 g of the obtained crude product was dissolved in 4 ml of chloroform, filtered through hydrophobic PTFE having a pore size of 0.50 μm, 2 ml of methanol was added, and the precipitate was collected by filtration, and 4,4′- 0.067 g of bis (4-t-butylstyryl) diphenylsulfone was obtained. Elemental analysis values are as follows.
Elemental analysis value (calculated value); C: 80.21% (80.86%), H: 7.32% (7.16%)

(Production Example 3) Production of Compound Example A3 10.0 g (73.4 mmol) of 4-methoxybenzaldehyde and 7.18 g (77.1 mmol) of aniline were mixed in 100 ml of methanol and heated under reflux for 3 hours to give 4-methoxybenzylideneaniline. 12.1 g (77.9%) was obtained.

Under a nitrogen atmosphere, 1.0 g (4.06 mmol) of p-tolylsulfone (manufactured by Tokyo Chemical Industry Co., Ltd.) and 1.72 g (8.12 mmol) of 4-methoxybenzylideneaniline in 0.9 ml of potassium t-butoxide in 20 ml of dimethylformamide ( (8.12 mmol) in the presence of 2 hours at room temperature. The reaction solution was added dropwise to 300 ml of ice water, hydrochloric acid was added to adjust to pH <4, and the mixture was stirred for 0.5 h. The precipitate was collected by filtration, washed and dried, then washed with 50 ml of tetrahydrofuran and dried to obtain 1.58 g (80.6%) of 4,4′-bis (4-methoxystyryl) diphenylsulfone represented by the following formula. . Elemental analysis values are as follows.
Elemental analysis value (calculated value); C: 74.57% (74.66%), H: 5.56% (5.43%)

(Production Example 4) Production of Compound Example A5 4-Butoxybenzaldehyde 10.0 g (56.1 mmol) and aniline 5.49 g (58.9 mmol) were mixed in 100 ml of methanol and heated under reflux for 3 hours to give 4-butoxybenzylideneaniline. 12.2 g (85.9%) were obtained.

  Under a nitrogen atmosphere, 2.0 g (8.12 mmol) of p-tolylsulfone (manufactured by Tokyo Chemical Industry Co., Ltd.) and 4.33 g (8.53 mmol) of 4-butoxybenzylideneaniline in 1.8 ml of potassium t-butoxide in 60 ml of dimethylformamide ( The reaction was allowed to proceed for 1.5 hours at room temperature in the presence of 16.24 mmol). The reaction solution was added dropwise to 300 ml of ice water, hydrochloric acid was added to adjust to pH <4, and the mixture was stirred for 0.5 h. The precipitate was collected by filtration, washed and dried, dissolved in 50 ml of chloroform, and 20 ml of methanol was added. The precipitate was collected by filtration, washed and dried, and 4,4′-bis (4-butoxystyryl) diphenyl represented by the following formula: 2.21 g (48.0%) of sulfone was obtained. Elemental analysis values are as follows.

  Elemental analysis value (calculated value); C: 76.42% (76.29%), H: 7.04% (6.76%)

(Production Example 5) Production of Compound Example A6

  4-octyloxybenzaldehyde (10.0 g, 42.7 mmol) and aniline (4.17 g, 44.84 mmol) were mixed in 100 ml of methanol and heated to reflux for 3 hours to give 4-octyloxybenzylideneaniline (12.0 g, 90.9%). )Obtained.

  Under nitrogen atmosphere, 2.0 g (8.12 mmol) of p-tolylsulfone (manufactured by Tokyo Chemical Industry Co., Ltd.) and 5.29 g (17.05 mmol) of 4-octyloxybenzylideneaniline in 1.8 ml of potassium tert-butoxide in 60 ml of dimethylformamide. The reaction was carried out at room temperature for 1.5 hours in the presence of (16.24 mmol). After adding 20 ml of dimethylformamide, the mixture was added dropwise to 400 ml of ice water, hydrochloric acid was added to adjust to pH <4, and the mixture was stirred for 0.5 hour. The precipitate was collected by filtration, washed and dried, then dissolved in 150 ml of chloroform again, 150 ml of methanol was added, the precipitate was collected by filtration, washed and dried, and 4,4′-bis (4-octyloxystyryl represented by the following formula: ) 4.04 g (73.3%) of diphenylsulfone was obtained.

  Elemental analysis value (calculated value); C: 78.20% (77.84%), H: 8.34% (8.02%)

Production Example 6 Production Example of Compound Example A8 4-Diethylaminobenzaldehyde 10.0 g (56.4 mmol) and aniline 5.78 g (62.04 mmol) were mixed in 100 ml of methanol and heated to reflux for 3 hours to give 4-diethylaminobenzylideneaniline. Of 9.6 g (67.7%).

  Under a nitrogen atmosphere, 2.0 g (8.12 mmol) of p-tolylsulfone (manufactured by Tokyo Chemical Industry Co., Ltd.) and 4.32 g (17.05 mmol) of 4-diethylaminobenzylideneaniline in 1.8 ml of potassium tert-butoxide in 60 ml of dimethylformamide ( In the presence of 16.24 mmol), the reaction was carried out at room temperature for 2.0 hours and at 60 ° C. for 1.0 hour. The reaction solution was added dropwise to 300 ml of ice water, hydrochloric acid was added to adjust the pH to <4, and the precipitate was collected by filtration, washed and dried to obtain a yellow powder. The obtained yellow powder was subjected to silica gel column chromatography using chloroform as a developing solvent. The target product was collected, the solvent was distilled off, washed with 30 ml of methanol and dried to obtain 1.31 g (28.5%) of a crude purified product of 4,4′-bis (4-diethylaminostyryl) diphenylsulfone.

  0.1 g of the crude product thus obtained was dissolved in 4 ml of chloroform, filtered through hydrophobic PTFE having a pore size of 0.50 μm, 3 ml of methanol was added, and the precipitate was collected by filtration, and 4,4′- 0.088 g of bis (4-diethylaminostyryl) diphenylsulfone was obtained as a yellow powder. Elemental analysis values are as follows.

  Elemental analysis value (calculated value); C: 75.60% (76.56%), H: 7.25% (7.14%), N; 4.92% (4.96%)

(Production Example 7) Production of Compound Example A11 10.0 g (65.7 mmol) of 4-methylthiobenzaldehyde and 6.42 g (69.99 mmol) of aniline were mixed in 100 ml of methanol and heated under reflux for 3 hours to give 4-methylthiobenzylideneaniline. 12.7 g (85.1%) was obtained.

In a nitrogen atmosphere, 2.0 g (8.12 mmol) of p-tolylsulfone (manufactured by Tokyo Chemical Industry Co., Ltd.) and 3.89 g (17.05 mmol) of 4-methylthiobenzylideneaniline in 1.8 ml of potassium t-butoxide in 60 ml of dimethylformamide ( In the presence of 16.24 mmol), the reaction was allowed to proceed at room temperature for 1.5 hours. The reaction solution was added dropwise to 300 ml of ice water and hydrochloric acid was added to adjust to pH <4. Then, the precipitate was filtered, washed and dried to obtain 2.7 g of a pale yellow powder. Washing with 30 ml of dimethylformamide and 30 ml of chloroform gave 2.01 g (48.1%) of 4,4′-bis (4-methylthiostyryl) diphenylsulfone represented by the following formula.
Elemental analysis value (calculated value); C: 69.86% (70.00%), H: 4.89% (5.09%)

(Production Example 8) Production of Compound Example A15 4-phenylbenzaldehyde 10.0 g (54.9 mmol) and aniline 5.36 g (57.65 mmol) were mixed in 100 ml of methanol and heated under reflux for 3 hours to give 4-phenylbenzylideneaniline. 14.0 g (99.0%) were obtained.

  Under a nitrogen atmosphere, 2.0 g (8.12 mmol) of p-tolylsulfone (manufactured by Tokyo Chemical Industry Co., Ltd.) and 4.39 g (17.05 mmol) of 4-phenylbenzylideneaniline in 1.8 ml of dimethylformamide 1.82 g of potassium t-butoxide ( The reaction was allowed to proceed for 1.5 hours at room temperature in the presence of 32.48 mmol). After adding 50 ml of dimethylformamide, the solution was added dropwise to 500 ml of ice water, adjusted to pH <4 with hydrochloric acid, filtered, washed and dried to obtain 4.2 g of a white solid.

