JP5162511B2 - Non-resonant two-photon absorption polymerization composition and three-dimensional optical recording medium using the same - Google Patents

Description

  The present invention relates to a material that exhibits a nonlinear optical effect, and particularly to an organic nonlinear optical material having a large non-resonant two-photon absorption cross-section and capable of three-dimensional refractive index modulation by photopolymerization caused by non-resonant two-photon absorption. The present invention relates to a two-photon absorption polymerizable composition.

  In general, the nonlinear optical effect is a non-linear optical response proportional to the square of the applied photoelectric field, the third power or more, and a second-order nonlinear optical effect proportional to the square of the applied photoelectric field. For example, second harmonic generation (SHG), optical rectification, photorefractive effect, Pockels effect, parametric amplification, parametric oscillation, optical sum frequency mixing, and optical difference frequency mixing are known. The third-order nonlinear optical effect proportional to the cube of the applied photoelectric field includes third harmonic generation (THG), optical Kerr effect, self-induced refractive index change, two-photon absorption, and the like.

  Many inorganic materials have been found so far as nonlinear optical materials exhibiting these nonlinear optical effects. However, inorganic materials are very difficult to put into practical use because so-called molecular design for optimizing desired nonlinear optical characteristics and various physical properties necessary for device fabrication is difficult. On the other hand, organic compounds can be optimized not only for the desired nonlinear optical properties by molecular design, but also for other physical properties, so they are highly practical and attract attention as promising nonlinear optical materials. Collecting.

  In recent years, the third-order nonlinear optical effect has attracted attention among the nonlinear optical characteristics of organic compounds, and among these, non-resonant two-photon absorption has attracted attention. Two-photon absorption is a phenomenon in which a compound is excited by simultaneously absorbing two photons, and the case where two-photon absorption occurs in an energy region where there is no (linear) absorption band of the compound is called non-resonant two-photon absorption. . In the following description, two-photon absorption refers to non-resonant two-photon absorption even if not specified.

By the way, the efficiency of non-resonant two-photon absorption is proportional to the square of the applied photoelectric field (square characteristic of two-photon absorption). For this reason, when a two-dimensional plane is irradiated with a laser, two-photon absorption occurs only at a position where the electric field strength is high in the central portion of the laser spot, and two-photon absorption is completely absent in a portion where the electric field strength is weak in the peripheral portion. Does not happen. On the other hand, in the three-dimensional space, two-photon absorption occurs only in the region where the electric field strength at the focal point where the laser light is collected by the lens is large, and no two-photon absorption occurs in the region outside the focal point because the electric field strength is weak. . Compared with linear absorption where excitation occurs at all positions in proportion to the intensity of the applied photoelectric field, non-resonant two-photon absorption results in excitation at only one point inside the space due to this square characteristic. , The spatial resolution is significantly improved.
Usually, when inducing non-resonant two-photon absorption, a short-pulse laser in the near-infrared region, which is longer than the wavelength region in which the (linear) absorption band of the compound exists and does not have absorption, is often used. The so-called transparent near-infrared light is used, so that the excitation light can reach the inside of the sample without being absorbed or scattered, and because of the square characteristic of non-resonant two-photon absorption, one point inside the sample has an extremely high spatial resolution. Can be excited.
Accordingly, if polymerization can be caused by using excitation energy obtained by non-resonant two-photon absorption, polymerization can be caused in an arbitrary place in a three-dimensional space, and a three-dimensional optical recording medium considered as an ultimate high-density recording medium, Application to fine three-dimensional stereolithography materials is also possible.

  An example in which two-photon photopolymerization is performed using a non-resonant two-photon absorption compound and applied to optical modeling and the like is described in the following literature (BH Cumpston et al., Nature. 1999, Vol. 398, 51 (Non-Patent Document 1)), K.K. D. Belfield et al. , J .; Phys. Org. Chem. 2000, 13: 837 [Non-Patent Document 2], C.I. Li et al. , Chem. Phys. Lett. 2001, 340, 444 [Non-Patent Document 3], K.K. D. Belfield et al. , J .; Am. Chem. Soc. 2000, 122, 1217 [Non-Patent Document 4], S.A. Maruo et al. , Opt. Lett. 1997, Vol. 22, p. 132 [Non-Patent Document 5]

However, these examples have the following problems.
1) The two-photon absorption compound has a small two-photon absorption cross-section 2) Without using the two-photon absorption compound, the polymerization initiator having a very low two-photon absorption cross-section is directly absorbed by two photons 3) A polymerization initiator Not used 4) Even if a polymerization initiator is used, since the matching with the two-photon absorption compound is poor, a high-efficiency two-photon absorption compound and an appropriate polymerization initiator are not used, the polymerization efficiency is poor, In order to perform stereolithography by polymerization, a strong laser had to be irradiated for a long time, which was a practical problem.
In addition, these documents do not devise such that the refractive index of the photopolymerized composition is modulated by the polymerization part and the non-polymerization part by photopolymerization, and there is no such description.

On the other hand, optical information recording media (optical discs) capable of recording information only once by laser light are known, and write-once CDs (so-called CD-Rs) and write-once DVDs (so-called DVD-Rs). Etc. have been put to practical use.
For example, the typical structure of DVD-R is such that the guide groove (pre-groove) for tracking the irradiated laser beam is narrower than half of CD-R (0.74-0.8 μm). Further, a recording layer made of a dye is formed on a transparent disk-shaped substrate, and a light reflecting layer is usually formed on the recording layer, and a protective layer is further formed if necessary.
Information is recorded on the DVD-R by irradiating with visible laser light (usually in the range of 630 nm to 680 nm), and the irradiated portion of the recording layer absorbs the light and the temperature rises locally. A change (eg, pit generation) occurs and changes its optical properties. On the other hand, reading (reproduction) of information is also performed by irradiating laser light having the same wavelength as the recording laser light, and the part where the optical characteristics of the recording layer have changed (recorded part) and the part not changed (unrecorded) Information is reproduced by detecting the difference in reflectance from (part). This difference in reflectivity is based on so-called “refractive index modulation”. The greater the difference in refractive index between the recorded portion and the non-recorded portion, the greater the ratio of the reflectance of light, that is, the S / N ratio of reproduction. Larger and preferable.

Recently, networks such as the Internet and high-definition TV are rapidly spreading. In addition, HDTV (High Definition Television) will soon be broadcast, and there is an increasing demand for a large-capacity recording medium for easily and inexpensively recording image information of 50 GB or more for consumer use.
Furthermore, for business use such as computer backup use and broadcast backup use, an optical recording medium capable of recording large-capacity information of about 1 TB or more at high speed and at low cost is required.
Under such circumstances, a conventional two-dimensional optical recording medium such as a DVD-R is about 25 GB at most even if the recording / reproducing wavelength is shortened due to the physical principle, and is sufficiently large enough to meet future demands. It cannot be said that capacity can be expected.

Under such circumstances, a three-dimensional optical recording medium has attracted attention as an ultimate high-density, high-capacity recording medium. Three-dimensional optical recording media can be recorded in dozens or hundreds of layers in the three-dimensional (film thickness) direction, resulting in tens or hundreds of times the ultra-high density and ultra-high capacity recording of conventional two-dimensional recording media. That is what we are trying to achieve. In order to provide a three-dimensional optical recording medium, it is necessary to be able to access and write at an arbitrary place in the three-dimensional (film thickness) direction. As a means for this, a method using a two-photon absorption material and holography (interference) There is a method of using.
In a three-dimensional optical recording medium using a two-photon absorption material, so-called bit recording is possible over tens or hundreds of times based on the physical principle described above, and higher density recording is possible. It can be said that this is the ultimate high-density, high-capacity optical recording medium.
As a three-dimensional optical recording medium using a two-photon absorption material, a method of reading with fluorescence using a fluorescent substance for recording / reproduction (Lewitch, Eugene, Polis et al., Special Table 2001-524245 [Patent Document 1], Pavel, Eugen et al., JP 2000-512061 [Patent Document 2]), a method of reading by absorption or fluorescence using a photochromic compound (Korotif, Nikolai Ai et al., JP 2001-522119 [Patent Document 3], Arsenoff U. Ladimir et al., JP 2001-508221 [Patent Document 4]) and the like have been proposed, but none of the specific two-photon absorption materials are presented, and two-photons presented abstractly. Examples of absorbing compounds also use two-photon absorbing compounds with extremely low two-photon absorption efficiency. There are problems such as the S / N ratio of the reproduction, it can not be said to be a method of utility as an optical recording medium.
In particular, in terms of non-destructive reading, long-term storage stability of recording, etc., it is preferable to reproduce by changing the reflectance (refractive index) using an irreversible material. Specifically, a two-photon absorption material having such a function is specifically described. There were no disclosed examples.
In addition, Kawada Jun, Kawada Yoshimasa, JP-A-6-28672, Kawada Jun, Kawada Yoshimasa et al. And JP-A-6-118306 disclose a recording apparatus, a reproducing apparatus, and a reading method for three-dimensional recording by refractive index modulation. However, there is no specific description about the method using the two-photon absorption polymerizable composition.

JP-T-2001-524245 Special table 2000-512061 gazette Special table 2001-522119 gazette Special table 2001-508221 gazette JP-A-6-28672 JP-A-6-118306

B. H. Cumpston et al. , Nature. 1999, 398, 51 K. D. Belfield et al. , J .; Phys. Org. Chem. 2000, vol. 13, p. 837 C. Li et al. , Chem. Phys. Lett. 2001, 340, 444 K. D. Belfield et al. , J .; Am. Chem. Soc. 2000, 122, 1217 S. Maruo et al. , Opt. Lett. 1997, Vol. 22, p. 132

As described above, if polymerization is caused by using excitation energy obtained by non-resonant two-photon absorption, and as a result, the refractive index can be modulated between the laser focus portion and the non-focus portion, any place in the three-dimensional space can be used. In addition, refractive index modulation can be generated with extremely high spatial resolution, and application to a three-dimensional optical recording medium that is considered to be the ultimate high-density recording medium is also possible. Furthermore, since non-destructive readout is possible and the material is an irreversible material, it can be expected to have good storage stability and is practical.
However, currently available two-photon absorption compounds have low two-photon absorption ability and polymerization initiating ability, are poor in matching with the polymerization initiator, and have extremely low polymerization efficiency. Therefore, a very high-power laser is required as a light source, and a long recording time is required.
In particular, for use in a three-dimensional optical recording medium, it is essential to construct a two-photon absorption polymerizable composition that can be photopolymerized with high sensitivity in order to achieve a high transfer rate.
It is also essential to construct a material containing a two-photon absorption compound having a function of irreversibly achieving three-dimensional refractive index modulation.

  An object of the present invention is to provide a two-photon absorption polymerizable composition characterized in that three-dimensional refractive index modulation is possible by photopolymerization caused by non-resonant two-photon absorption, and the two-photon absorption is further provided. It is to provide a three-dimensional optical recording medium using a polymerizable composition.

As a result of intensive studies by the inventors, a material that absorbs two photons with high efficiency, that is, a material having a large two-photon absorption cross section, a polymerization initiator that can efficiently cause polymerization from its excitation energy, and a desired refraction We have found polymerizable compounds and binders that can cause rate modulation.
Therefore, the above object of the present invention has been achieved by the following means.

式中、Ｒ ^１ 、Ｒ ^２ 、Ｒ ^３ 、Ｒ ^４ はそれぞれ独立に、水素原子、または置換基を表し、Ｒ ^１ 、Ｒ ^２ 、Ｒ ^３ 、Ｒ ^４ のうちのいくつかが互いに結合して環を形成してもよい。ｎおよびｍはそれぞれ独立に０〜４の整数を表し、ｎおよびｍが２以上の場合、複数個のＲ ^１ 、Ｒ ^２ 、Ｒ ^３ およびＲ ^４ は同一でもそれぞれ異なってもよい。ただし、ｎ、ｍ同時に０となることはない。Ｘ ^１ およびＸ ^２ は独立に、アリール基、ヘテロ環基、または下記一般式（２）で表される基を表す。

式中、Ｒ ^５ は水素原子または置換基を表し、Ｒ ^６ は水素原子、アルキル基、アルケニル基、アリール基、ヘテロ環基を表し、Ｚ ^１ は５または６員環を形成する原子群を表す。
［２］
該シアニン色素が下記一般式（３）にて、メロシアニン色素が下記一般式（４）にて、オキソノール色素が一般式（５）にて表されることを特徴とする、［１］記載の非共鳴２光子吸収重合用性組成物。