3.0 g of the obtained white solid was purified by Soxhlet washing with tetrahydrofuran as an extraction solvent for 55 hours, and 2.6 g (77.9) of 4,4′-bis (4-phenylstyryl) diphenylsulfone represented by the following formula: %)Obtained. Elemental analysis values are as follows.
Elemental analysis value (calculated value); C: 83.54% (83.59%), H: 5.27% (5.26%)

(Production Example 9) Production of Compound D7 4-dimethylaminocinnamaldehyde 10.0 g (57.1 mmol) and aniline 5.58 g (59.96 mmol) were mixed in 100 ml of methanol and heated to reflux for 3 hours. Obtained 11.1 g (77.7%) of myridenaniline.

  In a nitrogen atmosphere, 2.0 g (8.12 mmol) of p-tolylsulfone (manufactured by Tokyo Chemical Industry Co., Ltd.) and 4.28 g (17.05 mmol) of 4-dimethylaminocinnamylidaniline were added to 60 ml of dimethylformamide in potassium t-butoxide 1. The reaction was allowed to proceed at room temperature for 1.0 hour in the presence of .82 g (16.24 mmol). After adding 40 ml of dimethylformamide, the mixture was poured into 500 ml of ice water and adjusted to pH <4 by adding hydrochloric acid, and the precipitate was collected by filtration, washed and dried to obtain 2.0 g of an ocher powder. The obtained ocherous powder was subjected to silica gel column chromatography using chloroform as a developing solvent. After the solvent was distilled off, the residue was dispersed in 40 ml of 20% methanol in chloroform, the insoluble matter was collected by filtration, washed and dried, and 4,4′-bis (4-dimethylaminocinnamyl) diphenylsulfone represented by the following formula was changed to 0. 0.040 g (0.88%) was obtained. Elemental analysis values are as follows.

  Elemental analysis value (calculated value); C: 76.27% (77.11%), H: 6.69% (6.47%), N; 4.98% (5.00%)

(Production Example 10) Production of Compound Example A22 4-fluorobenzaldehyde 10.0 g (80.6 mmol) and aniline 7.88 g (84.63 mmol) were mixed in 100 ml of methanol and heated to reflux for 3 hours to give 4-fluorobenzylideneaniline. Obtained 9.3 g (57.9%).

  Under nitrogen atmosphere, 2.0 g (8.12 mmol) of p-tolylsulfone (manufactured by Tokyo Chemical Industry Co., Ltd.) and 3.41 g (17.05 mmol) of 4-fluorobenzylideneaniline in 1.8 ml of potassium t-butoxide in 60 ml of dimethylformamide ( In the presence of 16.24 mmol), the mixture was stirred at room temperature for 1.0 hour. The reaction solution was dropped into 300 ml of ice water and adjusted to pH <4 with hydrochloric acid. The precipitate was collected by filtration, washed and dried to obtain 4.1 g of a yellow powder. The obtained yellow powder was subjected to silica gel column chromatography using a chloroform / hexane mixed solvent as a developing solvent. The target product was collected and the solvent was distilled off. The residue was dissolved in 10 ml of chloroform, 20 ml of methanol was added, the precipitate was collected by filtration, washed and dried, and 4,4′-bis (4-fluorostyryl) represented by the following formula. 0.40 g (10.8%) of diphenyl sulfone was obtained. Elemental analysis values are as follows.

  Elemental analysis value (calculated value); C: 73.10% (73.43%), H: 4.13% (4.40%)

(Production Example 11) Production of Compound A23 2-trifluoromethylbenzaldehyde 10.0 g (57.4 mmol) and aniline 6.03 g (60.27 mmol) were mixed in 100 ml of methanol and heated to reflux for 3 hours to give 2-trifluoromethyl. 12.3 g (86.0%) of benzylidene aniline was obtained.

Under a nitrogen atmosphere, 2.0 g (8.12 mmol) of p-tolylsulfone (manufactured by Tokyo Chemical Industry Co., Ltd.) and 4.26 g (17.05 mmol) of 2-trifluoromethylbenzylideneaniline in potassium tert-butoxide 1.60 g in 60 ml of dimethylformamide. The mixture was stirred at room temperature for 1.0 hour in the presence of 82 g (16.24 mmol). The reaction solution was dropped into 300 ml of ice water and adjusted to pH <4 with hydrochloric acid. The precipitate was collected by filtration, washed and dried. The obtained solid was subjected to silica gel column chromatography using chloroform as a developing solvent. The target product was collected, the solvent was distilled off, dissolved in 5 ml of chloroform, 10 ml of methanol was added, the precipitate was filtered, washed and dried, and 4,4′-bis (2-trifluoromethyl) represented by the following formula: 0.95 g (20.9%) of styryl) diphenylsulfone was obtained. Elemental analysis values are as follows.
Elemental analysis value (calculated value); C: 64.8% (64.51%), H: 3.50% (3.61%)

Production Example 12 Production of Compound Example A16 2,4-dimethoxybenzaldehyde 10.0 g (60.2 mmol) and aniline 5.89 g (63.21 mmol) were mixed in 80 ml of methanol and heated to reflux for 3 hours. 13.4 g (92.2%) of dimethoxybenzylideneaniline was obtained.

  Under a nitrogen atmosphere, 2.0 g (8.12 mmol) of p-tolylsulfone (manufactured by Tokyo Chemical Industry Co., Ltd.) and 4.12 g (17.05 mmol) of 2,4-dimethoxybenzylideneaniline in potassium tert-butoxide 1.60 g in 60 ml of dimethylformamide. The mixture was stirred at room temperature for 2.0 hours in the presence of 82 g (16.24 mmol). The reaction solution was dropped into 300 ml of ice water and adjusted to pH <4 with hydrochloric acid. The precipitate was collected by filtration, washed and dried. 4.4 g of the obtained solid was subjected to silica gel column chromatography using chloroform as a developing solvent. The target product was collected and the solvent was distilled off. The residue was dissolved in 5 ml of dimethylformamide, poured into 100 ml of water, the precipitate was collected by filtration, washed and dried, and 4,4′-bis (2,4- 1.30 g (29.5%) of dimethoxystyryl) diphenylsulfone was obtained. Elemental analysis values are as follows.

  Elemental analysis value (calculated value); C: 70.96% (70.83%), H: 5.72% (5.57%)

Production Example 13 Production of Compound Example A17 3,4,5-Trimethoxybenzaldehyde 10.0 g (51.0 mmol) and aniline 4.98 g (53.55 mmol) were mixed in 70 ml of methanol and heated to reflux for 3 hours. , 4,5-Trimethoxybenzylideneaniline was obtained 11.9 g (86.2%).

Under a nitrogen atmosphere, 2.0 g (8.12 mmol) of p-tolylsulfone (manufactured by Tokyo Chemical Industry Co., Ltd.) and 4.64 g (17.05 mmol) of 3,4,5-trimethoxybenzylideneaniline in 60 ml of dimethylformamide in potassium t- The mixture was stirred at room temperature for 1.5 hours in the presence of 1.82 g (16.24 mmol) of butoxide. The reaction solution was dropped into 300 ml of ice water and adjusted to pH <4 with hydrochloric acid. The precipitate was collected by filtration, washed and dried. The obtained solid (4.9 g) was subjected to silica gel column chromatography using chloroform as a developing solvent. The target product was collected and the solvent was distilled off, then dissolved in 5 ml of dimethylformamide, poured into 100 ml of water, the precipitate was collected by filtration, washed and dried, and 4,4′-bis (3,4,4) represented by the following formula: 0.78 g (16.0%) of 5-trimethoxystyryl) diphenylsulfone was obtained. Elemental analysis values are as follows.
Elemental analysis value (calculated value); C: 67.47% (67.76%), H: 5.94% (5.69%)

(Production Example 14) Production of Compound Example A18 2,3,4-trimethoxybenzaldehyde 10.0 g (51.0 mmol) and aniline 4.98 g (53.55 mmol) were mixed in 60 ml of methanol and heated under reflux for 3 hours. Thus, 8.63 g (62.3%) of 3,4-trimethoxybenzylideneaniline was obtained.

Under a nitrogen atmosphere, 2.0 g (8.12 mmol) of p-tolylsulfone (manufactured by Tokyo Chemical Industry Co., Ltd.) and 4.64 g (17.05 mmol) of 2,3,4-trimethoxybenzylideneaniline in 60 ml of dimethylformamide in potassium t- The mixture was stirred at room temperature for 1 hour in the presence of 1.82 g (16.24 mmol) of butoxide. The reaction solution was dropped into 300 ml of ice water and adjusted to pH <4 with hydrochloric acid. The precipitate was collected by filtration, washed and dried. The obtained solid (4.9 g) was subjected to silica gel column chromatography using chloroform as a developing solvent. The target product was collected and the solvent was distilled off. The residue was dissolved in 10 ml of chloroform, 30 ml of methanol was added, the precipitate was collected by filtration, washed and dried, and 4,4′-bis (2,3,4) represented by the following formula: 1.70 g (34.8%) of -trimethoxystyryl) diphenylsulfone was obtained. Elemental analysis values are as follows.
Elemental analysis value (calculated value); C: 67.68% (67.76%), H: 5.70% (5.69%)

(Production Example 15) Production of Compound Example A19 2,5-dimethoxybenzaldehyde 10.0 g (60.2 mmol), aniline 4.98 g (63.21 mmol), and magnesium sulfate 1.0 g were mixed and stirred at room temperature for 3 hours. . The reaction solution was poured into 30 ml of chloroform, and magnesium sulfate was removed by filtration. The organic layer was washed with water, dehydrated with magnesium sulfate, evaporated to dryness, and then dried to obtain 13.0 g (89% of 2,5-dimethoxybenzylideneaniline). 0.7%).

Under a nitrogen atmosphere, 2.0 g (8.12 mmol) of p-tolylsulfone (manufactured by Tokyo Chemical Industry Co., Ltd.) and 4.12 g (17.05 mmol) of 2,5-dimethoxybenzylideneaniline in potassium tert-butoxide 1.60 g in 60 ml of dimethylformamide. The mixture was stirred at room temperature for 1 hour in the presence of 82 g (16.24 mmol). The reaction solution was dropped into 300 ml of ice water and adjusted to pH <4 with hydrochloric acid. The precipitate was collected by filtration, washed and dried. The obtained solid (5.0 g) was subjected to silica gel column chromatography using chloroform as a developing solvent. The target product was collected and the solvent was distilled off. The residue was dissolved in 5 ml of dimethylformamide and added dropwise to 50 ml of water. The precipitate was collected by filtration, washed and dried, and 4,4′-bis (2,5 0.3 g (6.8%) of -dimethoxystyryl) diphenylsulfone was obtained. Elemental analysis values are as follows.
Elemental analysis value (calculated value); C: 71.07% (70.83%), H: 5.49% (5.57%)

Production Example 16 Production of Compound Example A25 2-naphthaldehyde 10.0 g (64.0 mmol) and aniline 6.26 g (67.20 mmol) were mixed in 100 ml of methanol and heated to reflux for 3 hours. 50 ml of water was added dropwise to the reaction solution, and the precipitate was collected by filtration, washed and dried to obtain 13.5 g (91.2%) of 2-naphthethenylaniline.

Under a nitrogen atmosphere, 2.0 g (8.12 mmol) of p-tolylsulfone (manufactured by Tokyo Chemical Industry Co., Ltd.) and 3.96 g (17.05 mmol) of 2-naphthethenylaniline in 1.8 ml of potassium t-butoxide in 60 ml of dimethylformamide ( In the presence of 16.24 mmol), the mixture was stirred at room temperature for 1 hour. The reaction solution was dropped into 300 ml of ice water and adjusted to pH <4 with hydrochloric acid. The precipitate was collected by filtration, washed and dried. 4.6 g of the obtained solid was recrystallized twice from 60 ml of dimethylformamide to obtain 0.82 g (19.3%) of 4,4′-bis (2-naphthethenyl) diphenylsulfone represented by the following formula. Elemental analysis values are as follows.
Elemental analysis value (calculated value); C: 82.72% (82.73%), H: 4.77% (5.01%)

(Production Example 17) Production of Compound Example A20 3,4-diethoxybenzaldehyde 10.0 g (51.5 mmol), aniline 5.04 g (54.08 mmol), and magnesium sulfate 2.0 g were mixed and stirred at room temperature for 4 hours. did. The reaction solution was poured into 30 ml of chloroform, the magnesium sulfate was removed by filtration, the organic layer was washed with water, dehydrated with magnesium sulfate, the solvent was distilled off and dried, then poured into 100 ml of 10% aqueous methanol solution, stirred for 5 hours, Filtration, washing and drying yielded 9.35 g (67.4%) of 3,4-diethoxybenzylideneaniline.

Under nitrogen atmosphere, 2.0 g (8.12 mmol) of p-tolylsulfone (manufactured by Tokyo Chemical Industry Co., Ltd.) and 4.82 g (17.05 mmol) of 3,4-diethoxybenzylideneaniline in 60 ml of dimethylformamide 1 The mixture was stirred at room temperature for 1 hour in the presence of .82 g (16.24 mmol). The reaction solution was dropped into 300 ml of ice water and adjusted to pH <4 with hydrochloric acid. The precipitate was collected by filtration, washed and dried. The obtained solid (4.9 g) was subjected to silica gel column chromatography using chloroform as a developing solvent. The target product was collected and the solvent was distilled off. The residue was dissolved in 10 ml of chloroform, 20 ml of methanol was added, the precipitate was collected by filtration, washed and dried, and 4,4′-bis (3,4) represented by the following formula: 1.25 g (25.7%) of -diethoxystyryl) diphenylsulfone was obtained. Elemental analysis values are as follows.
Elemental analysis value (calculated value); C: 70.72% (72.21%), H: 6.46% (6.40%)

(Production Example 18) Production of Compound Example A7 4-Dimethylaminobenzaldehyde (14.9 g, 100 mmol) and aniline (9.31 g, 105 mmol) were mixed in 70 ml of methanol and heated to reflux for 3 hours. 30 ml of methanol and 30 ml of water were added to the reaction solution and stirred, and then the precipitate was collected by filtration, washed and dried to obtain a yellow solid. Furthermore, after dissolving in 100 ml of hot methanol and filtering, the precipitated crystals were collected by filtration to obtain 12.2 g (54.5%) of 4-dimethylaminobenzylideneaniline.

  Under nitrogen atmosphere, 2.0 g (8.12 mmol) of p-tolylsulfone (manufactured by Tokyo Chemical Industry Co., Ltd.) and 3.84 g (17.05 mmol) of 4-dimethylaminobenzylideneaniline in 1.8 ml of potassium tert-butoxide in 60 ml of dimethylformamide. The mixture was stirred at room temperature for 1 hour in the presence of (16.24 mmol). The reaction solution was dropped into 300 ml of ice water and adjusted to pH <4 with hydrochloric acid. The precipitate was collected by filtration, washed with chloroform and dried to obtain 0.15 g (3.6%) of 4,4′-bis (4-dimethylaminostyryl) diphenylsulfone represented by the following formula. Elemental analysis values are as follows.

  Elemental analysis value (calculated value); C: 74.29% (75.56%), H: 6.15% (6.34%), N: 4.80% (5.51%)

(Production Example 19) Production of Compound Example A9 4-Dibutylaminobenzaldehyde 5.0 g (21.4 mmol) and aniline 2.09 g (22.47 mmol) were mixed in 30 ml of methanol and heated to reflux for 3 hours. Methanol was distilled off under reduced pressure, 30 ml of chloroform was added, the organic layer was washed with water, dehydrated with magnesium sulfate, and the solvent was distilled off to obtain a brown liquid. Since the purity of the target product was about 60% from the integrated value of 1H NMR, aniline and magnesium sulfate were further added to the obtained brown liquid and reacted to give 12.2 g of 4-dibutylaminobenzylideneaniline at a purity of about 90% ( 54.5%).