一般式（３）〜（５）中、Ｚａ _１ 、Ｚａ _２ 及びＺａ _３ はそれぞれ５員または６員の含窒素複素環を形成する原子群を表わし、Ｚａ _４ 、Ｚａ _５ 及びＺａ _６ はそれぞれ５員または６員環を形成する原子群を表わす。Ｒａ _１ 、Ｒａ _２ 及びＲａ _３ はそれぞれ独立に、水素原子、アルキル基、アルケニル基、アリール基、ヘテロ環基を表す。
Ｍａ _１ 〜Ｍａ _１４ はそれぞれ独立にメチン基を表わし、置換基を有していても良く、他のメチン基と環を形成しても良い。ｎａ ^１ 、ｎａ ^２ 及びｎａ ^３ はそれぞれ０または１であり、ｋａ ^１ 、及びｋａ ^３ はそれぞれ０〜３の整数を表わす。ｋａ ^１ が２以上の時、複数のＭａ _３ 、Ｍａ _４ は同じでも異なってもよく、ｋａ ^３ が２以上の時、複数のＭａ _１２ 、Ｍａ _１３ は同じでも異なってもよい。ｋａ ^２ は０〜８の整数を表わし、ｋａ ^２ が２以上の時、複数のＭａ _１０ 、Ｍａ _１１ は同じでも異なってもよい。
ＣＩは電荷を中和するイオンを表わし、ｙは電荷の中和に必要な数を表わす。
［３］
該非共鳴２光子吸収重合用組成物において、重合性化合物とバインダーの屈折率が異なり、レーザー光を用いた非共鳴２光子吸収により起こる光重合によって、レーザー焦点部と非焦点部にて重合性化合物及びその重合反応物とバインダーとの組成比の不均一化が起こることにより、３次元的屈折率変調が可能なことを特徴とする［１］または［２］に記載の非共鳴２光子吸収重合用組成物。
［４］
該重合性化合物の少なくとも１つが沸点100℃以上の液体であることを特徴とする、［１］〜［３］のいずれか一項に記載の非共鳴２光子吸収重合用組成物。
［５］
該バインダーが該重合性化合物より低屈折率であり、バインダーがセルロースエステル、ポリビニルアルコール、ポリビニルアセテート、ポリビニルブチラール、ポリビニルホルマールおよびフッ素を含む高分子から選ばれる少なくとも１つのポリマーであることを特徴とする、［１］〜［４］のいずれか一項に記載の非共鳴２光子吸収重合用組成物。
［６］
前記重合開始剤が少なくとも１種のラジカルを発生する重合開始剤を含み、重合性化合物が少なくとも１種のラジカルにより重合するラジカル重合性化合物を含むことを特徴とする［１］〜［５］のいずれか一項に記載の非共鳴２光子吸収重合用組成物。
［７］
該重合開始剤が少なくとも１種の酸を発生する重合開始剤を含み、重合性化合物が少なくとも１種の酸により重合するカチオン重合性化合物を含むことを特徴とする［１］〜［６］のいずれか一項に記載の非共鳴２光子吸収重合用組成物。
［８］
［１］〜［７］のいずれか一項に記載の非共鳴２光子吸収重合用組成物を含むことを特徴とする３次元光記録媒体。
なお、本発明は上記［１］〜［８］に関するものであるが、参考のためその他の事項（例えば下記の事項）についても記載した。
（１） 少なくとも非共鳴２光子吸収化合物、重合開始剤、重合性化合物及びバインダーを有し、非共鳴２光子吸収により起こる光重合により３次元的屈折率変調が可能であることを特徴とする非共鳴２光子吸収重合用組成物。
但し、該非共鳴２光子吸収化合物がシアニン色素、メロシアニン色素、オキソノール色素、フタロシアニン色素または下記一般式（１）にて表される化合物である。 [1]
A non-resonant two-photon having at least a non-resonant two-photon absorption compound, a polymerization initiator, a polymerizable compound and a binder, and capable of three-dimensional refractive index modulation by photopolymerization caused by non-resonant two-photon absorption Composition for absorption polymerization.
However, the non-resonant two-photon absorption compound is a cyanine dye, a merocyanine dye, an oxonol dye, a phthalocyanine dye or a compound represented by the following general formula (1), and the polymerizable compound contains at least one aryl group, aromatic A heterocyclic group, a chlorine atom, a bromine atom, an iodine atom, or a sulfur atom, and the binder does not contain them.

In the formula, each of R ¹ , R ² , R ³ and R ⁴ independently represents a hydrogen atom or a substituent, and some of R ¹ , R ² , R ³ and R ⁴ are bonded to each other to form a ring. May be formed. n and m each independently represent an integer of 0 to 4, and when n and m are 2 or more, a plurality of R ¹ , R ² , R ³ and R ⁴ may be the same or different. However, n and m are not 0 simultaneously. X ¹ and X ² independently represent an aryl group, a heterocyclic group, or a group represented by the following general formula (2).

In the formula, R ⁵ represents a hydrogen atom or a substituent, R ⁶ represents a hydrogen atom, an alkyl group, an alkenyl group, an aryl group, or a heterocyclic group, and Z ¹ represents an atomic group forming a 5- or 6-membered ring. .
[2]
The cyanine dye is represented by the following general formula (3), the merocyanine dye is represented by the following general formula (4), and the oxonol dye is represented by the general formula (5). Resonant two-photon absorption polymerization composition.

In the general formulas (3) to (5), Za ₁ , Za ₂ and Za ₃ each represent an atomic group forming a 5-membered or 6-membered nitrogen-containing heterocycle, and Za ₄ , Za ₅ and Za ₆ are each 5 A group of atoms forming a member or six-membered ring is represented. Ra ₁ , Ra ₂ and Ra ₃ each independently represent a hydrogen atom, an alkyl group, an alkenyl group, an aryl group or a heterocyclic group.
Ma ₁ to Ma ₁₄ each independently represent a methine group which may have a substituent, may be formed with other methine groups and rings. na ¹ , na ² and na ³ are each 0 or 1, and ka ¹ and ka ³ each represent an integer of 0 to 3. When ka ¹ is 2 or more, the plurality of Ma ₃ and Ma ₄ may be the same or different, and when ka ³ is 2 or more, the plurality of Ma ₁₂ and Ma ₁₃ may be the same or different. ka ² represents an integer of 0 to 8, and when ka ² is 2 or more, a plurality of Ma ₁₀ and Ma ₁₁ may be the same or different.
CI represents an ion for neutralizing the electric charge, and y represents a number necessary for neutralizing the electric charge.
[3]
In the composition for non-resonant two-photon absorption polymerization, the polymerizable compound and the binder have different refractive indexes, and the polymerizable compound in the laser focal part and the non-focus part by photopolymerization caused by non-resonant two-photon absorption using laser light. And non-resonant two-photon absorption polymerization according to [1] or [2], wherein the composition ratio between the polymerization reaction product and the binder is non-uniform, thereby enabling three-dimensional refractive index modulation. Composition.
[4]
The composition for nonresonant two-photon absorption polymerization according to any one of [1] to [3], wherein at least one of the polymerizable compounds is a liquid having a boiling point of 100 ° C. or higher.
[5]
The binder has a lower refractive index than the polymerizable compound, and the binder is at least one polymer selected from polymers containing cellulose ester, polyvinyl alcohol, polyvinyl acetate, polyvinyl butyral, polyvinyl formal, and fluorine. The composition for non-resonant two-photon absorption polymerization according to any one of [1] to [4].
[6]
[1] to [5], wherein the polymerization initiator includes a polymerization initiator that generates at least one radical, and the polymerizable compound includes a radical polymerizable compound that is polymerized by at least one radical. The composition for non-resonant two-photon absorption polymerization according to any one of the above.
[7]
[1] to [6], wherein the polymerization initiator includes a polymerization initiator that generates at least one acid, and the polymerizable compound includes a cationic polymerizable compound that is polymerized by at least one acid. The composition for non-resonant two-photon absorption polymerization according to any one of the above.
[8]
[3] A three-dimensional optical recording medium comprising the composition for nonresonant two-photon absorption polymerization according to any one of [1] to [7].
In addition, although this invention is related to said [1]-[8], the other matter (for example, the following matter) was also described for reference.
(1) It has at least a non-resonant two-photon absorption compound, a polymerization initiator, a polymerizable compound, and a binder, and is capable of three-dimensional refractive index modulation by photopolymerization caused by non-resonant two-photon absorption. A composition for resonance two-photon absorption polymerization.
However, the non-resonant two-photon absorption compound is a cyanine dye, a merocyanine dye, an oxonol dye, a phthalocyanine dye, or a compound represented by the following general formula (1).

In the formula, each of R ¹ , R ² , R ³ and R ⁴ independently represents a hydrogen atom or a substituent, and some of R ¹ , R ² , R ³ and R ⁴ are bonded to each other to form a ring. May be formed. n and m each independently represent an integer of 0 to 4, and when n and m are 2 or more, a plurality of R ¹ , R ² , R ³ and R ⁴ may be the same or different. However, n and m are not 0 simultaneously. X ¹ and X ² independently represent an aryl group, a heterocyclic group, or a group represented by General Formula (2).
General formula (2)

In the formula, R ⁵ represents a hydrogen atom or a substituent, R ⁶ represents a hydrogen atom, an alkyl group, an alkenyl group, an aryl group, or a heterocyclic group, and Z ¹ represents an atomic group forming a 5- or 6-membered ring. Represent.
(2) In the compound represented by the general formula (1), linked by R ¹ and R ³ and forming a ring (1) non-resonant two-photon absorption polymerizable composition according.
(3) In the compound represented by the general formula (1), linked by R ¹ and R ^3, and forming a cyclopentanone ring together with the carbonyl group (2) non-resonant two-photon absorption according polymerizable composition.
( 4 ) The non-resonant according to any one of ( 1 ) to ( 3 ), wherein X ¹ and X ² of the compound represented by the general formula (1) are represented by the general formula (2) A composition for non-resonant two-photon absorption polymerization capable of three-dimensional refractive index modulation by photopolymerization caused by two-photon absorption.
( 5 ) In the compound represented by the general formula (1), X ¹ and X ² are represented by the general formula (2), R ⁶ is an alkyl group, and the ring formed by Z ¹ is an indolenine ring , Azaindolenin ring, pyrazoline ring, benzothiazole ring, thiazole ring, thiazoline ring, benzoxazole ring, oxazole ring, oxazoline ring, benzimidazole ring, thiadiazole ring, quinoline ring ( 4 ) The composition for non-resonant two-photon absorption polymerization according to ( 4 ).
( 6 ) In the compound represented by the general formula (1), X ¹ and X ² are represented by the general formula (2), R ⁶ is an alkyl group, and the ring formed by Z ¹ is an indolenine ring The composition for non-resonant two-photon absorption polymerization according to ( 5 ), which is represented by any one of: azaindolenin ring, benzothiazole ring, benzoxazole ring, and benzimidazole ring.
( 7 ) In ( 1 ), the cyanine dye is represented by the following general formula (3), the merocyanine dye is represented by the following general formula (4), and the oxonol dye is represented by the general formula (5). The composition for non-resonant two-photon absorption polymerization according to ( 1 ).

In the general formulas (3) to (5), Za ₁ , Za ₂ and Za ₃ each represent an atomic group forming a 5-membered or 6-membered nitrogen-containing heterocycle, and Za ₄ , Za ₅ and Za ₆ are each 5 A group of atoms forming a member or six-membered ring is represented. Ra ₁ , Ra ₂ and Ra ₃ each independently represent a hydrogen atom, an alkyl group, an alkenyl group, an aryl group or a heterocyclic group.
Ma _{1 to} Ma ₁₄ each independently represent a methine group, may have a substituent, and may form a ring with another methine group. na ¹ , na ² and na ³ are each 0 or 1, and ka ¹ and ka ³ each represent an integer of 0 to 3. When ka ¹ is 2 or more, the plurality of Ma ₃ and Ma ₄ may be the same or different, and when ka ³ is 2 or more, the plurality of Ma ₁₂ and Ma ₁₃ may be the same or different. ka ² represents an integer of 0 to 8, and when ka ² is 2 or more, a plurality of Ma ₁₀ and Ma ₁₁ may be the same or different.
CI represents an ion for neutralizing the electric charge, and y represents a number necessary for neutralizing the electric charge.
(8) In the composition for non-resonant two-photon absorption polymerization, the polymerizable compound and the binder have different refractive indexes, and the photopolymerization caused by non-resonant two-photon absorption causes a polymerizable compound and its The composition for non-resonant two-photon absorption polymerization according to any one of (1) to (7), wherein three-dimensional refractive index modulation is possible due to non-uniform composition ratio of the polymerization reaction product and the binder .
(9) Either the polymerizable compound or the binder contains at least one aryl group, aromatic heterocyclic group, chlorine atom, bromine atom, iodine atom, or sulfur atom, and the other one contains them. The composition for nonresonant two-photon absorption polymerization according to any one of (1) to (8), which is not contained.
(10) The polymerizable compound contains at least one aryl group, aromatic heterocyclic group, chlorine atom, bromine atom, iodine atom, or sulfur atom, and the binder does not contain them.
(9) The composition for nonresonant two-photon absorption polymerization according to (9).
(11) The composition for non-resonant two-photon absorption polymerization according to any one of (1) to (10), wherein at least one of the polymerizable compounds is a liquid having a boiling point of 100 ° C. or higher.
(12) The binder has a lower refractive index than the polymerizable compound, and the binder contains a polymer containing cellulose ester, polyvinyl alcohol, polyvinyl acetate, polyvinyl butyral, polyvinyl formal, or fluorine, (1) The composition for nonresonant two-photon absorption polymerization according to any one of to (11).
(13) The polymerizable compound contains at least one aryl group, aromatic heterocyclic group, chlorine atom, bromine atom, iodine atom, or sulfur atom, the binder has a lower refractive index than the polymerizable compound, and the binder Comprising a polymer containing cellulose ester, polyvinyl alcohol, polyvinyl acetate, polyvinyl butyral, polyvinyl formal, or fluorine, characterized by three-dimensional refractive index modulation by photopolymerization caused by non-resonant two-photon absorption according to (12) A composition for non-resonant two-photon absorption polymerization.
(14) The non-resonant two-photon absorption polymerizable composition according to any one of the non-resonant two-photon absorption compound is characterized by having at least one hydrogen bonding group (1) to (13).
( 15 ) The non-resonant capable of three-dimensional refractive index modulation by photopolymerization caused by non-resonant two-photon absorption according to ( 14 ), wherein the hydrogen bonding group is a —COOH group or a —CONH ₂ group A composition for two-photon absorption polymerization.
( 16 ) The polymerization initiator is 1) a ketone polymerization initiator, 2) an organic peroxide polymerization initiator, 3) a bisimidazole polymerization initiator, 4) a trihalomethyl-substituted triazine polymerization initiator, and 5) a diazonium. Salt-based polymerization initiator, 6) diaryl iodonium salt-based polymerization initiator, 7) sulfonium salt-based polymerization initiator, 8) triphenylalkyl borate-based polymerization initiator, 9) diaryl iodonium organic boron complex-based polymerization initiator, 10) sulfonium organic boron complex polymerization initiator, 11) cationic two-photon absorption compound organic boron complex polymerization initiator, 12) anionic two-photon absorption compound onium salt complex polymerization initiator, 13) metal arene complex polymerization initiator, 14) sulfonic acid ester-based polymerization initiator, in either, characterized in that either (1) to (15) Non-resonant two-photon absorption polymerizable composition for the mounting.
( 17 ) The polymerization initiator is 1) a ketone polymerization initiator, 3) a bisimidazole polymerization initiator, 4) a trihalomethyl-substituted triazine polymerization initiator, 6) a diaryliodonium salt polymerization initiator, 7) a sulfonium salt. ( 16 ) a polymerization initiator, 11) a cationic two-photon absorption compound, an organic boron complex polymerization initiator, and 12) an anionic two-photon absorption compound, an onium salt complex polymerization initiator. A composition for non-resonant two-photon absorption polymerization capable of three-dimensional refractive index modulation by photopolymerization caused by non-resonant two-photon absorption.
( 18 ) The polymerization initiator includes a polymerization initiator that generates at least one radical, and the polymerizable compound includes a radical polymerizable compound that is polymerized by at least one radical. The composition for nonresonant two-photon absorption polymerization according to any one of 17 ).
( 19 ) In ( 18 ), the radical polymerization initiator that generates at least one radical is 1) a ketone polymerization initiator, 2) an organic peroxide polymerization initiator, 3) a bisimidazole polymerization initiator, 4) Trihalomethyl-substituted triazine polymerization initiator, 5) Diazonium salt polymerization initiator, 6) Diaryliodonium salt polymerization initiator, 7) Sulfonium salt polymerization initiator, 8) Triphenylalkylborate polymerization initiator 9) Diaryliodonium organic boron complex polymerization initiator, 10) Sulfonium organic boron complex polymerization initiator, 11) Cationic two-photon absorption compound, organic boron complex polymerization initiator, 12) Anionic two-photon absorption compound, onium ( 18 ) Description: A salt complex polymerization initiator, or 13) a metal arene complex polymerization initiator, The composition for nonresonant two-photon absorption polymerization described in the above.
( 20 ) In ( 19 ), the radical polymerization initiator generating at least one radical is 1) a ketone polymerization initiator, 3) a bisimidazole polymerization initiator, 4) a trihalomethyl-substituted triazine polymerization initiator, 6) diaryliodonium salt polymerization initiator, 7) sulfonium salt polymerization initiator, 11) cationic two-photon absorption compound, organic boron complex polymerization initiator, 12) anionic two-photon absorption compound, onium salt complex polymerization initiator ( 19 ) The composition for nonresonant two-photon absorption polymerization capable of three-dimensional refractive index modulation by photopolymerization caused by nonresonant two-photon absorption according to ( 19 ).
( 21 ) In ( 19 ), the radical polymerization initiator that generates at least one radical is 3) a bisimidazole polymerization initiator, 6) a diaryliodonium salt polymerization initiator, 7) a sulfonium salt polymerization initiator, The non-resonant 2 according to ( 19 ), which is any one of 11) a cationic two-photon absorption compound, an organic boron complex-based polymerization initiator, and 12) an anionic two-photon absorption compound, an onium salt complex-based polymerization initiator. A composition for non-resonant two-photon absorption polymerization capable of three-dimensional refractive index modulation by photopolymerization caused by photon absorption.
( 22 ) The polymerization initiator includes a polymerization initiator that generates at least one acid, and the polymerizable compound includes a cationic polymerizable compound that is polymerized with at least one acid. (17) The composition for nonresonant two-photon absorption polymerization according to any one of (17).
( 23 ) In ( 22 ), the radical polymerization initiator that generates at least one acid is 4) a trihalomethyl-substituted triazine polymerization initiator, 5) a diazonium salt polymerization initiator, or 6) a diaryl iodonium salt polymerization. The nonresonant two-photon according to ( 22 ), which is any one of an initiator, 7) a sulfonium salt polymerization initiator, 13) a metal arene complex polymerization initiator, and 14) a sulfonate ester polymerization initiator. A composition for non-resonant two-photon absorption polymerization capable of three-dimensional refractive index modulation by photopolymerization caused by absorption.
( 24 ) In ( 22 ), the radical polymerization initiator that generates at least one radical and an acid is either 6) a diaryliodonium salt polymerization initiator or 7) a sulfonium salt polymerization initiator. ( 22 ) The composition for nonresonant two-photon absorption polymerization capable of three-dimensional refractive index modulation by photopolymerization caused by nonresonant two-photon absorption.
(25) at least, non-resonant two-photon absorption compound, a polymerizable compound, a binder, non-resonant two-photon, wherein the non-resonance by photopolymerization caused by two-photon absorption is possible three-dimensional refractive index modulation absorbent polymerization composition.
( 26 ) In ( 25 ), the non-resonant two-photon absorption compound is represented by the cyanine dye represented by the general formula (4), the merocyanine dye represented by the general formula (4), and the general formula (5). The composition for non-resonant two-photon absorption polymerization according to ( 25 ) , wherein the composition is any one of the following compounds:
( 27 ) The composition for nonresonant two-photon absorption polymerization according to any one of (1) to ( 26 ), wherein the amount of refractive index modulation to be formed is 0.005 or more.
( 28 ) A three-dimensional optical recording medium comprising the composition for nonresonant two-photon absorption polymerization according to any one of (1) to ( 27 ).