Under nitrogen atmosphere, 1.5 g (6.09 mmol) of p-tolylsulfone (manufactured by Tokyo Chemical Industry Co., Ltd.) and 4.40 g (12.79 mmol) of 4-dibutylaminobenzylideneaniline in 1.60 g of potassium tert-butoxide in 60 ml of dimethylformamide. The mixture was stirred at room temperature for 1 hour in the presence of (12.18 mmol). The reaction solution was dropped into 300 ml of ice water and adjusted to pH <4 with hydrochloric acid. The precipitate was extracted with 150 ml of chloroform, washed with 300 ml of water, dehydrated with magnesium sulfate, and the solvent was distilled off to obtain 3.6 g of a brown liquid. The obtained liquid was subjected to silica gel column chromatography using chloroform as a developing solvent. The target product was collected and the solvent was distilled off, followed by recrystallization from hot ethanol, and 0.40 g (9.7%) of 4,4′-bis (4-dibutylaminostyryl) diphenylsulfone represented by the following formula. Obtained. Elemental analysis values are as follows.
Elemental analysis value (calculated value); C: 78.08% (78.06%), H: 8.79% (8.34%), N: 3.89% (4.14%)

(Production Example 20) Production of Compound Example A21 2-t-butylthiobenzaldehyde 9.0 g (46.3 mmol), aniline 4.53 g (48.62 mmol), and magnesium sulfate 1.0 g were mixed and stirred with heating for 3 hours. Chloroform was distilled off under reduced pressure after adding chloroform to the reaction mixture and filtering. After adding 100 ml of 10% aqueous methanol solution to the obtained solid, the mixture was stirred for 2 h on an ice bath, the precipitate was collected by filtration, washed and dried, and 9.71 g (77.9) of 2-t-butylthiobenzylideneaniline was obtained. %)Obtained.

Under a nitrogen atmosphere, 2.0 g (8.12 mmol) of p-tolylsulfone (manufactured by Tokyo Chemical Industry Co., Ltd.) and 4.61 g (17.05 mmol) of 2-t-butylthiobenzylideneaniline in 60 ml of dimethylformamide 1 The mixture was stirred at room temperature for 0.5 hours in the presence of .82 g (16.24 mmol). The reaction solution was dropped into 300 ml of ice water and adjusted to pH <4 with hydrochloric acid. The precipitate was collected by filtration, washed and dried to obtain 5.7 g of a brown solid. The obtained solid was subjected to silica gel column chromatography using a mixed solvent of chloroform / hexane as a developing solvent. The target product was collected, the solvent was distilled off, washed with 100 ml of methanol, dried, and 2.85 g (58.6) of 4,4′-bis (2-tert-butylthiostyryl) diphenylsulfone represented by the following formula: %)Obtained. Elemental analysis values are as follows.
Elemental analysis value (calculated value); C: 72.02% (72.20%), H: 6.27% (6.40%)

  (Production Example 21) Production of Compound Example A12

  10.0 g (60.2 mmol) of 4-ethylthiobenzaldehyde and 5.89 g (63.21 mmol) of aniline were mixed in 50 ml of methanol and heated to reflux for 3 hours. To the reaction solution, 20 ml of methanol and 20 ml of water were added and stirred, and then the precipitate was collected by filtration, washed and dried to obtain 13.20 g (90.8%) of 4-ethylthiobenzylideneaniline.

Under nitrogen atmosphere, 2.0 g (8.12 mmol) of p-tolylsulfone (manufactured by Tokyo Chemical Industry Co., Ltd.) and 4.13 g (17.05 mmol) of 4-ethylthiobenzylideneaniline in 1.8 ml of potassium tert-butoxide in 60 ml of dimethylformamide. The mixture was stirred at room temperature for 0.5 hours in the presence of (16.24 mmol). The reaction solution was dropped into 300 ml of ice water and adjusted to pH <4 with hydrochloric acid. The precipitate was collected by filtration, washed and dried to obtain 4.7 g of a yellow solid. The obtained solid was subjected to silica gel column chromatography using a mixed solvent of chloroform / hexane as a developing solvent. The target product was collected, the solvent was distilled off, washed with 50 ml of chloroform and dried. 0.04 g (0.9%) of 4,4′-bis (4-ethylthiostyryl) diphenylsulfone represented by the following formula Obtained. Elemental analysis values are as follows.
Elemental analysis value (calculated value); C: 69.78% (70.81%), H: 5.45% (5.57%)

Production of heterodisubstituted diphenylsulfone derivatives (Production Example 22) Production of Compound Example A26

  4-hydroxybenzaldehyde 20.0 g (164 mmol) and aniline 5.78 g (172 mmol) were mixed in 200 ml of methanol and heated under reflux for 3 hours to obtain 4-hydroxybenzylideneaniline.

  Under a nitrogen atmosphere, 2.0 g (8.12 mmol) of p-tolylsulfone (manufactured by Tokyo Chemical Industry Co., Ltd.) and 3.37 g (17.09 mmol) of 4-hydroxybenzylideneaniline in 60 ml of dimethylformamide, 3.64 g of potassium t-butoxide ( In the presence of 32.48 mmol), the mixture was stirred at room temperature for 1.0 hour. The reaction solution was dropped into 300 ml of ice water and adjusted to pH <4 with hydrochloric acid. The precipitate was collected by filtration, washed and dried. The obtained solid was subjected to silica gel column chromatography using a mixed solvent of tetrahydrofuran / hexane as a developing solvent. The target product was collected, the solvent was distilled off, washed with chloroform and dried to give 4- (4-hydroxystyryl) -4'-methyldiphenylsulfone.

  Under a nitrogen atmosphere, 2.0 g (5.71 mmol) of 4- (4-hydroxystyryl) -4′-methyldiphenylsulfone and 1.56 g (11.42 mmol) of 1-bromobutane in 1.57 g of potassium carbonate in 30 ml of dimethylformamide (11.42 mmol) was allowed to react at room temperature for 15 hours. After adding 100 ml of water, the precipitate was collected by filtration, washed and dried, then dissolved again in 20 ml of chloroform and added with 80 ml of methanol, and the precipitate was collected by filtration, washed and dried, and 4- (4- 1.89 g (81.5%) of butoxystyryl) -4′-methyldiphenylsulfone was obtained.

  In a nitrogen atmosphere, 1.54 g (3.80 mmol) of 4- (4-butoxystyryl) -4 ′-(methyl) diphenylsulfone and 1.05 g (4.18 mmol) of 4-diethylaminobenzylideneaniline were added to potassium in 60 ml of dimethylformamide. The mixture was stirred at 90 ° C. for 1 hour in the presence of 2.25 g (19.00 mmol) of t-butoxide. The reaction solution was dropped into 300 ml of ice water and adjusted to pH <4 with hydrochloric acid. The precipitate was collected by filtration, washed and dried, again dissolved in 20 ml of chloroform, added with 30 ml of methanol, and the precipitate was collected by filtration, washed and dried to obtain 0.55 g of a yellow powder. The obtained powder was subjected to silica gel column chromatography using chloroform as a developing solvent. The target product was collected and the solvent was distilled off, followed by washing and drying, and 55 mg (2.6%) of 4- (4-butoxystyryl) -4 ′-(4-diethylaminostyryl) diphenylsulfone represented by the following formula: Obtained. Elemental analysis values are as follows.

  Elemental analysis value (calculated value); C: 76.29% (76.42%), H: 7.12% (6.95%), N: 2.11% (2.48%), S: 6 .09% (5.67%)

  (Production Example 23) Production of Compound Example A27

  Under a nitrogen atmosphere, 6.0 g (17.12 mmol) of 4- (4-hydroxystyryl) -4′-methyldiphenylsulfone and 6.60 g (34.16 mmol) of 1-bromooctane were added in 40 ml of dimethylformamide with 5. The reaction was carried out in the presence of 73 g (41.46 mmol) at room temperature for 15 hours and at 50 ° C. for 3 hours. After adding 150 ml of water, the precipitate was collected by filtration, washed and dried, then dissolved in 40 ml of chloroform again, 60 ml of methanol was added, the precipitate was collected by filtration, washed and dried, and 4- (4-octyloxystyryl)- 6.67 g (84.3%) of 4′-methyldiphenyl sulfone was obtained.