  It can be seen that by using the two-photon absorption polymerizable composition of the present invention, the refractive index at the laser focus portion and the non-focus portion can be three-dimensionally modulated.

The composition for nonresonant two-photon absorption polymerization , which is capable of three-dimensional refractive index modulation by photopolymerization caused by nonresonant two-photon absorption of the present invention, will be described in detail below.
The composition for non-resonant two-photon absorption polymerization of the present invention has at least a non-resonant two-photon absorption compound, a polymerization initiator, a polymerizable compound, and a binder, and is three-dimensional by photopolymerization caused by non-resonant two-photon absorption. Refractive index modulation is possible, and the non-resonant two-photon absorption compound is a cyanine dye, merocyanine dye, oxonol dye, phthalocyanine dye, or a compound represented by the above general formula (1). Other matters are also described for reference for understanding the present invention.

The two-photon absorption polymerizable composition of the present invention includes a two-photon absorption compound, a radical or cationic polymerization initiator that generates radicals or acids using its excitation energy, a polymerizable compound that polymerizes by radicals or cations, and a polymer compound. If necessary, additives such as a chain transfer agent, a heat stabilizer, a plasticizer, and a solvent are used.
In the two-photon absorption polymerization composition of the present invention, the polymerizable compound and the binder preferably have different refractive indexes. As a result, the photopolymerization caused by non-resonant two-photon absorption causes non-uniformity in the composition ratio of the polymerizable compound and its polymerization reaction product and the binder in the laser focal portion and non-focal portion, and three-dimensional refractive index modulation. Is possible.
The formed refractive index modulation is preferably greater than 0.005, more preferably greater than 0.01, and even more preferably greater than 0.05.
The difference in the refractive index between the polymerizable compound and the binder may be either the refractive index of the polymerizable compound is larger or the refractive index of the binder is larger, but the polymerizable compound is more binder. It is more preferable that the refractive index is larger than that.

First, the two-photon absorption compound in the two-photon absorption polymerizable composition of the present invention will be described.
The two-photon absorption compound of the present invention is a compound that performs non-resonant two-photon absorption (a phenomenon in which two photons are simultaneously excited in an energy region where no (linear) absorption band of the compound exists).

The two-photon absorption compound of the present invention is preferably an organic compound.
In the present invention, when a specific portion is referred to as a “group”, unless otherwise specified, it may be substituted with one or more (up to the maximum possible) substituents. It means that it is not necessary. For example, “alkyl group” means a substituted or unsubstituted alkyl group. Moreover, the substituent which can be used for the compound in the present invention may be any substituent regardless of the presence or absence of substitution.
In the present invention, when a specific moiety is referred to as “ring”, or when “group” includes “ring”, it may be monocyclic or condensed unless otherwise specified. May not be substituted.
For example, the “aryl group” may be a phenyl group, a naphthyl group, or a substituted phenyl group.

The two-photon absorption compound of the present invention is more preferably a dye. In addition, a pigment | dye here is a general term with respect to the compound which has a part of absorption in visible region (400-700 nm) or near-infrared region (700-2000 nm).
Any dye may be used as the dye in the present invention. , Allopolar dye, oxonol dye, hemioxonol dye, squalium dye, croconium dye, azamethine dye, coumarin dye, arylidene dye, anthraquinone dye, triphenylmethane dye, xanthene dye, azo dye, azomethine dye, spiro compound, metallocene dye, Fluorenone dye, fulgide dye, perylene dye, phenazine dye, phenothiazine dye, quinone dye, indigo dye, diphenylmethane dye, polyene color , Acridine dyes, acridinone dyes, diphenylamine dyes, quinacridone dyes, quinophthalone dyes, phenoxazine dyes, phthaloperylene dyes, porphyrin dyes, chlorophyll dyes, phthalocyanine dyes or metal complex dyes.

  Preferably, cyanine dye, hemicyanine dye, streptocyanine dye, styryl dye, merocyanine dye, trinuclear merocyanine dye, tetranuclear merocyanine dye, rhodacyanine dye, oxonol dye, squalium dye, arylidene dye, triphenylmethane dye, xanthene dye, azo Dyes, porphyrin dyes, phthalocyanine dyes, or metal complex dyes, more preferably cyanine dyes, hemicyanine dyes, streptocyanine dyes, styryl dyes, merocyanine dyes, trinuclear merocyanine dyes, quadruple merocyanine dyes, rhodacyanine dyes, oxonol dyes , Squalium dyes, arylidene dyes, methine dyes, phthalocyanine dyes, azo dyes, and more preferably cyanine dyes, merocyanine dyes, or orange dyes. It is a Sonoru dye.

  For more information on these dyes, see FMHarmer, “Heterocyclic Compounds-Cyanine Dyes and Related Compounds”, John Willie &・ John Wiley & Sons-New York, London, 1964, DMSturmer, "Heterocyclic Compounds-Special Topics in Heterocyclic Compounds-Special topics in repeating chemistry), Chapter 18, Section 14, 482-515, John Wiley & Sons-New York, London, 1977, "Rods Chemistry of Carbon Compounds (Rodd's Chemistry of Carbon Compounds), 2nd.Ed vol. IV, part B, 1977, Chapter 15, pages 369 to 422, published by Elsevier Science Publishing Company Inc., New York, and the like.

  Specific examples of the cyanine dye, merocyanine dye, or oxonol dye include those described in F.M. Harmer, Heterocyclic Compounds-Cyanine Dyes and Related Compounds, John & Wiley & Sons, New York, London, 1964.

  The general formulas of cyanine dye and merocyanine dye are those shown in (XI) and (XII) on pages 21 and 22 of US Pat. No. 5,340,694 (however, the number of n12 and n15 is not limited and is an integer of 0 or more) (Preferably an integer of 0 to 4)).

  When the two-photon absorption compound of the present invention is a cyanine dye, it is preferably represented by the general formula (3).

In the general formula (3), Za ₁ and Za ₂ each represent an atomic group forming a 5-membered or 6-membered nitrogen-containing heterocycle. The 5-membered or 6-membered nitrogen-containing heterocycle formed is preferably an oxazole nucleus having 3 to 25 carbon atoms (hereinafter referred to as C number) (for example, 2-3-methyloxazolyl, 2-3-ethyloxazolyl). , 2-3,4-diethyloxazolyl, 2-3-methylbenzoxazolyl, 2-3-ethylbenzoxazolyl, 2-3-sulfoethylbenzoxazolyl, 2-3-sulfopropyl Benzoxazolyl, 2-3-methylthioethylbenzoxazolyl, 2-3-methoxyethylbenzoxazolyl, 2-3-sulfobutylbenzoxazolyl, 2-3-methyl-β-naphthoxazolyl 2-3-methyl-α-naphthoxazolyl, 2-3-sulfopropyl-β-naphthoxazolyl, 2-3-sulfopropyl-β-naphthoxazolyl, 2-3- ( -Naphthoxyethyl) benzoxazolyl, 2-3,5-dimethylbenzoxazolyl, 2-6-chloro-3-methylbenzoxazolyl, 2-5-bromo-3-methylbenzoxazolyl, 2- 3-ethyl-5-methoxybenzoxazolyl, 2-5-phenyl-3-sulfopropylbenzoxazolyl, 2-5- (4-bromophenyl) -3-sulfobutylbenzoxazolyl, 2-3 -Dimethyl-5,6-dimethylthiobenzoxazolyl), thiazole nuclei having 3 to 25 carbon atoms (for example, 2-methylthiazolyl, 2-3-ethylthiazolyl, 2-3-sulfopropylthiazolyl, 2- 3-sulfobutylthiazolyl, 2-3,4-dimethylthiazolyl, 2-3,4,4-trimethylthiazolyl, 2-3-carboxyethylthiazolyl, 2 -3-methylbenzothiazolyl, 2-3-ethylbenzothiazolyl, 2-3-butylbenzothiazolyl, 2-3-sulfopropylbenzothiazolyl, 2-3-sulfobutylbenzothiazolyl , 2-3-methyl-β-naphthothiazolyl, 2-3-sulfopropyl-γ-naphthothiazolyl, 2-3- (1-naphthoxyethyl) benzothiazolyl, 2-3,5-dimethylbenzothiazolyl, 2-6-chloro -3-methylbenzothiazolyl, 2-6-iodo-3-ethylbenzothiazolyl, 2-5-bromo-3-methylbenzothiazolyl, 2-3-ethyl-5-methoxybenzothiazolyl 2-5-phenyl-3-sulfopropylbenzothiazolyl, 2-5- (4-bromophenyl) -3-sulfobutylbenzothiazolyl, 2-3-dimethyl-5,6- Dimethylthiobenzothiazolyl), imidazole nucleus having 3 to 25 carbon atoms (for example, 2-1,3-diethylimidazolyl, 2-1,3-dimethylimidazolyl, 2-1-methylbenzimidazolyl, 2- 1,3,4-triethylimidazolyl, 2-1,3-diethylbenzimidazolyl, 2-1,3,5-trimethylbenzimidazolyl, 2-6-chloro-1,3-dimethylbenzimidazolyl, 2-5,6-dichloro- 1,3-diethylbenzimidazolyl, 2-1,3-disulfopropyl-5-cyano-6-chlorobenzimidazolyl, etc.), C10-30 indolenine nucleus (for example, 3,3-dimethylindolenine) ), A quinoline nucleus having 9 to 25 carbon atoms (for example, 2-1-methylquinolyl, 2-1-ethylquinolyl) 2-1-methyl 6-chloroquinolyl, 2-1,3-diethylquinolyl, 2-1-methyl-6-methylthioquinolyl, 2-1-sulfopropylquinolyl, 4-1-methylquinolyl, 4-1 And sulfoethylquinolyl, 4-1-methyl-7-chloroquinolyl, 4-1,8-diethylquinolyl, 4-1-methyl-6-methylthioquinolyl, 4-1-sulfopropylquinolyl, etc.) , A C 3-25 selenazole nucleus (for example, 2-3methylbenzoselenazolyl etc.), a C 5-25 pyridine nucleus (for example, 2-pyridyl etc.) and the like can be mentioned. In addition, thiazoline nucleus, oxazoline nucleus, selenazoline nucleus, tellurazoline nucleus, tellurazole nucleus, benzotelrazole nucleus, imidazoline nucleus, imidazo [4,5-quino Zarin] nucleus, an oxadiazole nucleus, a thiadiazole nucleus, a tetrazole nucleus, may be mentioned pyrimidine nucleus.