  In a nitrogen atmosphere, 2.31 g (5.00 mmol) of 4- (4-octyloxystyryl) -4′-methyldiphenylsulfone and 1.35 g (6.00 mmol) of 4-dimethylaminobenzylideneaniline in 80 ml of dimethylformamide in potassium The mixture was stirred at 30 ° C. for 1 hour in the presence of 1.24 g (11.00 mmol) of t-butoxide. The reaction solution was dropped into 300 ml of ice water and adjusted to pH <4 with hydrochloric acid. The precipitate was collected by filtration, washed and dried to obtain 2.9 g of a yellow solid. The obtained solid was put into 100 ml of dimethylformamide, stirred for 0.5 hour, filtered, washed and dried, and 4- (4-octyloxystyryl) -4 ′-(4-dimethylaminostyryl) represented by the following formula: 1.61 g (54.2%) of diphenylsulfone was obtained. Elemental analysis values are as follows.

  Elemental analysis value (calculated value); C: 77.28% (76.86%), H: 7.28% (7.30%), N: 2.55% (2.36%)

  (Production Example 24) Production of Compound Example A28

  Under a nitrogen atmosphere, 2.00 g (4.32 mmol) of 4- (4-octyloxystyryl) -4 ′-(methyl) diphenylsulfone and 1.18 g (4.73 mmol) of 2-trifluoromethylbenzylideneaniline were added to 80 ml of dimethylformamide. The mixture was stirred at 30 ° C. for 1 hour in the presence of 0.97 g (8.46 mmol) of potassium t-butoxide. The reaction solution was dropped into 300 ml of ice water and adjusted to pH <4 with hydrochloric acid. The precipitate was collected by filtration, washed and dried to obtain 2.3 g of a yellow solid. The obtained solid was subjected to silica gel column chromatography using chloroform as a developing solvent. The target product was collected and the solvent was distilled off. The residue was again dissolved in 15 ml of chloroform, 30 ml of methanol was added, and the precipitate was collected by filtration, washed and dried to obtain 0.6 g of a milky white solid. The solid obtained was dissolved in 10 ml of chloroform, extracted with 200 ml of ethanol, the solvent was distilled off, and 4- (4-octyloxystyryl) -4 ′-(2-trifluoromethylstyryl) diphenyl represented by the following formula was used. 30 mg (1.1%) of sulfone was obtained. Elemental analysis values are as follows.

  Elemental analysis value (calculated value); C: 70.98% (71.82%), H: 6.24% (6.03%)

  (Production Example 25) Production of Compound Example A29

  76.08 g (0.50 mol) of vanillin and 48.89 g (0.525 mol) of aniline were mixed in 400 ml of methanol and heated to reflux for 4 hours to give 107.2 g (94.3%) of 4-hydroxy-3-methoxybenzylideneaniline. Obtained.

  Under a nitrogen atmosphere, 2.46 g (10.00 mmol) of p-tolylsulfone (manufactured by Tokyo Chemical Industry Co., Ltd.) and 2.27 g (10.00 mmol) of 4-hydroxy-3-methoxybenzylideneaniline in 60 ml of dimethylformamide in potassium t-butoxide The reaction was carried out at 70 ° C. for 1.5 hours in the presence of 2.24 g (20.00 mmol). The reaction solution was dropped into 60 ml of ice water and hydrochloric acid was added to adjust to pH <4. Then, the precipitate was filtered, washed and dried to obtain 3.2 g of an ocherous solid. The obtained solid was subjected to silica gel column chromatography using chloroform as a developing solvent. The target product was collected, the solvent was distilled off, washed with 20 ml of methanol and dried, and 0.29 g (7.6%) of 4- (4-hydroxy-3-methoxystyryl) -4 ′-(methyl) diphenylsulfone was obtained. )Obtained

  Under nitrogen atmosphere, 1.00 g (2.63 mmol) of 4- (4-hydroxy-3-methoxystyryl) -4′-methyldiphenylsulfone and 1.05 g (2.63 mmol) of 4-diethylaminobenzylideneaniline in 30 ml of dimethylformamide In the presence of 2.70 g (23.67 mmol) of potassium t-butoxide, the mixture was stirred at 90 ° C. for 4 hours. The reaction solution was added dropwise to 200 ml of ice water and adjusted to pH <4 with hydrochloric acid. The precipitate was collected by filtration, washed and dried to obtain 1.7 g of an ocher solid. The obtained solid was subjected to silica gel column chromatography using chloroform as a developing solvent. The target product was collected and the solvent was distilled off, followed by washing and drying, and 0.16 g of 4- (4-hydroxy-3-methoxystyryl) -4 ′-(4-diethylaminostyryl) diphenylsulfone represented by the following formula. (11.3%) was obtained. Elemental analysis values are as follows.

  Elemental analysis value (calculated value); C: 72.51% (73.44%), H: 6.34% (6.16%), N: 2.60% (2.60%), S: 5 .95% (5.94%)

  (Production Example 26) Production of Compound Example A30

  Under nitrogen atmosphere, 1.35 g (3.56 mmol) of 4- (4-hydroxy-3-methoxystyryl) -4′-methyldiphenylsulfone and 1.08 g (4.27 mmol) of 4-butoxybenzylideneaniline in 20 ml of dimethylformamide In the presence of 2.80 g (24.95 mmol) of potassium t-butoxide, the mixture was stirred at room temperature for 1 hour and at 50 ° C. for 4 hours. The reaction solution was added dropwise to 200 ml of ice water and adjusted to pH <4 with hydrochloric acid. The precipitate was collected by filtration, washed and dried to obtain 1.9 g of an ocher solid. The obtained solid was subjected to silica gel column chromatography using chloroform as a developing solvent. The target product was collected, the solvent was distilled off, washed and dried, then dissolved again in chloroform 15 ml, methanol 25 ml was added, the precipitate was collected by filtration, washed and dried, and 4- (4-hydroxy) represented by the following formula: 0.96 g (50.0%) of -3-methoxystyryl) -4 ′-(4-butoxystyryl) diphenylsulfone was obtained. Elemental analysis values are as follows.

  Elemental analysis value (calculated value); C: 73.57% (73.31%), H: 6.17% (5.97%), S: 5.92% (5.93%)

  (Production Example 27) Production of Compound Example A31

  4- (4-Hydroxy-3-methoxystyryl) -4 ′-(4-butoxystyryl) diphenylsulfone 0.15 g (0.277 mmol), 1-bromooctane 0.107 g (0.554 mmol) in dimethylformamide 5 ml In the presence of 0.077 g (0.554 mmol) of potassium carbonate, the mixture was reacted at room temperature for 0.5 hours and at 50 ° C. for 5.5 hours. After adding 20 ml of water, the precipitate was collected by filtration, washed and dried, and 0.17 g (95 of 4- (4-octyloxystyryl) -4 ′-(4-butoxystyryl) diphenylsulfone represented by the following formula: 0.0%). Elemental analysis values are as follows.

  Elemental analysis value (calculated value); C: 75.17% (75.43%), H: 7.76% (7.41%), S; 5.27% (4.91%)

Refractive index measurement The refractive index of the measurement sample was measured with an Abbe refractometer (Atago Co., Ltd., DR-A1) at a room temperature of 24 ° C. The refractive index of each solution was approximated by the refractive index of only a solvent such as chloroform, 1.0N sulfuric acid solution, 0.1N sodium hydroxide solution. Each sample was measured three times, and the average value was used as the refractive index.

Absorbance measurement The one-photon absorption spectrum was measured using an ultraviolet-visible spectrophotometer UV-1700 manufactured by Shimadzu Corporation. Table 5 shows the results of the one-photon absorption wavelength and molar extinction coefficient of the homodisubstituted diphenylsulfone derivative, Table 6 shows the results of the one-photon absorption wavelength and molar extinction coefficient of the heterodisubstituted diphenylsulfone derivative, and is outside the scope of the present invention. Table 7 shows the results of the one-photon absorption wavelength and the molar extinction coefficient using the hetero monosubstituted diphenylsulfone derivative as a comparative compound.

(One-photon absorption wavelength and molar extinction coefficient of homodisubstituted diphenylsulfone derivatives)

(One-photon absorption wavelength and molar extinction coefficient of heterodisubstituted diphenylsulfone derivatives)

The structure and production method of the comparative compound used for the production measurement of the hetero monosubstituted diphenylsulfone derivative (comparative compound) are as follows.

Comparative compound 1
4-Hydroxybenzaldehyde (20.0 g, 164 mmol) and aniline (5.78 g, 172 mmol) were mixed in 200 ml of methanol and heated to reflux for 3 hours to obtain 30.4 g (94.1%) of 4-hydroxybenzylideneaniline.

Under a nitrogen atmosphere, 2.0 g (8.12 mmol) of p-tolylsulfone (manufactured by Tokyo Chemical Industry Co., Ltd.) and 3.37 g (17.09 mmol) of 4-hydroxybenzylideneaniline in 60 ml of dimethylformamide, 3.64 g of potassium t-butoxide ( In the presence of 32.48 mmol), the mixture was stirred at room temperature for 1.0 hour. The reaction solution was dropped into 300 ml of ice water and adjusted to pH <4 with hydrochloric acid. The precipitate was collected by filtration, washed and dried. The obtained solid was subjected to silica gel column chromatography using a mixed solvent of tetrahydrofuran / hexane as a developing solvent. The target product was collected, the solvent was distilled off, washed with chloroform and dried to obtain 0.10 g (3.5%) of 4- (4-hydroxystyryl) -4′-methyldiphenylsulfone represented by the following formula. It was. Elemental analysis values are as follows.
Elemental analysis value (calculated value); C: 71.88% (71.98%), H: 5.36% (5.18%), S: 9.37% (9.15%)

Comparative compound 2
Under a nitrogen atmosphere, 2.0 g (5.71 mmol) of 4- (4-hydroxystyryl) -4′-methyldiphenylsulfone and 1.56 g (11.42 mmol) of 1-bromobutane in 1.57 g of potassium carbonate in 30 ml of dimethylformamide (11.42 mmol) was allowed to react at room temperature for 15 hours. After adding 100 ml of water, the precipitate was collected by filtration, washed and dried, then dissolved again in 20 ml of chloroform and added with 80 ml of methanol, and the precipitate was collected by filtration, washed and dried, and 4- (4- 1.89 g (81.5%) of butoxystyryl) -4′-methyldiphenylsulfone was obtained. Elemental analysis values are as follows.
Elemental analysis value (calculated value); C: 73.92% (73.86%), H: 6.36% (6.45%)

Comparative compound 3
Under a nitrogen atmosphere, 6.0 g (17.12 mmol) of 4- (4-hydroxystyryl) -4′-methyldiphenylsulfone and 6.60 g (34.16 mmol) of 1-bromooctane were added in 40 ml of dimethylformamide with 5. The reaction was carried out in the presence of 73 g (41.46 mmol) at room temperature for 15 hours and at 50 ° C. for 3 hours. After adding 150 ml of water, the precipitate was collected by filtration, washed and dried, then dissolved in 40 ml of chloroform again, 60 ml of methanol was added, the precipitate was collected by filtration, washed and dried, and 4- (4- 6.67 g (84.3%) of octyloxystyryl) -4′-methyldiphenylsulfone was obtained. Elemental analysis values are as follows.
Elemental analysis value (calculated value); C: 75.01% (75.29%), H: 7.66% (7.41%), N; 7.39% (6.93%)

Comparative compound 4
Under a nitrogen atmosphere, 4- (4-hydroxystyryl) -4′-methyldiphenylsulfone 3.30 g (9.42 mmol) and 1-bromo-2-ethylhexane 3.64 g (18.84 mmol) were added in 30 ml of dimethylformamide. The reaction was carried out in the presence of 3.90 g (28.26 mmol) of potassium carbonate at room temperature for 15 hours and at 60 ° C. for 6 hours. After adding 150 ml of water, the precipitate was collected by filtration, washed and dried, then dissolved in 20 ml of chloroform again, 40 ml of methanol was added, the precipitate was collected by filtration, washed and dried, and 4- (4- 3.31 g (71.3%) of (2-ethylhexyloxy) styryl) -4′-methyldiphenylsulfone was obtained. Elemental analysis values are as follows.
Elemental analysis value (calculated value); C: 75.04% (75.29%), H: 7.26% (7.41%)

Comparative compound 5
76.08 g (0.50 mol) of vanillin and 48.89 g (0.525 mol) of aniline were mixed in 400 ml of methanol and heated to reflux for 4 hours to give 107.2 g (94.3%) of 4-hydroxy-3-methoxybenzylideneaniline. Obtained.

Under a nitrogen atmosphere, 2.46 g (10.00 mmol) of p-tolylsulfone (manufactured by Tokyo Chemical Industry Co., Ltd.) and 2.27 g (10.00 mmol) of 4-hydroxy-3-methoxybenzylideneaniline in 60 ml of dimethylformamide in potassium t-butoxide The reaction was carried out at 70 ° C. for 1.5 hours in the presence of 2.24 g (20.00 mmol). The reaction solution was dropped into 60 ml of ice water and hydrochloric acid was added to adjust to pH <4. Then, the precipitate was filtered, washed and dried to obtain 3.2 g of an ocherous solid. The obtained solid was subjected to silica gel column chromatography using chloroform as a developing solvent. The target product was collected, the solvent was distilled off, washed with 20 ml of methanol, dried, and 0.29 g of 4- (4-hydroxy-3-methoxystyryl) -4 ′-(methyl) diphenylsulfone represented by the following formula. (7.6%) was obtained. Elemental analysis values are as follows.
Elemental analysis value (calculated value); C: 69.63% (69.45%), H: 5.34% (5.30%), S: 8.72% (8.43%)

Comparative compound 6
5.00 g (22.51 mmol) of 3- (1,1,2,2-tetrafluoroethoxy) benzaldehyde, 2.20 g (23.62 mmol) of aniline and 1.0 g of magnesium sulfate were mixed and heated and stirred for 3 hours. The reaction solution is poured into 20 ml of hexane, magnesium sulfate is removed by filtration, the organic layer is washed with water, dehydrated with magnesium sulfate, and the solvent is distilled off. 3- (1,1,2,2-tetrafluoroethoxy) benzylideneaniline 5.50 g (82.2%) was obtained.

Under a nitrogen atmosphere, 1.20 g (4.87 mmol) of p-tolylsulfone (manufactured by Tokyo Chemical Industry Co., Ltd.) and 3.04 g (10.23 mmol) of 3- (1,1,2,2-tetrafluoroethoxy) benzylideneaniline were converted to dimethyl The reaction was carried out in 30 ml of formamide in the presence of 6.60 g (58.82 mmol) of potassium t-butoxide at 50 ° C. for 2 hours and at 100 ° C. for 2 hours. The reaction solution is added dropwise to 60 ml of ice water, adjusted to pH <4 by adding hydrochloric acid, the precipitate is filtered and washed, dissolved in 100 ml of chloroform, the organic layer is washed with dilute hydrochloric acid, dehydrated with magnesium sulfate, and the solvent is distilled off. A brown liquid was obtained. The obtained liquid was subjected to silica gel column chromatography using a chloroform / hexane mixed solvent as a developing solvent. The target product was collected, the solvent was distilled off, washed with methanol, dried, and 4- (3- (1,1,2,2-tetrafluoroethoxy) styryl) -4 ′-(methyl) represented by the following formula: ) 90 mg (4.1%) of diphenylsulfone was obtained. Elemental analysis values are as follows.
Elemental analysis value (calculated value); C: 61.26% (61.33%), H: 3.82% (4.03%)

(One-photon absorption wavelength and molar extinction coefficient of hetero monosubstituted diphenylsulfone derivatives)

Fluorescence spectrum and fluorescence quantum yield measurement The one-photon fluorescence spectrum was measured using a Shimadzu fluorescence spectrophotometer RF5300-PC. Examples of fluorescent standards include W.W. H. Melhuish, J. et al. Opt. Soc. Am. , 1964, 54, 183. A 1.0 N sulfuric acid solution of quinine sulfate having a quantum yield of 0.55 at an excitation wavelength of 313 nm and 366 nm in a dilute solution as described was used. The fluorescence spectrum was corrected by using a correction function of the spectrometer, and the relative fluorescence quantum yield was calculated using the obtained correction spectrum. All sample solutions were used under air saturation. The results are shown in Table 8.