  These may be substituted, and the substituent is preferably, for example, an alkyl group (preferably an alkyl group having 1 to 20 carbon atoms, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, n-pentyl, benzyl, 3- Sulfopropyl, 4-sulfobutyl, carboxymethyl, 5-carboxypentyl), alkenyl group (preferably having 2 to 20 carbon atoms, such as vinyl, allyl, 2-butenyl, 1,3-butadienyl), cycloalkyl group (preferably C 3-20, for example cyclopentyl, cyclohexyl), aryl groups (preferably C 6-20, for example phenyl, 2-chlorophenyl, 4-methoxyphenyl, 3-methylphenyl, 1-naphthyl), heterocyclic groups ( Preferably C number 1-20, for example pyridyl, thienyl, furyl, thiazolyl, imida Lyl, pyrazolyl, pyrrolidino, piperidino, morpholino), alkynyl group (preferably having 2 to 20 carbon atoms, such as ethynyl, 2-propynyl, 1,3-butadiynyl, 2-phenylethynyl), halogen atom (for example, F, Cl Br, I), amino group (preferably C 0-20, for example, amino, dimethylamino, diethylamino, dibutylamino, anilino), cyano group, nitro group, hydroxyl group, mercapto group, carboxyl group, sulfo group, Phosphonic acid group, acyl group (preferably C 1-20, such as acetyl, benzoyl, salicyloyl, pivaloyl), alkoxy group (preferably C 1-20, such as methoxy, butoxy, cyclohexyloxy), aryloxy group (Preferably C number 6-26, for example, phenoxy, 1 Naphthoxy), alkylthio group (preferably C number 1-20, for example, methylthio, ethylthio), arylthio group (preferably C number 6-20, for example, phenylthio, 4-chlorophenylthio), alkylsulfonyl group (preferably C number) 1-20, such as methanesulfonyl, butanesulfonyl), arylsulfonyl groups (preferably C number 6-20, such as benzenesulfonyl, paratoluenesulfonyl), sulfamoyl groups (preferably C number 0-20, such as sulfamoyl, N-methylsulfamoyl, N-phenylsulfamoyl), carbamoyl group (preferably having 1 to 20 carbon atoms, for example, carbamoyl, N-methylcarbamoyl, N, N-dimethylcarbamoyl, N-phenylcarbamoyl), acylamino group (Preferably C number 1 -20, such as acetylamino, benzoylamino), imino group (preferably C 2-20, such as phthalimino), acyloxy group (preferably C 1-20, such as acetyloxy, benzoyloxy), alkoxycarbonyl group (preferably Is C 2-20, such as methoxycarbonyl, phenoxycarbonyl), carbamoylamino group (preferably C 1-20, such as carbamoylamino, N-methylcarbamoylamino, N-phenylcarbamoylamino), more preferably Is an alkyl group, aryl group, heterocyclic group, halogen atom, cyano group, carboxyl group, sulfo group, alkoxy group, sulfamoyl group, carbamoyl group, or alkoxycarbonyl group.

  These heterocycles may be further condensed. Preferred examples of the condensed ring include a benzene ring, a benzofuran ring, a pyridine ring, a pyrrole ring, an indole ring, and a thiophene ring.

More preferably, the 5- or 6-membered nitrogen-containing heterocyclic ring formed by Za ₁ and Za ₂ is an oxazole nucleus, an imidazole nucleus, a thiazole nucleus, or an indolenine ring, and more preferably an oxazole nucleus, an imidazole nucleus, or an indolenine ring. A ring, most preferably an oxazole nucleus.

Ra ₁ and Ra ₂ are each independently a hydrogen atom or an alkyl group (preferably having a C number of 1 to 20, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, n-pentyl, benzyl, 3-sulfopropyl. , 4-sulfobutyl, 3-methyl-3-sulfopropyl, 2′-sulfobenzyl, carboxymethyl, 5-carboxypentyl), alkenyl group (preferably having 2 to 20 carbon atoms, for example, vinyl, allyl), aryl group ( Preferably C number 6-20, for example, phenyl, 2-chlorophenyl, 4-methoxyphenyl, 3-methylphenyl, 1-naphthyl), heterocyclic group (preferably C number 1-20, for example, pyridyl, thienyl, furyl , Thiazolyl, imidazolyl, pyrazolyl, pyrrolidino, piperidino, morpholino), more preferably Alkyl group (preferably an alkyl group having a C number of 1 to 6) or a sulfoalkyl group (preferably 3-sulfopropyl, 4-sulfobutyl, 3-methyl-3-sulfopropyl, 2'-sulfobenzyl) is.

Ma _{1 to} Ma ₇ each represent a methine group and may have a substituent (examples of preferred substituents are the same as examples of substituents on Za ₁ and Za ₂ ), and the substituent is preferably an alkyl group , Halogen atom, nitro group, alkoxy group, aryl group, nitro group, heterocyclic group, aryloxy group, acylamino group, carbamoyl group, sulfo group, hydroxy group, carboxy group, alkylthio group, cyano group, etc. More preferably, it is an alkyl group.
Ma _{1 to} Ma ₇ are preferably unsubstituted methine groups or alkyl groups (preferably having a C number of 1 to 6) substituted methine groups, more preferably unsubstituted, ethyl group-substituted, or methyl group-substituted methine groups.
Ma _{1 to} Ma ₇ may be linked to each other to form a ring, and preferred examples of the ring formed include a cyclohexene ring, a cyclopentene ring, a benzene ring, and a thiophene ring.

na ¹ and na ² are 0 or 1, preferably 0.

ka ¹ represents an integer of 0 to 3, more preferably ka ¹ represents ¹ to 3, and further preferably ka ¹ represents 1 or 2.
When ka ¹ is 2 or more, the plurality of Ma ₃ and Ma ₄ may be the same or different.

  CI represents an ion for neutralizing the electric charge, and y represents a number necessary for neutralizing the electric charge.

  When the two-photon absorption compound of the present invention is a merocyanine dye, it is preferably represented by the general formula (4).

In the general formula (1), Za ₃ represents an atomic group forming a nitrogen-containing heterocyclic ring of 5- or _6-membered, is Za 1, Za ₂ synonymous (preferable examples _Za 1, Za ₂ and the same), These may be substituted (examples of preferred substituents are the same as examples of substituents on Za ₁ and Za ₂ ), and these heterocyclic rings may be further condensed.

More preferably, the 5- or 6-membered nitrogen-containing heterocyclic ring formed by Za ₃ is an oxazole nucleus, an imidazole nucleus, a thiazole nucleus, or an indolenine ring, and more preferably an oxazole nucleus or an indolenine ring.

Za ₄ represents an atomic group forming a 5-membered or 6-membered ring. The ring formed from Za ₄ is a moiety generally referred to as an acidic nucleus, and is defined by James, The Theory of the Photographic Process, 4th edition, McMillan, 1977, p. 198. Za ₄ is preferably 2-pyrazolone-5-one, pyrazolidine-3,5-dione, imidazolin-5-one, hydantoin, 2 or 4-thiohydantoin, 2-iminooxazolidine-4-one, 2-oxazoline- 5-one, 2-thiooxazoline-2,4-dione, isorhodanine, rhodanine, indan-1,3-dione, thiophen-3-one, thiophen-3-one-1,1-dioxide, indoline-2-one Indoline-3-one, 2-oxoindazolium, 5,7-dioxo-6,7-dihydrothiazolo [3,2-a] pyrimidine, 3,4-dihydroisoquinolin-4-one, 1,3 -Dioxane-4,6-dione, barbituric acid, 2-thiobarbituric acid, coumarin-2,4-dione, indazoline-2 One, pyrido [1,2-a] pyrimidine-1,3-dione, pyrazolo [1,5-b] quinazolone include nuclei such pyrazolopyridone.
More preferably, the ring formed from Za ₄ is 2-pyrazolone-5-one, pyrazolidine-3,5-dione, rhodanine, indan-1,3-dione, thiophen-3-one, thiophen-3-one- 1,1-dioxide, 1,3-dioxane-4,6-dione, barbituric acid, 2-thiobarbituric acid, coumarin-2,4-dione, more preferably pyrazolidine-3,5-dione, Indan-1,3-dione, 1,3-dioxane-4,6-dione, barbituric acid, 2-thiobarbituric acid, most preferably pyrazolidine-3,5-dione, barbituric acid, 2- Thiobarbituric acid.

The ring formed from Za ₄ may be substituted (preferred examples of the substituent are the same as those of the substituent on Za ₃ ). More preferably, the substituent is preferably an alkyl group, an aryl group, a heterocyclic group, a halogen. An atom, a cyano group, a carboxyl group, a sulfo group, an alkoxy group, a sulfamoyl group, a carbamoyl group, and an alkoxycarbonyl group.

  These heterocycles may be further condensed. Preferred examples of the condensed ring include a benzene ring, a benzofuran ring, a pyridine ring, a pyrrole ring, an indole ring, and a thiophene ring.

Ra ₃ is each independently a hydrogen atom, an alkyl group, an alkenyl group, an aryl group, or a heterocyclic group (preferred examples are the same as Ra ₁ and Ra ₂ ), more preferably an alkyl group (preferably having a C number of 1 to 1). 6 alkyl group) or a sulfoalkyl group (preferably 3-sulfopropyl, 4-sulfobutyl, 3-methyl-3-sulfopropyl, 2′-sulfobenzyl).

Ma _{8 to} Ma ₁₁ each represent a methine group and may have a substituent (examples of preferred substituents are the same as examples of substituents on Za ₁ and Za ₂ ), and the substituent is preferably an alkyl group , Halogen atom, nitro group, alkoxy group, aryl group, nitro group, heterocyclic group, aryloxy group, acylamino group, carbamoyl group, sulfo group, hydroxy group, carboxy group, alkylthio group, cyano group, etc. More preferably, it is an alkyl group.
Ma _{8 to} Ma ₁₁ are preferably unsubstituted methine groups or alkyl groups (preferably having a C number of 1 to 6) substituted methine groups, more preferably unsubstituted, ethyl group-substituted, and methyl group-substituted methine groups.
Ma _{8 to} Ma ₁₁ may be linked to each other to form a ring, and preferred examples of the ring formed include a cyclohexene ring, a cyclopentene ring, a benzene ring, and a thiophene ring.

na ³ is 0 or 1, preferably 0.

ka ² represents an integer of 0 to 8, preferably an integer of 0 to 4, more preferably an integer of 2 to 4.
When ka ² is 2 or more, the plurality of Ma ₁₀ and Ma ₁₁ may be the same or different.

  CI represents an ion for neutralizing the electric charge, and y represents a number necessary for neutralizing the electric charge.

  When the two-photon absorption compound of the present invention is an oxonol dye, it is preferably represented by the general formula (5).

In the general formula (5), Za ₅ and Za ₆ each represent an atomic group forming a 5-membered or 6-membered ring, and are synonymous with Za ₄ (preferred examples are also the same as Za ₄ ), and these may be substituted. Good (examples of preferred substituents are the same as examples of substituents on Za ₄ ), and these heterocycles may be further condensed.
More preferably, the ring formed from Za ₅ and Za ₆ is 2-pyrazolone-5-one, pyrazolidine-3,5-dione, rhodanine, indan-1,3-dione, thiophen-3-one, thiophene-3. -One-1,1-dioxide, 1,3-dioxane-4,6-dione, barbituric acid, 2-thiobarbituric acid, coumarin-2,4-dione, more preferably barbituric acid, 2- Thiobarbituric acid, most preferably barbituric acid.

Ma _{12 to} Ma ₁₄ each represents a methine group and may have a substituent (preferred examples of the substituent are the same as the examples of the substituents on Za ₅ and Za ₆ ), and preferably alkyl. Group, halogen atom, nitro group, alkoxy group, aryl group, nitro group, heterocyclic group, aryloxy group, acylamino group, carbamoyl group, sulfo group, hydroxy group, carboxy group, alkylthio group, cyano group, etc. More preferred are an alkyl group, a halogen atom, an alkoxy group, an aryl group, a heterocyclic group, a carbamoyl group and a carboxy group, and further preferred are an alkyl group, an aryl group and a heterocyclic group.
Ma _{12 to} Ma ₁₄ are preferably unsubstituted methine groups.
Ma _{12 to} Ma ₁₄ may be linked to each other to form a ring, and preferred examples of the ring formed include a cyclohexene ring, a cyclopentene ring, a benzene ring, and a thiophene ring.

ka ³ represents an integer of 0 to 3, preferably represents an integer of 0 to 2, more preferably represents 1 or 2, and most preferably represents 2.
When ka ³ is 2 or more, Ma ₁₂ and Ma ₁₃ may be the same or different.

  CI represents an ion for neutralizing the electric charge, and y represents a number necessary for neutralizing the electric charge.

  Moreover, it is also preferable that the compound of this invention is represented by General formula (1).

In the general formula (1), R ¹ , R ² , R ³ and R ⁴ each independently represent a hydrogen atom or a substituent, and the substituent is preferably an alkyl group (preferably having 1 to 20 carbon atoms, for example, Methyl, ethyl, n-propyl, isopropyl, n-butyl, n-pentyl, benzyl, 3-sulfopropyl, 4-sulfobutyl, 3-methyl-3-sulfopropyl, 2'-sulfobenzyl, carboxymethyl, 5-carboxy Pentyl), an alkenyl group (preferably C 2-20, such as vinyl, allyl), a cycloalkyl group (preferably C 3-20, such as cyclopentyl, cyclohexyl), an aryl group (preferably C 6-20, For example, phenyl, 2-chlorophenyl, 4-methoxyphenyl, 3-methylphenyl, 1-naphthyl), heterocyclic group Preferably having a C number of 1 to 20, for example, pyridyl, thienyl, furyl, thiazolyl, imidazolyl, pyrazolyl, pyrrolidino, piperidino, morpholino).
R ¹ , R ² , R ³ and R ⁴ are preferably a hydrogen atom or an alkyl group. Some (preferably two) of R ¹ , R ² , R ³ and R ⁴ may be bonded to each other to form a ring. In particular, R ¹ and R ³ are preferably bonded to form a ring, and the ring formed with the carbonyl carbon atom is preferably a 6-membered ring, a 5-membered ring or a 4-membered ring, and a 5-membered ring or A 4-membered ring is more preferable, and a 5-membered ring is most preferable.