(One-photon fluorescence wavelength and quantum yield of homodisubstituted diphenylsulfone derivatives)

(One-photon fluorescence wavelength and quantum yield of heterodisubstituted diphenylsulfone derivatives)

(One-photon fluorescence wavelength and quantum yield of hetero monosubstituted diphenylsulfone derivatives)

Evaluation of Two-Photon Absorption Cross Section The evaluation of the two-photon absorption cross section of the two-photon absorption compound of the present invention was performed using a fluorescence method.

Evaluation of the two-photon absorption cross section by the fluorescence method A. Albota et al. , Appl. Opt. 1998, 37, 7352. The description was made with reference to the method described. This measurement method is a method for comparing the intensity of light emission from an excited state induced by non-resonant two-photon absorption between a reference substance and a substance to be measured. This measurement method can be measured only by a compound that causes two-photon emission, but is simpler than other methods and has a feature that a relatively accurate value can be obtained.
Using a Ti: sapphire pulse laser (pulse width: <100 fs, repetition frequency: 80 MHz ± 1 MHz) as a light source for measuring the two-photon absorption cross section, the two-photon absorption cross section was measured in a wavelength range of 690 nm to 960 nm. The excitation light intensity was adjusted with a half-wave plate and a polarizing beam splitter, and the beam transmitted through the objective lens and the blank solution was collected and measured with a power meter. The cuvette used for the measurement is a fluorescent quartz cell with an optical path length of 1 mm, and the condenser lens is N.P. A. = 0.45 objective lens was used.
The fluorescence generated from the sample is emitted in all directions, but the front fluorescence incident on the objective lens is separated from the excitation light by using a 45 ° cold mirror, and then collected by the lens at the end of the optical fiber connected to the spectrometer. The spectrum was obtained by light. The dependence of the fluorescence intensity on the square of the excitation light intensity was confirmed within a range of 5 to 30 mW. Spectral sensitivity correction of the spectroscope was performed on the whole fluorescence observation optical system including a lens, a mirror, and an optical fiber by making tungsten halogen light having a color temperature of 3000 K incident on the objective lens from the position of the measurement sample. The evaluation of the two-photon absorption cross section was measured using fluorescein as a standard substance. The value described in the literature was applied to the two-photon absorption cross-sectional area of fluorescein, and calculation was performed by comparing the two-photon fluorescence intensity of fluorescein and each compound. The values of refractive index and fluorescence quantum yield were also used for calculating the two-photon absorption cross section.
As a sample for two-photon absorption measurement, a solution in which a compound was dissolved in chloroform at a concentration of 0.5 to 1 × 10 ⁻⁴ M was used. The two-photon absorption cross section of fluorescein was measured by using a solution dissolved in 0.1N sodium hydroxide solution at a concentration of 0.0145 mM.

  The two-photon absorption cross section was calculated using the following formula.

η：蛍光量子収率
σ(λ)：二光子吸収断面積
φst：標準物質の蛍光捕集効率
ηst：標準物質の蛍光量子収率
σst(λ)：標準物質の二光子吸収断面積
Ｃst：標準物質の濃度
＜Ｐst＞：標準物質の平均レーザーパワー
＜Ｆ＞：平均蛍光強度
ｎst：標準物質の屈折率
φ：蛍光捕集効率
Ｃ：濃度
＜Ｐ＞：平均レーザーパワー
＜Ｆst＞：標準物質の平均蛍光強度

η: Fluorescence quantum yield σ (λ): Two-photon absorption cross section φst: Fluorescence collection efficiency of standard material ηst: Fluorescence quantum yield of standard material σst (λ): Two-photon absorption cross section of standard material Cst: Standard Concentration of substance <Pst>: Average laser power <F> of standard substance: Average fluorescence intensity nst: Refractive index φ of standard substance: Fluorescence collection efficiency C: Concentration <P>: Average laser power <Fst>: of standard substance Average fluorescence intensity

(Two-photon excitation maximum wavelength and two-photon absorption cross section of homodisubstituted diphenylsulfone derivatives)

(Two-photon excitation maximum wavelength and two-photon absorption cross section of heterodisubstituted diphenylsulfone derivatives)

(Two-photon excitation maximum wavelength and two-photon absorption cross section of hetero monosubstituted diphenylsulfone derivatives)

Evaluation of Two-Photon Polymerization Threshold An example of two-photon polymerization using only a monofunctional monomer and a two-photon absorbing material will be shown.

Example 1
A photocurable resin composition was prepared as follows.
Dimethylacrylamide 100 parts by weight Compound Example A8 0.1 parts by weight

  The photocurable resin composition was filtered with a disposable filter (DISMIC PTFE pore size 0.5 μm, manufactured by Advantech Co., Ltd.) as a resin composition for evaluation. For the sample for polymerization, the above resin composition was injected between the slide glass and the cover glass by the method described in JP 2010-065083 A. A polyimide film having a thickness of 25 μm was used.

  As the two-photon polymerization apparatus, a similar optical apparatus was produced according to the description in JP-A-2010-065083. Laser light (700 nm or 800 nm) is incident from the back of an Olympus epi-illumination fluorescent tube BX-RFA, and the laser light is reflected by 45 ° by a dichroic mirror. 0.95) is irradiated toward the sample for polymerization. The polymerization sample is fixed on an XYZ triaxial drive automatic stage to adjust the laser focusing point, and an arbitrary three-dimensional cured product can be obtained by scanning the stage. In order to observe the fluorescence obtained by two-photon excitation on the opposite side of the polymerization sample with respect to the dichroic mirror, a short-pass filter and a CCD camera are installed so that the polymerization sample-dichroic mirror-CCD camera are aligned. did. The presence or absence of the cured resin was determined using an Olympus objective lens UPlanSApo20X. The intensity of the laser light applied to the sample was determined based on the light intensity immediately before the objective lens. The transmittance of the objective lens was 85% at a wavelength of 700 nm and 55% at a wavelength of 800 nm. The light intensity immediately before the objective lens and the light intensity at the monitor position differ in wavelength dispersion, but the relationship between the two was previously investigated and corrected. The moving speed of the focal position with respect to the resin was appropriately adjusted so that a cured product with good visibility was obtained.

Comparative Example 1
A photocurable resin composition was prepared as follows.
Dimethylacrylamide 100 parts by mass The composition was subjected to the same operation as in Example 1 for two-photon polymerization.

Example 2
A photocurable resin composition was prepared as follows.
100 parts by mass of acryloylmorpholine Compound Example A2 0.05 parts by mass This composition was subjected to the same operation as in Example 1 for two-photon polymerization.

Comparative Example 2
A photocurable resin composition was prepared as follows.
100 parts by mass of acryloylmorpholine This composition was subjected to the same operation as in Example 1 for two-photon polymerization.

  An example of two-photon polymerization using a monofunctional monomer, a polyfunctional monomer, and a two-photon absorbing material is shown.

Example 3
A photocurable resin composition was prepared as follows.
Dimethylacrylamide 20 parts by mass Isocyanuric acid EO-modified di- and triacrylate 80 parts by mass Compound Example A8 0.1 part by mass This composition was subjected to the same operation as in Example 1 to carry out two-photon polymerization.

Comparative Example 3
A photocurable resin composition was prepared as follows.
Dimethylacrylamide 20 parts by mass Isocyanuric acid EO-modified di- and triacrylate 80 parts by mass This composition was subjected to the same operation as in Example 1 for two-photon polymerization.

Example 4
A photocurable resin composition was prepared as follows.
80 parts by mass of acryloylmorpholine 20 parts by mass of pentaerythritol tetraacrylate Compound Example A2 0.04 parts by mass This composition was subjected to the same operation as in Example 1 to carry out two-photon polymerization.

Comparative Example 4
A photocurable resin composition was prepared as follows.
Acryloylmorpholine 80 parts by mass Pentaerythritol tetraacrylate 20 parts by mass This composition was subjected to the same operation as in Example 1 to carry out two-photon polymerization.

Example 5
A photocurable resin composition was prepared as follows.
n-Butyl acrylate 60 parts by weight Trimethylolpropane triacrylate 40 parts by weight Compound Example A5 0.04 parts by weight This composition was subjected to the same operation as in Example 1 to carry out two-photon polymerization.

Comparative Example 5
A photocurable resin composition was prepared as follows.
n-Butyl acrylate 60 parts by weight Trimethylolpropane triacrylate 40 parts by weight This composition was subjected to the same operation as in Example 1 for two-photon polymerization.

Example 6
A photocurable resin composition was prepared as follows.
Tetrahydrofurfuryl acrylate 60 parts by weight Trimethylolpropane triacrylate 40 parts by weight Compound Example A22 0.1 part by weight The same operation as in Example 1 was performed on this composition to perform two-photon polymerization.

Comparative Example 6
A photocurable resin composition was prepared as follows.
Tetrahydrofurfuryl acrylate 60 parts by mass Trimethylolpropane triacrylate 40 parts by mass This composition was subjected to the same operation as in Example 1 to carry out two-photon polymerization.

The photocurable resin composition prepared by two-photon polymerization measurement is injected between two sheets of glass, and the resin is cured inside the photocurable resin composition by operating the sample stage while focusing the laser on the composition. A product was made. The presence or absence of the production | generation of resin cured | curing material was determined visually through the 20 times objective lens. The results are shown in the table below.

The refractive index measurement chloroform solution was 1.443, 0.1N sodium hydroxide solution was 1.334, 1.0N sulfuric acid solution was 1.339.

Absorbance measurement Regarding Compound Example A7, Compound Example A8, and Compound Example A9 having an alkylamino group, the absorption maximum wavelength was about 400 nm. Compound Example A1, Compound Example A2, Compound Example A3, Compound Example A5, Compound Example A6, Compound Example A16, Compound Example A19, Compound Example A20, Compound Example which are unsubstituted or have an alkyl group, an alkoxy group or an alkylthio group Regarding A17, Compound Example A18, Compound Example A11, Compound Example A12, and Compound Example A21, the absorption maximum wavelength was about 360 nm or less.

Fluorescence spectrum and fluorescence quantum yield measurement The results of fluorescence spectrum and fluorescence quantum yield measurement of homodisubstituted diphenylsulfone derivatives are shown in Table 8, and the fluorescence spectrum and fluorescence quantum yield measurement results of heterodisubstituted diphenylsulfone derivatives are shown in Table 8. The results of measurement of the fluorescence spectrum and fluorescence quantum yield of the hetero monosubstituted diphenylsulfone derivative are shown in Table 10.

For Compound Example A7, Compound Example A8, and Compound Example A9 having a two-photon excitation maximum wavelength and a two-photon absorption cross-section dialkylamino group, two-photon absorption is achieved by two-photon excitation of the two-photon absorbing material in the laser wavelength region. We were able to estimate the maximum wavelength. These two-photon absorption cross sections were sufficiently larger than the two-photon absorption cross sections at the two-photon absorption maximum wavelength of fluorescein, which is a standard substance.

  Compound Example A1, Compound Example A2, Compound Example A3, Compound Example A5, Compound Example A6, Compound Example A16, Compound Example A19, Compound Example A20, Compound Example which are unsubstituted or have an alkyl group, an alkoxy group or an alkylthio group With regard to A18, Compound Example A17, Compound Example A11, Compound Example A12, and Compound Example A21, the one-photon absorption band was at a short wavelength, and thus the two-photon absorption maximum wavelength could not be estimated in the excitation laser wavelength region. However, the two-photon absorption cross section near 700 nm was equal to or greater than the two-photon absorption cross section of fluorescein at the two-photon absorption maximum wavelength.

  The results of the two-photon excitation maximum wavelength and the two-photon absorption cross-section of the homodisubstituted diphenylsulfone derivative are 11, and the results of the two-photon excitation maximum wavelength and the two-photon absorption cross-section of the heterodisubstituted diphenylsulfone derivative are shown in Table 12. Table 13 shows the results of the two-photon excitation maximum wavelength and the two-photon absorption cross section of the monosubstituted diphenylsulfone derivative.

  In a homodisubstituted diphenylsulfone derivative, in a compound to which a dialkylamino group was added, a substituent having a carbon number of C2 or more had a larger two-photon absorption cross section than C1. In the compound provided with an alkoxy group, C4 had a larger two-photon absorption cross-sectional area than C1, but C8 had the same degree as C1. In the alkylthio group, C2 was smaller than C1.

  Since the two-photon absorbing material according to the present invention has a high two-photon absorption cross section, it is suitable for a photocurable resin composition, a light emitting material, an optical recording material, a fluorescent dye material for a microscope, a light limiting material, and the like. Can be used.

Claims (13)

A two-photon absorbing material containing a diphenylsulfone derivative represented by the following formula (1).

[Wherein m represents 1 or 2, n represents 1 or 2,
R ^{1 to} R ⁵ and R ^{6 to} R ¹⁰ may be the same or different and each is a hydrogen atom, a halogen atom, a hydroxyl group, an alkyl group, an alkoxyl group, an amino group, a monoalkylamino group, a dialkylamino group, or an alkylthio group. , Phenyl group, —NHCOR ^′ (wherein R ′ represents an alkyl group), or R ¹ and R ² , R ² and R ³ , R ³ and R ⁴ , or R ⁴ and R ⁵ together May form a 5- to 7-membered condensed ring, and R ⁶ and R ⁷ , R ⁷ and R ⁸ , R ⁸ and R ⁹ , or R ⁹ and R ¹⁰ together form a 5- to 7-membered ring. The condensed ring may be formed. ] At least one of the substituents R ³ and R ⁸ is an alkyl group, an alkoxyl group, an amino group, a monoalkylamino group, a dialkylamino group, an alkylthio group, a phenyl group, —NHCOR ^′ (where R ′ represents an alkyl group) The two-photon absorbing material according to claim 1, which is an electron donating substituent selected from: The two-photon absorption property according to claim 1 or 2, wherein the substituents R ³ and R ⁸ are the same electron-donating substituent selected from an alkyl group, an alkoxyl group, a dialkylamino group, an alkylthio group, and a phenyl group. material. The two-photon absorbing material according to any one of claims 1 to 3, wherein at least one of the substituents R ³ and R ⁸ is a dialkylamino group. Wherein a substituent R ³ and R ⁸ are both dialkylamino group, two-photon absorption material according to claim 1.   The two-photon absorbing material according to any one of claims 1 to 5, wherein the alkyl group constituting the monoalkylamino group or dialkylamino group is an alkyl group having 2 to 6 carbon atoms. The two-photon absorbing material according to claim ¹ , wherein the substituents R ¹ , R ² , R ⁴ , R ⁵ and R ⁶ , R ⁷ , R ⁹ , R ¹⁰ are hydrogen. The two-photon absorbing material according to any one of claims 1 to 7, wherein the diphenylsulfone derivative has a molar extinction coefficient at a maximum wavelength at 250 to 800 nm of 55000 mol ^-1 dm ³ cm ^-1 or more.   The photocurable resin composition containing the two-photon absorptive material in any one of Claims 1-8.   The luminescent material containing the two-photon absorptive material in any one of Claims 1-8.   An optical recording material comprising the two-photon absorbing material according to claim 1.   A fluorescent dye material for a microscope, comprising the two-photon absorbing material according to claim 1.   The light limiting material containing the two-photon absorptive material in any one of Claims 1-8.

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