In General formula (1), n and m represent the integer of 0-4 each independently, Preferably the integer of 1-4 is represented. However, n and m are not 0 simultaneously.
When n and m are 2 or more, a plurality of R ¹ , R ² , R ³ and R ⁴ may be the same or different.

X ¹ and X ² are independently an aryl group [preferably a C 6-20, preferably a substituted aryl group (for example, a substituted phenyl group, a substituted naphthyl group, a substituent of Ma ₁ to Ma ₇ preferably as an example of a substituent) And more preferably an alkyl group, an aryl group, a heterocyclic group, a halogen atom, an amino group, a hydroxyl group, an alkoxy group, an aryloxy group, an aryl group substituted with an acylamino group, and more preferably an alkyl group Represents an aryl group substituted with an amino group, a hydroxyl group, an alkoxy group or an acylamino group, and most preferably a phenyl group substituted with a dialkylamino group or a diarylamino group at the 4-position. At that time, a plurality of substituents may be linked to form a ring, and a preferred ring formed includes a julolidine ring. ], A heterocyclic group (preferably having 1 to 20 carbon atoms, preferably 3 to 8 membered ring, more preferably 5 or 6 membered ring such as pyridyl, thienyl, furyl, thiazolyl, imidazolyl, pyrazolyl, pyrrolyl, indolyl, carbazolyl, Phenothiazino, pyrrolidino, piperidino, morpholino, more preferably indolyl, carbazolyl, pyrrolyl, phenothiazino, the heterocycle may be substituted, and preferred substituents are the same as in the case of the aryl group), or the general formula (2) Represents a group represented by

In the general formula (2), R ⁵ represents a hydrogen atom or a substituent (preferred examples are the same as those of R ^{1 to} R ⁴ ), preferably a hydrogen atom or an alkyl group, and more preferably a hydrogen atom.
R ⁶ represents a hydrogen atom, an alkyl group, an alkenyl group, an aryl group, or a heterocyclic group (preferable examples of these substituents are the same as those for R ^{1 to} R ⁴ ), preferably an alkyl group (preferably having a C number of 1 to 1). 6 alkyl groups).

Z ¹ represents an atomic group forming a 5- or 6-membered ring.
The heterocycle formed is preferably an indolenine ring, azaindolenine ring, pyrazoline ring, benzothiazole ring, thiazole ring, thiazoline ring, benzoxazole ring, oxazole ring, oxazoline ring, benzimidazole ring, imidazole ring, thiadiazole ring Quinoline ring, pyridine ring, more preferably indolenine ring, azaindolenine ring, pyrazoline ring, benzothiazole ring, thiazole ring, thiazoline ring, benzoxazole ring, oxazole ring, oxazoline ring, benzimidazole ring, thiadiazole ring A quinoline ring, most preferably an indolenine ring, an azaindolenine ring, a benzothiazole ring, a benzoxazole ring, or a benzimidazole ring.
The heterocycle formed by Z ¹ may have a substituent (examples of preferred substituents are the same as examples of substituents on Za ₁ and Za ₂ ), and more preferably, an alkyl group, aryl A group, a heterocyclic group, a halogen atom, a carboxyl group, a sulfo group, an alkoxy group, a carbamoyl group, and an alkoxycarbonyl group.

X ¹ and X ² are each preferably an aryl group or a group represented by the general formula (2), more preferably an aryl group substituted with a dialkylamino group or a diarylamino group at the 4-position or the general formula (2) Represented by the group represented.

The two-photon absorption compound of the present invention preferably has a hydrogen bonding group in the molecule. Here, the hydrogen-bonding group represents a group that donates hydrogen or a group that accepts hydrogen in a hydrogen bond, and a group having both properties is more preferable.
Further, the compound having a hydrogen bonding group of the present invention preferably has an associative interaction by the interaction between hydrogen bonding groups in a solution or in a solid state, and may be an intramolecular interaction or an intermolecular interaction. The interaction is more preferable.

The hydrogen bonding group of the present invention is preferably —COOH, —CONHR ¹¹ , —SO ₃ H, —SO ₂ NHR ¹² , —P (O) (OH) OR ¹³ , —OH, —SH, —NHR. ¹⁴ , —NHCOR ¹⁵ , —NR ¹⁶ C (O) NHR ¹⁷ . Here, R ¹¹ and R ¹² are each independently a hydrogen atom, an alkyl group (preferably 1 to 20 carbon atoms (hereinafter referred to as C number), for example, methyl, ethyl, n-propyl, isopropyl, n-butyl, n -Pentyl, benzyl, 3-sulfopropyl, 4-sulfobutyl, carboxymethyl, 5-carboxypentyl), alkenyl group (preferably C2-20, such as vinyl, allyl), aryl group (preferably C6 20, for example, phenyl, 2-chlorophenyl, 4-methoxyphenyl, 3-methylphenyl, 1-naphthyl), a heterocyclic group (preferably having 1 to 20 carbon atoms, such as pyridyl, thienyl, furyl, thiazolyl, imidazolyl, pyrazolyl) , Pyrrolidino, piperidino, morpholino), —COR ¹⁸ or —SO ₂ R ¹⁹ , R ^{13 to} R ¹⁹ each independently represent a hydrogen atom, an alkyl group, an alkenyl group, an aryl group or a heterocyclic group (the preferred examples are the same as those for R ¹¹ and R ¹² ).

R ¹¹ preferably represents a hydrogen atom, an alkyl group, an aryl group, a —COR ¹⁸ group, or a —SO ₂ R ¹⁹ group. In this case, R ¹⁸ and R ¹⁹ are preferably an alkyl group or an aryl group.
R ¹¹ is more preferably a hydrogen atom, an alkyl group, or a —SO ₂ R ¹⁹ group, and most preferably a hydrogen atom.
R ¹² preferably represents a hydrogen atom, an alkyl group, an aryl group, a —COR ¹⁸ group, or a —SO ₂ R ¹⁹ group. In this case, R ¹⁸ and R ¹⁹ are preferably an alkyl group or an aryl group.
R ¹² is more preferably a hydrogen atom, an alkyl group, or a —COR ¹⁸ group, and most preferably a hydrogen atom.
R ¹³ preferably represents a hydrogen atom, an alkyl group, or an aryl group, more preferably a hydrogen atom.
R ¹⁴ preferably represents a hydrogen atom, an alkyl group, or an aryl group.
R ¹⁵ preferably represents an alkyl group or an aryl group.
R ¹⁶ preferably represents a hydrogen atom, and R ¹⁷ preferably represents a hydrogen atom, an alkyl group, or an aryl group.

More preferably, the hydrogen bonding group is any one of —COOH, —CONHR ¹¹ , —SO ₂ NHR ¹² , —NHCOR ¹⁵ , —NR ¹⁶ C (O) NHR ¹⁷ , and more preferably —COOH, —CONHR ¹¹ , —SO ₂ NHR ¹² , and most preferably —COOH or —CONH ₂ .

The two-photon absorption compound of the present invention may be used in a monomer state or in an associated state.
Here, the dye chromophores are fixed in a specific spatial arrangement by a bond such as a covalent bond or a coordinate bond, or various intermolecular forces (hydrogen bond, van der Waals force, Coulomb force, etc.) This state is generally referred to as an association (or aggregation) state.
The two-photon absorption compound of the present invention has two or more chromophores that perform two-photon absorption in a molecule even when used in an intermolecular association state, and is used in a state in which they absorb two-photons in an intramolecular association state. May be.

For reference, the meeting is explained below. As for the association, for example, James, “The Theory of the Photographic Process”, 4th edition, Macmillan Publishers, 1977, Chapter 8, 218. Pp. 222 and “J-Aggregates” written by Takayoshi Kobayashi, World Scientific Publishing Co. Pte. Ltd., 1996). .
A monomer means a monomer. From the viewpoint of the absorption wavelength of the aggregate, an aggregate whose absorption shifts to a short wavelength with respect to monomer absorption is defined as an H aggregate (a dimer is specially called a dimer), and an aggregate whose shift is shifted to a long wavelength. Called coalescence.

  From the viewpoint of the structure of the aggregate, in the brick aggregate, when the deviation angle of the aggregate is small, it is called a J aggregate, but when the deviation angle is large, it is called an H aggregate. There is a detailed description of brickwork aggregates in Chemical Physics Letters, Vol. 6, page 183 (1970). In addition, there is a ladder or staircase aggregate as an aggregate having a structure similar to that of a brickwork aggregate. Ladder or staircase structures are described in detail in Zeitschiff for Physikaliche Chemie, Vol. 49, p. 324 (1941).

Moreover, as what forms other than a brickwork aggregate | assembly, the aggregate | assembly (it can call an arrowhead aggregate | assembly) etc. which take an arrow (Herringbone) structure etc. are known.
The Herringbone association is described in Charles Reich, Photographic Science and Engineering Vol. 18, No. 3, p. 335 (1974). Has been. The arrowhead aggregate has two absorption maxima derived from the aggregate.

Whether or not it is in an associated state can be confirmed by a change in absorption (absorption λmax, ε, absorption type) from the monomer state as described above.
The compound of the present invention may be either short-wavelength (H-association) or long-wavelength (J-association) or both by association, but it is more preferable to form a J-aggregate.

The intermolecular association state of a compound can be formed in various ways.
For example, in a solution system, an aqueous solution to which a matrix such as gelatin is added (for example, gelatin 0.5 wt% · compound 10 ⁻⁴ M aqueous solution), an aqueous solution to which a salt such as KCl is added (for example, KCl 5% · compound 2 × 10 ^−3). M aqueous solution), a method of dissolving a compound in a good solvent, a method of adding a poor solvent afterwards (for example, DMF-water system, chloroform-toluene system, etc.) and the like.
Examples of the film system include polymer dispersion systems, amorphous systems, crystal systems, and LB film systems.
Furthermore, molecules can be adsorbed, chemically bonded, or self-assembled into bulk or fine particle (μm to nm size) semiconductors (eg, silver halide, titanium oxide, etc.), bulk or fine particle metals (eg, gold, silver, platinum, etc.). Inter-association states can also be formed. Spectral sensitization by cyanine dye J-associative adsorption on silver halide crystals in a color silver salt photograph utilizes this technique.
The number of compounds involved in the intermolecular association may be two or a very large number of compounds.

  Although the preferable specific example of the two-photon absorption compound used by this invention is given to the following, this invention is not limited to these.

Next, the polymerization initiator in the two-photon absorption polymerizable composition of the present invention will be described. The polymerization initiator of the present invention is a radical or acid (Bronsted acid) by performing energy transfer or electron transfer (giving or receiving electrons) from the excited state of a two-photon absorption compound generated by non-resonant two-photon absorption. Or a Lewis acid) and a compound capable of initiating polymerization of a polymerizable compound.
The polymerization initiator of the present invention is preferably a radical polymerization initiator capable of generating radicals to initiate radical polymerization of polymerizable compounds, and cationic polymerization of polymerizable compounds by generating only acids without generating radicals. Either a cationic polymerization initiator capable of initiating only radicals or a polymerization initiator capable of generating both radicals and acids to initiate both radical and cationic polymerization.

  The polymerization initiator of the present invention preferably includes the following 14 systems. In addition, you may use these polymerization initiators as 2 or more types of mixtures by arbitrary ratios as needed.

1) Ketone polymerization initiator 2) Organic peroxide polymerization initiator 3) Bisimidazole polymerization initiator 4) Trihalomethyl-substituted triazine polymerization initiator 5) Diazonium salt polymerization initiator 6) Diaryliodonium salt polymerization Initiator 7) sulfonium salt polymerization initiator 8) borate polymerization initiator 9) diaryliodonium organic boron complex polymerization initiator 10) sulfonium organic boron complex polymerization initiator 11) cationic two-photon absorption compound organic boron Complex polymerization initiator 12) Anionic two-photon absorption compound onium salt complex polymerization initiator 13) Metal arene complex polymerization initiator 14) Sulfonic acid ester polymerization initiator

  The preferred system described above will be specifically described below.

  1) Ketone-based polymerization initiator

Preferred examples of the ketone polymerization initiator include aromatic ketones and aromatic diketones.
Preferred examples include, for example, benzophenone derivatives (for example, benzophenone, Michler's ketone), benzoin derivatives (for example, benzoin methyl ether, benzoin ethyl ether, α-methylbenzoin, α-allylbenzoin, α-phenylbenzoin), acetoin derivatives (acetoin, pivaloin, 2-hydroxy-2-methylpropiophenone, 1-hydroxycyclohexyl phenyl ketone), acyloin ether derivatives (eg diethoxyacetophenone), α-diketone derivatives (diacetyl, benzyl, 4,4′-dimethoxybenzyl, benzyldimethyl ketal) , 2,3-bornanedione (camphorquinone), 2,2,5,5-tetramethyltetrahydro-3,4-furanic acid (imidazole trione)), xanthone derivative (For example, xanthone), thioxanthone derivatives (for example, thioxanthone, 2-chlorothioxanthone), ketocoumarin derivatives, and the like.

  Examples of commercially available products include Irgacure 184, 651, and 907 represented by the following formula marketed by Ciba Geigy.

  Preferred examples include quinone polymerization initiators (eg, 9,10-anthraquinone, 1-chloroanthraquinone, 2-chloroanthraquinone, 2-methylanthraquinone, 2-ethylanthraquinone, 2-t-butylanthraquinone. Quinone, octamethylanthraquinone, 1,4-naphthoquinone, 9,10-phenanthrenequinone, 1,2-benzanthraquinone, 2,3-benzanthraquinone, 2-methyl-1,4-naphthoquinone, 2, 3-dichloronaphthoquinone, 1,4-dimethylanthraquinone, 2,3-dimethylanthraquinone, 2-phenylanthraquinone, 2,3-dimethylanthraquinone, sodium salt of anthraquinone alpha-sulfonic acid, 3-chloro-2 -Methylanthraquinone, Rethenequinone, 7,8,9,10-tetrahydronaphthacene Non, as well as 1,2,3,4-tetrahydrobenz (a) anthracene-7,12-dione).

  2) Organic peroxide polymerization initiator

  Preferable examples include benzoyl peroxide, di-t-butyl peroxide, 3,3 ′, 4,4′-tetra (t-) described in JP-A-59-189340 and JP-A-60-76503. Butylperoxycarbonyl) benzophenone and the like.

  3) Bisimidazole polymerization initiator

  Preferable bisimidazole-based polymerization initiators are bis (2,4,5-triphenyl) imidazole derivatives, such as bis (2,4,5-triphenyl) imidazole, 2- (o-chlorophenyl)- 4,5-bis (m-methoxyphenyl) -imidazole dimer (CDM-HABI), 1,1'-biimidazole, 2,2'-bis (o-chlorophenyl) -4,4'5,5'-tetra Examples include phenyl (o-Cl-HABI), 1H-imidazole, 2,5-bis (o-chlorophenyl) -4- [3,4-dimethoxyphenyl] -dimer (TCTM-HABI), and the like.

  The bisimidazole polymerization initiator is preferably used together with a hydrogen donor. Preferred examples of the hydrogen donor include 2-mercaptobenzoxazole, 2-mercaptobenzothiazole, 4-methyl-4H-1,2,4-triazole-3-thiol, and the like.

  4) Trihalomethyl-substituted triazine polymerization initiator

  The trihalomethyl-substituted triazine polymerization initiator is preferably represented by the following general formula (11).

In general formula (11), R ₂₁ , R ₂₂ , and R ₂₃ each independently represent a halogen atom, preferably a chlorine atom. R ₂₄ and R ₂₅ each independently represent a hydrogen atom, —CR ₂₁ R ₂₂ R ₂₃ , or a substituent (preferred examples are the same as the substituents on Za ¹ ). R ₂₄ is preferably a _-CR 21 _R 22 _{R 23,} more preferably represents a ₃ group _{-CCl, R 25} is preferably, _-CR 21 _R 22 _{R 23,} an alkyl group, an alkenyl group, an aryl group.

  Specific examples of the trihalomethyl-substituted triazine polymerization initiator include 2-methyl-4,6-bis (trichloromethyl) -1,3,5-triazine, 2,4,6-tris (trichloromethyl) -1, 3,5-triazine, 2-phenyl-4,6-bis (trichloromethyl) -1,3,5-triazine, 2- (4′-methoxyphenyl) -4,6-bis (trichloromethyl) -1, 3,5-triazine, 2- (4′-trifluoromethylphenyl) -4,6-bis (trichloromethyl) -1,3,5-triazine, 2,4-bis (trichloromethyl) -6- (p -Methoxyphenylvinyl) -1,3,5-triazine, 2- (4'-methoxy-1'-naphthyl) -4,6-bis (trichloromethyl) -1,3,5-triazine, etc. . Preferable examples also include compounds described in British Patent No. 1388492 and JP-A No. 53-133428.

  5) Diazonium salt polymerization initiator

  The diazonium salt polymerization initiator is preferably represented by the following general formula (12).

R ₂₆ represents an aryl group or a heterocyclic group (the preferred examples are the same as the substituents on Za ¹ ), preferably an aryl group, and more preferably a phenyl group.
R ₂₇ represents a substituent (preferred examples are the same as those of the substituent on Za ^1), a21 represents an integer of 0 to 5, preferably an integer of 0 to 2. a21 is when 2 or more, the plurality of R ₂₇ may be the same or different and may form a ring.
X ₂₁ ⁻ is an anion in which HX ₂₁ becomes an acid having a pKa of 4 or less (in water, 25 ° C.), preferably 3 or less, more preferably 2 or less, preferably, for example, chloride, bromide, iodide, tetrafluoroborate, hexa Fluorophosphate, hexafluoroarsenate, hexafluoroantimonate, perchlorate, trifluoromethanesulfonate, 9,10-dimethoxyanthracene-2-sulfonate, methanesulfonate, benzenesulfonate, 4-trifluoromethylbenzenesulfonate, tosylate, tetra ( Pentafluorophenyl) borate and the like.

  Specific examples of the diazonium-based polymerization initiator include benzenediazonium, 4-methoxydiazonium, the above X21-salt of 4-methyldiazonium, and the like.

  6) Diaryliodonium salt polymerization initiator

  The diaryliodonium salt polymerization initiator is preferably represented by the following general formula (13).

In the general formula _{(13), X 21} ^- is a general formula (12) interchangeably. R ₂₈ and R ₂₉ each independently represent a substituent (preferred examples are the same as those for Za ¹ ), and preferably represent an alkyl group, an alkoxy group, a halogen atom, a cyano group, or a nitro group. a22 and a23 each independently represent an integer of 0 to 5, preferably an integer of 0 to 1. When a22 and a23 are each 2 or more, the plurality of R ₂₈ and R ₂₉ may be the same or different, and may be connected to each other to form a ring.

Specific examples of the diaryliodonium salt polymerization initiator include diphenyliodonium, 4,4′-dichlorodiphenyliodonium, 4,4′-dimethoxydiphenyliodonium, 4,4′-dimethyldiphenyliodonium, 4,4′-t- Chlorides such as butyldiphenyliodonium, 3,3′-dinitrodiphenyliodonium, phenyl (p-methoxyphenyl) iodonium, bis (p-cyanophenyl) iodonium, bromide, iodide, tetrafluoroborate, hexafluorophosphate, hexafluoroarsenate , Hexafluoroantimonate, perchlorate, trifluoromethanesulfonate, 9,10-dimethoxyanthracene-2-sulfonate, methanesulfonate, benzenesulfonate, 4-trifluoromethane Examples include tilbenzene sulfonate, tosylate, and tetra (pentafluorophenyl) borate.
Further, compounds described in “Macromolecules”, Vol. 10, p1307 (1977), Japanese Patent Application Laid-Open Nos. 58-29803, 1-287105, and Japanese Patent Application No. 3-5569. And diaryliodonium salts as described in 1).

  7) Sulfonium salt polymerization initiator

  The sulfonium salt polymerization initiator is preferably represented by the following general formula (14).

In the general formula _{(14), X 21} ^- is a general formula (12) interchangeably. R ₃₀ , R ₃₁ , and R ₃₂ each independently represent an alkyl group, an aryl group, or a heterocyclic group (the preferred examples are the same as the substituents on Za ¹ ), and preferably an alkyl group, a phenacyl group, or an aryl group. Represent.

  Specific examples of the sulfonium salt polymerization initiator include triphenylsulfonium, diphenylphenacylsulfonium, dimethylphenacylsulfonium, benzyl-4-hydroxyphenylmethylsulfonium, 4-tertiarybutyltriphenylsulfonium, tris (4-methylphenyl). ) Chloride, bromide, tetrafluoroborate, hexafluorophosphate of sulfonium salts such as sulfonium, tris (4-methoxyphenyl) sulfonium, 4-phenylthiotriphenylsulfonium, bis-1- (4- (diphenylsulfonium) phenyl) sulfide , Hexafluoroarsenate, hexafluoroantimonate, perchlorate, trifluoromethanesulfonate, 9,10-dimethoxyanthracene-2-sulfo Over DOO, methanesulfonyl rate, benzenesulfonate, 4-trifluoromethylbenzenesulfonate, tosylate, etc. tetra (pentafluorophenyl) borate.

  8) Borate polymerization initiator

  The borate polymerization initiator is preferably represented by the following general formula (15).

In the general formula (15), R ₃₃ , R ₃₄ , R ₃₅ , and R ₃₆ each independently represents an alkyl group, an alkenyl group, an alkynyl group, a cycloalkyl group, or an aryl group (preferred examples are substitutions on Za ¹ ). The same as the group), preferably an alkyl group or an aryl group. However, all of R ₃₃ , R ₃₄ , R ₃₅ , and R ₃₆ do not become an aryl group at the same time. X ₂₂ ⁺ represents a cation.
More preferably, R ₃₃ , R ₃₄ and R ₃₅ are aryl groups, R ₃₆ is an alkyl group, most preferably R ₃₃ , R ₃₄ and R ₃₅ are phenyl groups, and R ₃₆ is an n-butyl group. is there.

  Specific examples of the borate polymerization initiator include tetrabutylammonium n-butyltriphenylborate, tetramethylammonium sec-butyltriphenylborate and the like.

  9) Diaryliodonium organoboron complex polymerization initiator

  The diaryliodonium organoboron complex salt polymerization initiator is preferably represented by the following general formula (16).

In General Formula (16), R ₂₈ , R ₂₉ , a22, and a23 have the same meaning as in General Formula (13), and R ₃₃ , R ₃₄ , R ₃₅ , and R ₃₆ have the same meaning as in General Formula (15).

  Specific examples of the diaryliodonium organic boron complex salt polymerization initiator include I-1 to I-3 shown below.

  Furthermore, iodonium organoboron complexes such as diphenyliodonium (n-butyl) triphenylborate described in JP-A-3-704 are also preferable examples.

  10) Sulfonium organoboron complex polymerization initiator

  The sulfonium organic boron complex salt polymerization initiator is preferably represented by the following general formula (17).

In general formula (17), R ₃₃ , R ₃₄ , R ₃₅ , and R ₃₆ have the same _{meaning as} in general formula (15). R ₃₇ , R ₃₈ and R ₃₉ are each independently an alkyl group, aryl group, alkenyl group, alkynyl group, cycloalkyl group, alkoxy group, aryloxy group, alkylthio group, arylthio group or amino group (and more preferred examples) Is the same as the substituent on Za ¹ ), more preferably an alkyl group, a phenacyl group, an aryl group or an alkenyl group. R ₃₇ , R ₃₈ and R ₃₉ may be connected to each other to form a ring. R ₄₀ represents an oxygen atom or a lone electron pair.

  Specific examples of the sulfonium organic boron complex salt polymerization initiator include I-4 to I-10 shown below.

  Furthermore, preferred examples include sulfonium organoboron complexes described in JP-A-5-255347 and JP-A-5-213861.

  11) Cationic two-photon absorption compound organoboron complex polymerization initiator

When the polymerization initiator of the present invention is a cationic two-photon absorption compound organic boron complex polymerization initiator, the cationic two-photon absorption compound may serve as the two-photon absorption compound of the present invention.
The cationic two-photon absorption compound organoboron complex polymerization initiator is preferably represented by the general formula (18).

In the general formula (18), (Dye-1) ⁺ performs non-resonant two-photon absorption and is a cationic compound. Preferred examples are as described above. R ₃₃ , R ₃₄ , R ₃₅ , and R ₃₆ have the same _{meaning as} in general formula (15).

  Specific examples of the cationic two-photon absorption compound organoboron complex polymerization initiator include I-11, I-12, I-13, and I-14 shown below.

  Specific examples include cationic dye-borate anion complexes described in JP-A-62-143044 and 62-150242.

  12) Anionic two-photon absorption compound onium salt complex polymerization initiator

When the polymerization initiator of the present invention is an anionic two-photon absorption compound onium salt complex polymerization initiator, the anionic two-photon absorption compound may serve as the two-photon absorption compound of the present invention.
The anionic two-photon absorption compound onium salt-based polymerization initiator is preferably represented by the general formula (19).

In the general formula (19), (Dye-2 ) - is carried out an anionic compound non-resonant two-photon absorption, it is as previously described are preferred examples. X ₂₃ ⁺ represents a cation part of the diazonium salt of the general formula (12), a cation part of the diaryliodonium salt of the general formula (13), and a cation part of the sulfonium salt of the general formula (14) (all preferred examples are described above). A cation moiety of the diaryliodonium salt of the general formula (13) or a cation moiety of the sulfonium salt of the general formula (14).

  Specific examples of the anionic two-photon absorption compound onium salt-based polymerization initiator include I-15 to I-32 shown below.

  13) Metal arene complex polymerization initiator

  As the metal arene complex polymerization initiator, the metal is preferably iron or titanium. Specifically, JP-A-1-54440, European Patent No. 109851, European Patent No. 126712 and “Journal of Imaging Science (J. Imag. Sci.)”, Vol. 30, page 174 ( 1986), an iron arene complex described in “Organometallics”, Vol. 8, page 2737 (1989), “Prog. Polym. Sci, Vol. 21, 7- Preferable examples include iron arene complex salts described on page 8 (1996), titanones described in JP-A No. 61-151197, and the like.

  14) Sulfonic acid ester polymerization initiator

  Preferred examples of the sulfonic acid ester polymerization initiator include sulfonic acid esters, sulfonic acid nitrobenzyl esters, imide sulfonates, and the like.

  Specific examples of sulfonic acid esters are preferably benzoin tosylate, pyrogallol trimesylate, and specific examples of sulfonic acid nitrobenzyl esters are preferably o-nitrobenzyl tosylate, 2,6-dinitrobenzyl tosylate, Specific examples of 2 ′, 6′-dinitrobenzyl-4-nitrobenzenesulfonate, p-nitrobenzyl-9,10-diethoxyanthracene-2-sulfonate, 2-nitrobenzyltrifluoromethylsulfonate, and imidosulfonate are preferably N. -Tosylphthalimide, 9-fluorenylideneaminotosylate, α-cyanobenzylidenetosylamine, and the like.

  15) Other polymerization initiators

Examples of polymerization initiators other than the above 1) to 14) include organic azide compounds such as 4,4′-diazidochalcone, aromatic carboxylic acids such as N-phenylglycine, polyhalogen compounds (CI ₄ , CHI ₃ , CBrCI ₃ ), pyridinium salts such as 1-benzyl-2-cyanopyridinium salt hexafluoroantimonate, phenylisoxazolone, silanol aluminum complexes, and aluminate complexes described in JP-A-3-209477.

Here, the polymerization initiator of the present invention is
a) Polymerization initiator capable of activating radical polymerization b) Polymerization initiator capable of activating only cationic polymerization c) Polymerization initiator capable of simultaneously activating radical polymerization and cationic polymerization can be classified.

a) A polymerization initiator capable of activating radical polymerization means energy transfer or electron transfer from an excited state of a two-photon absorption compound generated by non-resonant two-photon absorption (giving an electron to the two-photon absorption compound or from a two-photon absorption compound) It is a polymerization initiator capable of generating radicals by performing (to receive electrons) and initiating radical polymerization of the polymerizable compound.
Among the above, the following systems are polymerization initiator systems that can activate radical polymerization.
1) Ketone polymerization initiator 2) Organic peroxide polymerization initiator 3) Bisimidazole polymerization initiator 4) Trihalomethyl-substituted triazine polymerization initiator 5) Diazonium salt polymerization initiator 6) Diaryliodonium salt polymerization Initiator 7) sulfonium salt polymerization initiator 8) borate polymerization initiator 9) diaryliodonium organic boron complex polymerization initiator 10) sulfonium organic boron complex polymerization initiator 11) cationic two-photon absorption compound organic boron Complex polymerization initiator 12) Anionic two-photon absorption compound onium salt complex polymerization initiator 13) Metal arene complex polymerization initiator

More preferably as a polymerization initiator capable of activating radical polymerization,
1) Ketone-based polymerization initiator 3) Bisimidazole-based polymerization initiator 4) Trihalomethyl-substituted triazine-based polymerization initiator 6) Diaryliodonium salt-based polymerization initiator 7) Sulfonium salt-based polymerization initiator 11) Cationic two-photon absorption compound Organoboron complex polymerization initiator 12) anionic two-photon absorption compound onium salt complex polymerization initiator, more preferably,
3) Bisimidazole-based polymerization initiator 6) Diaryliodonium salt-based polymerization initiator 7) Sulfonium salt-based polymerization initiator 11) Cationic two-photon absorption compound Organic boron complex-based polymerization initiator 12) Anionic two-photon absorption compound onium salt A complex polymerization initiator is mentioned.

  A polymerization initiator capable of activating only cationic polymerization is an acid (Bronsted acid or Lewis) without generating a radical by performing energy transfer or electron transfer from the excited state of a two-photon absorption compound generated by non-resonant two-photon absorption. It is a polymerization initiator capable of generating an acid) and initiating cationic polymerization of the polymerizable compound with the acid.

Among the above systems, the following systems are polymerization initiator systems that can activate only cationic polymerization.
14) Sulfonic acid ester polymerization initiator

Examples of the cationic polymerization initiator include “UV curing; science and technology (UV
CURING; SCIENCE AND TECHNOLOGY) "[p. 23-76, S.M. Edited by S. PETER PAPPAS, A TECHNOLOGY MARKING PUBLICATION] and "Comments Inorg. Chem." [B. Klingelt, M.M. Reedy Car and A. Rolov (B. KLINGERT, M. RIEDICER and A. ROLOFF), Volume 7, No. 3, p109-138 (1988)] and the like can also be used.

  A polymerization initiator capable of simultaneously activating radical polymerization and cationic polymerization is a radical or acid (Bronsted acid or Lewis) by performing energy transfer or electron transfer from the excited state of a two-photon absorption compound generated by non-resonant two-photon absorption. Acid) is a polymerization initiator capable of simultaneously generating radical polymerization of the polymerizable compound by the generated radical, and cationic polymerization of the polymerizable compound by the generated acid.

Among the above systems, the following systems are polymerization initiator systems that can simultaneously activate radical polymerization and cationic polymerization.
4) Trihalomethyl-substituted triazine polymerization initiator 5) Diazonium salt polymerization initiator 6) Diaryliodonium salt polymerization initiator 7) Sulfonium salt polymerization initiator 13) Metal arene complex polymerization initiator

As a polymerization initiator that can activate radical polymerization and cationic polymerization,
6) Diaryliodonium salt polymerization initiators 7) Sulfonium salt polymerization initiators.

Next, the polymerizable compound in the two-photon absorption polymerizable composition of the present invention will be described.
In the two-photon absorption polymerization composition of the present invention, the polymerizable compound and the binder preferably have different refractive indexes. As a result, the photopolymerization caused by non-resonant two-photon absorption causes non-uniformity in the composition ratio of the polymerizable compound and its polymerization reaction product and the binder in the laser focal portion and non-focal portion, and three-dimensional refractive index modulation. Is possible.
The difference in the refractive index between the polymerizable compound and the binder may be either the refractive index of the polymerizable compound is larger or the refractive index of the binder is larger, but the polymerizable compound is more binder. It is more preferable that the refractive index is larger than that.
In order to increase the refractive index modulation, the refractive index difference in the bulk of the polymerizable compound and the binder is preferably large, the refractive index difference is preferably 0.01 or more, more preferably 0.05 or more, more preferably 0.1 or more More preferably.
For this purpose, either the polymerizable compound or the binder contains at least one aryl group, aromatic heterocyclic group, chlorine atom, bromine atom, iodine atom, sulfur atom, and the other one does not contain them. More preferably, the polymerizable compound preferably contains at least one aryl group, aromatic heterocyclic group, chlorine atom, bromine atom, iodine atom or sulfur atom, and the binder does not contain them.
In order to increase the refractive index modulation, it is preferable that the polymerizable compound easily moves in the two-photon polymerization composition.

The polymerizable compound of the present invention can be oligomerized or polymerized by causing addition polymerization with a radical or acid (Bronsted acid or Lewis acid) generated by irradiating light to a two-photon absorption compound and a polymerization initiator. It is a simple compound.
The polymerizable compound of the present invention may be monofunctional or polyfunctional, may be a single component or a multicomponent, and may be a monomer, a prepolymer (eg, a dimer or oligomer), or a mixture thereof, but is a monomer. It is preferable.
The form may be liquid or solid at room temperature, but it is preferably a liquid having a boiling point of 100 ° C. or higher, or a mixture of a liquid monomer having a boiling point of 100 ° C. or higher and a solid monomer. .

The polymerizable compound of the present invention is roughly classified into a polymerizable compound capable of radical polymerization and a polymerizable compound capable of cationic polymerization.
In the following, for each polymerizable compound capable of radical polymerization and polymerizable compound capable of cationic polymerization, A) refractive index: polymerizable compound> binder, and B) refractive index: binder> polymerizable compound. Examples of preferable polymerizable compounds will be described.

    A) Refractive index: Polymerizable compound> Preferred examples of radical polymerizable compound in the case of binder

  In this case, the radical polymerizable compound preferably has a high refractive index, and the high refractive index radical polymerizable compound of the present invention has at least one ethylenically unsaturated double bond in the molecule, and at least 1 A compound containing an aryl group, an aromatic heterocyclic group, a chlorine atom, a bromine atom, an iodine atom or a sulfur atom is preferred, and a liquid having a boiling point of 100 ° C. or higher is preferred.

  Specific examples thereof include the following polymerizable monomers and prepolymers (dimers, oligomers, etc.) comprising them.

  As the high refractive index radical polymerizable monomer, styrene, 2-chlorostyrene, 2-bromostyrene, methoxystyrene, phenyl acrylate, p-chlorophenyl acrylate, 2-phenylethyl acrylate, 2-phenoxyethyl acrylate, 2-phenoxyethyl methacrylate, phenol ethoxylate acrylate, 2- (p-chlorophenoxy) ethyl acrylate, benzyl acrylate, 2- (1-naphthyloxy) ethyl acrylate, 2,2-di (p-hydroxyphenyl) Propane diacrylate or dimethacrylate, 2,2-di (p-hydroxyphenyl) propane dimethacrylate, polyoxyethyl-2,2-di (p-hydroxyphenyl) propane dimethacrylate, di (2-methacryloxy) of bisphenol-A Ethyl) ether, ethoxylated bisphenol-A diacrylate, bisphenol-A di (3-acryloxy-2-hydroxypropyl) ether, bisphenol-A di (2-acryloxyethyl) ether, tetrachloro-bisphenol-A Di (3-acryloxy-2-hydroxypropyl) ether, di (2-methacryloxyethyl) ether of tetrachloro-bisphenol-A, di (3-methacryloxy-2-hydroxypropyl) ether of tetrabromo-bisphenol-A, tetrabromo -Di (2-methacryloxyethyl) ether of bisphenol-A, di (3-methacryloxy-2-hydroxypropyl) ether of diphenolic acid, 1,4-benzenediol dimethacrylate, 1,4-diisopropenyl vinyl And 1,3,5-triisopropenylbenzene, benzoquinone monomethacrylate, 2- [β- (N-carbazyl) propionyloxy] ethyl acrylate, phenylthioacrylate, 4-iodophenylacrylate, and the like. Preferably 2-phenoxyethyl acrylate, 2-phenoxyethyl methacrylate, phenol ethoxylate acrylate, 2- (p-chlorophenoxy) ethyl acrylate, p-chlorophenyl acrylate, phenyl acrylate, 2-phenyl acrylate Examples include ethyl, di (2-acryloxyethyl) ether of bisphenol-A, ethoxylated bisphenol-A diacrylate, and 2- (1-naphthyloxy) ethyl acrylate.

  The polymerizable compounds useful in the present invention are liquids, but they are N-vinylcarbazole, H.P. An ethylenically unsaturated carbazole monomer, as disclosed in Journal of Polymer Science: Polymer Chemistry Edition, Vol. 18, pages 9-18 (1979), 2-naphthyl acrylate, pentachlorophenyl acrylate, acrylic acid 2, It may be used in admixture with a second solid polymerizable compound such as 4,6-tribromophenyl, bisphenol-A diacrylate, 2- (2-naphthyloxy) ethyl acrylate, and N-phenylmaleimide.

  B) Refractive index: Preferable example of radical polymerizable compound in the case of binder> polymerizable compound

In this case, the radical polymerizable compound preferably has a low refractive index, and the low refractive index radical polymerizable compound of the present invention has at least one ethylenically unsaturated double bond in the molecule, and further has an aryl group. It is preferable that no aromatic heterocyclic group, chlorine atom, bromine atom, iodine atom or sulfur atom is contained.
Moreover, it is preferable that it is a liquid whose boiling point is 100 degreeC or more.
Specific examples thereof include the following polymerizable monomers and prepolymers (dimers, oligomers, etc.) comprising them.

  The low refractive index radical polymerizable monomer is preferably t-butyl acrylate, cyclohexyl acrylate, iso-bornyl acrylate, 1,5-pentanediol diacrylate, N, N-diethylaminoethyl acrylate, ethylene glycol diacrylate, 1 , 4-butanediol diacrylate, diethylene glycol diacrylate, hexamethylene glycol diacrylate, 1,3-propanediol diacrylate, decamethylene glycol diacrylate, 1,4-cyclohexyldiol diacrylate, 2,2-dimethylolpropane diacrylate Acrylate, glycerol diacrylate, trimethylolpropane diacrylate, pentaerythritol triacrylate, polyoxyethylated trimethylolpropane triacrylate And trimethacrylate and related compounds disclosed in US Pat. No. 3,380,831, pentaerythritol tetraacrylate, triethylene glycol diacrylate, triethylene glycol dimethacrylate, polyoxypropyltrimethylolpropane diacrylate (462), Ethylene glycol dimethacrylate, butylene glycol dimethacrylate, 1,3-propanediol dimethacrylate, 1,2,4-butanetriol trimethacrylate, 2,2,4-trimethyl-1,3-propanediol dimethacrylate, pentaerythritol tri Methacrylate, pentaerythritol tetramethacrylate, trimethylolpropane trimethacrylate, 1,5-pentanediol dimethacrylate, diary fumarate 1H, 1H-perfluorooctyl acrylate, 1H, 1H, 2H, 2H-perfluorooctyl methacrylate, and 1-vinyl-2-pyrrolidinone, more preferably decanediol diacrylate, isoacrylate -Bornyl, triethylene glycol diacrylate, diethylene glycol diacrylate, triethylene glycol dimethacrylate, ethoxyethoxyethyl acrylate, triacrylate ester of ethoxylated trimethylolpropane, and 1-vinyl-2-pyrrolidine.

  Useful polymerizable compounds are liquids, but they may be used in admixture with a second solid polymerizable compound monomer, such as N-vinylcaprolactam.

  The cationically polymerizable compound of the present invention is a compound in which polymerization is initiated by an acid generated by a two-photon absorption compound and a cationic polymerization initiator. For example, “Chemtech. Oct.” [J. V. JV Crivello, p. 624, (1980)], JP-A No. 62-149784, Journal of the Adhesion Society of Japan [Vol. 26, No. 5, pp. 179-187 (1990)] and the like.

  The cationically polymerizable compound of the present invention is preferably a compound having at least one oxirane ring, oxetane ring, vinyl ether group or N-vinylcarbazole moiety in the molecule, more preferably a compound having an oxirane ring moiety.

  A) Refractive index: polymerizable compound> preferred example of cationic polymerizable compound in the case of binder

  In this case, the cationic polymerizable compound preferably has a high refractive index, and the high refractive index radical polymerizable compound of the present invention has at least one ethylenically unsaturated double bond in the molecule, and further has at least 1 A compound containing an aryl group, an aromatic heterocyclic group, a chlorine atom, a bromine atom, an iodine atom or a sulfur atom is preferred, and at least one aryl group is preferred. Moreover, it is preferable that it is a liquid whose boiling point is 100 degreeC or more.

  Specific examples thereof include the following polymerizable monomers and prepolymers (dimers, oligomers, etc.) comprising them.

  Preferred as a high refractive index cationic polymerizable monomer having an oxirane ring is phenyl glycidyl ether, p-t-butylphenyl glycidyl ether, phthalic acid diglycidyl ester, resorcin diglycidyl ether, dibromophenyl glycidyl ether, dibromoneopentyl glycol diglycidyl. Ether, 4,4′-bis (2,3-epoxypropoxyperfluoroisopropyl) diphenyl ether, p-bromostyrene oxide, bisphenol-A-diglycidyl ether, tetrabromobisphenol-A-diglycidyl ether, bisphenol-F-di Examples thereof include glycidyl ether.

  Specific examples of the high refractive index cationic polymerizable monomer having an oxetane ring include compounds in which the oxirane ring in the specific examples of the high refractive index cationic polymerizable monomer having an oxirane ring is replaced with an oxetane ring.

  Specific examples of the high refractive index cationically polymerizable monomer having a vinyl ether group moiety include, for example, vinyl-2-chloroethyl ether, 4-vinyl ether styrene, hydroquinone divinyl ether, phenyl vinyl ether, bisphenol A divinyl ether, tetrabromobisphenol A divinyl ether. Bisphenol F divinyl ether, phenoxyethylene vinyl ether, p-bromophenoxyethylene vinyl ether, and the like.

In addition, N-vinylcarbazole is also preferable as the high refractive index cationic polymerizable monomer.
B) Refractive index: Preferable example of cationically polymerizable compound in the case of binder> polymerizable compound

  In this case, the cation polymerizable compound preferably has a low refractive index, and the low refractive index radical polymerizable compound of the present invention has at least one ethylenically unsaturated double bond in the molecule, and further has an aryl group. A compound containing no aromatic heterocyclic group, no chlorine atom, no bromine atom, no iodine atom and no sulfur atom is preferred. Moreover, it is preferable that it is a liquid whose boiling point is 100 degreeC or more.

  Specific examples thereof include the following polymerizable monomers and prepolymers (dimers, oligomers, etc.) comprising them.

  Specific examples of the low refractive index cationically polymerizable monomer having an oxirane ring include glycerol diglycidyl ether, glyceryl triglycidyl ether, diglycerol triglycidyl ether, diglycerol polyglycidyl ether, pentaerythritol polyglycidyl ether, 1,4 -Bis (2,3-epoxypropoxyperfluoroisopropyl) cyclohexane, sorbitol tetraglycidyl ether, trimethylolpropane diglycidyl ether, trimethylolpropane monoglycidyl ether, trimethylolpropane triglycidyl ether, 1,6-hexanediol diglycidyl ether , Ethylene glycol diglycidyl ether, ethylene glycol monoglycidyl ether, polyethylene glycol diglycidyl Ether, propylene glycol diglycidyl ether, propylene glycol monoglycidyl ether, neopentyl glycol diglycidyl ether, neopentyl glycol monoglycidyl ether, adipic acid diglycidyl ester, 1,2,7,8-diepoxyoctane, 1, 6-dimethylol perfluorohexane diglycidyl ether, vinylcyclohexene dioxide, 3,4-epoxycyclohexylmethyl-3 ′, 4′-epoxycyclohexanecarboxylate, 3,4-epoxycyclohexyloxirane, bis (3,4-epoxy Cyclohexyl) adipate, bis (3,4-epoxy-6-methyl-cyclohexylmethyl) adipate, 2,2-bis [4- (2,3-epoxypropoxy) cyclohexyl] propane 2,2-bis [4- (2,3-epoxypropoxy) cyclohexyl] hexafluoropropane, 1,2,5,6-diepoxy-4,7-methanoperhydroindene, 2- (3,4-epoxycyclohexyl) ) -3 ′, 4′-epoxy-1,3-dioxane-5-spirocyclohexane, 1,2-ethylenedioxy-bis (3,4-epoxycyclohexylmethane), 4 ′, 5′-epoxy-2 ′ -Methylcyclohexylmethyl-4,5-epoxy-2-methylcyclohexanecarboxylate, ethylene glycol-bis (3,4-epoxycyclohexanecarboxylate), bis- (3,4-epoxycyclohexylmethyl) adipate, di-2, 3-epoxycyclopentyl ether, vinyl glycidyl ether, allyl glycidyl ether, 2-ethylhexyl glyci Ether, 1,3-bis - (3 ', 4'-epoxycyclohexyl-ethyl) -1,1,3,3, - tetramethyl disiloxane and the like.

  Specific examples of the low refractive index cationic polymerizable monomer having an oxetane ring include compounds in which the oxirane ring in the specific examples of the low refractive index cationic polymerizable monomer having an oxirane ring is replaced with an oxetane ring.

  Specific examples of the low refractive index cationically polymerizable monomer having a vinyl ether group moiety include, for example, vinyl-n-butyl ether, vinyl t-butyl ether, ethylene glycol divinyl ether, ethylene glycol monovinyl ether, propylene glycol divinyl ether, propylene glycol mono Vinyl ether, neopentyl glycol divinyl glycol, neopentyl glycol monovinyl glycol, glycerol divinyl ether, glycerol trivinyl ether, triethylene glycol divinyl ether, trimethylol ethane trivinyl ether, trimethylolpropane monovinyl ether, trimethylolpropane divinyl ether, trimethylolpropane tri Vinyl ether, diglycerol trivinyl ether Ether, sorbitol tetravinyl ether, allyl vinyl ether, 2,2-bis (4-cyclohexanol) propane divinyl ether, 2,2-bis (4-cyclohexanol) trifluoropropane divinyl ether, 1,4-cyclohexanedimethanol divinyl ether Etc.

The binder in the two-photon absorption polymerizable composition of the present invention is usually used for the purpose of improving the film-forming property, film thickness uniformity, and storage stability of the composition before polymerization. As the binder, those having good compatibility with the polymerizable compound, the polymerization initiator, and the two-photon absorption compound are preferable.
As the binder, a solvent-soluble thermoplastic polymer is preferable and can be used alone or in combination with each other.

As described above, the binder of the present invention preferably has a refractive index different from that of the polymerizable compound, and the polymerizable compound may have a higher refractive index or the binder may have a higher refractive index. However, it is more preferable that the polymerizable compound has a higher refractive index than the binder.
For this purpose, either the polymerizable compound or the binder contains at least one aryl group, aromatic heterocyclic group, chlorine atom, bromine atom, iodine atom, sulfur atom, and the other one does not contain them. More preferably, the polymerizable compound preferably contains at least one aryl group, aromatic heterocyclic group, chlorine atom, bromine atom, iodine atom or sulfur atom, and the binder does not contain them.

  Examples of preferred binders will be described below in the case of A) refractive index: polymerizable compound> binder and B) refractive index: binder> polymerizable compound.

  A) Preferred examples of the binder in the case of refractive index: polymerizable compound> binder.

  Specific examples of preferred low refractive index binders include acrylate and alpha-alkyl acrylate esters and acidic polymers and interpolymers (eg, polymethyl methacrylate and polyethyl methacrylate, methyl methacrylate and other (meth) acrylic acid alkyl esters). Copolymers), polyvinyl esters (eg, polyvinyl acetate, polyacetic acid / vinyl acrylate, polyacetic acid / vinyl methacrylate and hydrolyzable polyvinyl acetate), ethylene / vinyl acetate copolymers, saturated and unsaturated polyurethanes, High molecular weight poly (ethylene oxide), epoxides of butadiene and isoprene polymers and copolymers and polyglycols having a weight average molecular weight of approximately 4,000 to 1,000,000 (eg, epoxidation having acrylate or methacrylate groups) ), Polyamide (eg, N-methoxymethyl polyhexamethylene adipamide), cellulose ester (eg, cellulose acetate, cellulose acetate succinate and cellulose acetate butyrate), cellulose ether (eg, methyl cellulose, ethyl cellulose, ethyl benzyl cellulose) , Polycarbonates, polyvinyl acetals (eg, polyvinyl butyral and polyvinyl formal), polyvinyl alcohol, polyvinyl pyrrolidone, acid-containing polymers and copolymers described in US Pat. No. 3,458,311 and US Pat. No. 4,273,857. And amphoteric polymer binders disclosed in U.S. Pat. No. 4,293,635, more preferably cellulose acetate butyrate polymer, cellulose Acetate lactate polymer, polymethyl methacrylate, acrylic polymer and interpolymer including methyl methacrylate / methacrylic acid and methyl methacrylate / acrylic acid copolymer, methyl methacrylate / acrylic acid or C2-C4 alkyl methacrylate / Examples thereof include terpolymers of acrylic acid or methacrylic acid, polyvinyl acetate, polyvinyl acetal, polyvinyl butyral, polyvinyl formal, and mixtures thereof.

  A fluorine atom-containing polymer is also preferable as the low refractive index binder. Preferably, fluoroolefin is an essential component, and one or more selected from alkyl vinyl ether, alicyclic vinyl ether, hydroxy vinyl ether, olefin, haloolefin, unsaturated carboxylic acid and ester thereof, and carboxylic acid vinyl ester It is a polymer soluble in an organic solvent having the unsaturated monomer as a copolymerization component. Preferably, the weight average molecular weight is 5,000 to 200,000, and the fluorine atom content is 5 to 70% by mass.

  As the fluoroolefin in the fluorine atom-containing polymer, tetrafluoroethylene, chlorotrifluoroethylene, vinyl fluoride, vinylidene fluoride, or the like is used. In addition, as other copolymerization components, alkyl vinyl ethers include ethyl vinyl ether, isobutyl vinyl ether, n-butyl vinyl ether, alicyclic vinyl ethers such as cyclohexyl vinyl ether and derivatives thereof, hydroxy vinyl ethers such as hydroxybutyl vinyl ether, olefins and halo. Examples of olefins include ethylene, propylene, isobutylene, vinyl chloride, and vinylidene chloride. Examples of carboxylic acid vinyl esters include vinyl acetate and n-vinyl butyrate. Examples of unsaturated carboxylic acids and esters include (meth) acrylic acid and crotonic acid. Unsaturated carboxylic acids and methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, iso (meth) acrylate C1 to C18 alkyl esters of (meth) acrylic acid such as lopyr, butyl (meth) acrylate, hexyl (meth) acrylate, octyl (meth) acrylate, lauryl (meth) acrylate, hydroxyethyl (meth) C2-C8 hydroxyalkyl esters of (meth) acrylic acid such as acrylate, hydroxypropyl (meth) acrylate, N, N-dimethylaminoethyl (meth) acrylate, N, N-diethylaminoethyl (meth) acrylate, etc. Can be mentioned. These radical polymerizable monomers may be used alone or in combination of two or more, and if necessary, a part of the monomer may be used as another radical polymerizable monomer such as styrene, α -You may substitute with vinyl compounds, such as methylstyrene, vinyl toluene, and (meth) acrylonitrile. Further, as other monomer derivatives, carboxylic acid group-containing fluoroolefin, glycidyl group-containing vinyl ether, and the like can also be used.

  Specific examples of the fluorine atom-containing polymer include, for example, an organic solvent-soluble “Lumiflon” series having a hydroxyl group (for example, Lumiflon LF200, weight average molecular weight: about 50,000, manufactured by Asahi Glass Co., Ltd.). In addition, organic solvent-soluble fluorine atom-containing polymers are also marketed by Daikin Industries, Ltd., Central Glass Co., Ltd., and Penwort Co., Ltd., and these can also be used.

  B) Refractive index: A preferred example of a binder in the case of binder> polymerizable compound.

Specific examples of preferable high refractive index binders include polystyrene polymers and copolymers such as acrylonitrile, maleic anhydride, acrylic acid, methacrylic acid and esters thereof, and vinylidene chloride copolymers (eg, vinylidene chloride / acrylonitrile copolymer). Polymer, vinylidene chloride / methacrylate copolymer, vinylidene chloride / vinyl acetate copolymer), polyvinyl chloride and copolymers (eg, polyvinyl chloride / acetate, vinyl chloride / acrylonitrile copolymer), polyvinyl benzal synthetic rubber (For example, butadiene / acrylonitrile copolymer, acrylonitrile / butadiene / styrene copolymer, methacrylate / acrylonitrile / butadiene / styrene copolymer, 2-chlorobutadiene-1,3 polymer, chlorinated rubber, styrene Styrene / butadiene / styrene, styrene / isoprene / styrene block copolymer), copolyesters (eg, polymethylene glycol of the formula HO (CH ₂ ) nOH where n is an integer from 2 to 10), and ( 1) produced from reaction products of hexahydroterephthalic acid, sebacic acid and terephthalic acid, (2) terephthalic acid, isophthalic acid and sebacic acid, (3) terephthalic acid and sebacic acid, (4) terephthalic acid and isophthalic acid And (5) mixtures of the glycols and (i) terephthalic acid, isophthalic acid and sebacic acid and (ii) copolyesters prepared from terephthalic acid, isophthalic acid, sebacic acid and adipic acid), poly N-vinylcarbazole And its copolymers, and H.I. Examples include carbazole-containing polymerization as disclosed in Journal of Polymer Science: Polymer Chemistry Edition, Vol. 18, pages 9 to 18 (1979) by Kamogawa et al., More preferably polystyrene, poly (styrene / acrylonitrile), poly (polystyrene). (Styrene / methyl methacrylate) and polyvinyl benzal and mixtures thereof.

In general, the proportion of each component in the two-photon absorption polymerizable composition of the present invention is preferably in the following% range based on the total mass of the composition.
Binder: preferably 0 to 90% by mass, more preferably 45 to 75% by mass,
Polymerizable compound: preferably 5 to 60% by mass, more preferably 15 to 50% by mass,
Two-photon absorption compound: preferably 0.01 to 10% by mass, more preferably 0.1 to 7% by mass Polymerization initiator: preferably 0.01 to 10% by mass, preferably 0.1 to 7% by mass

  In the two-photon absorption polymerizable composition of the present invention, additives such as a chain transfer agent, a heat stabilizer, a plasticizer, and a solvent can be appropriately used as necessary.

In some cases, the two-photon absorption polymerizable composition of the present invention preferably uses a chain transfer agent. Preferred chain transfer agents are thiols such as 2-mercaptobenzoxazole, 2-mercaptobenzthiazole, 2-mercaptobenzimidazole, 4-methyl-4H-1,2,4-triazole-3-thiol, 4 , 4-thiobisbenzenethiol, p-bromobenzenethiol, thiocyanuric acid, 1,4-bis (mercaptomethyl) benzene, p-toluenethiol, etc., as described in US Pat. Thiols, disulfides described in JP-A-2-291561, thiones described in USP 3,558,322 and JP-A 64-17048, O-acylthiohydroxamates and N-alkoxy described in JP-A-2-291560 Also included are pyridinethiones.
In particular, when the polymerization initiator is 2,4,5-triphenylimidazolyl dimer, it is preferable to use a chain transfer agent.
As for the usage-amount of a chain transfer agent, 1.0-30 mass% is preferable with respect to the whole composition.

A heat stabilizer (thermal polymerization inhibitor) can be added to the two-photon absorption polymerizable composition of the present invention for the purpose of preventing polymerization during storage and maintaining storage stability.
Useful heat stabilizers include hydroquinone, phenidone, p-methoxyphenol, alkyl and aryl substituted hydroquinones and quinones, catechol, t-butylcatechol, pyrogallol, 2-naphthol, 2,6-di-t-butyl-p. -Cresol, phenothiazine, chloranneal and the like. Dinitroso dimers, as described in Pazos US Pat. No. 4,168,982, are also useful.
The heat stabilizer is preferably added in the range of 0.001 to 5 parts by mass with respect to 100 parts by mass of the compound having an unsaturated bond.

Plasticizers are used to change the adhesion, flexibility, hardness, and other mechanical properties of the two-photon polymerizable composition. In addition, there is an effect of promoting the movement of the polymerizable compound and increasing the refractive index modulation amount.
Examples of the plasticizer include triethylene glycol dicaprylate, triethylene glycol bis (2-ethylhexanoate), tetraethylene glycol diheptanoate, diethyl sebacate, dibutyl suberate, tris (2-ethylhexyl) phosphate, Examples include tricresyl phosphate and dibutyl phthalate.

The two-photon absorption polymerizable composition of the present invention may be prepared by a usual method. For example, the above-mentioned essential components and optional components can be prepared as they are or by adding a solvent as necessary.
Examples of the solvent include ketone solvents such as methyl ethyl ketone, methyl isobutyl ketone, acetone and cyclohexanone, ester solvents such as ethyl acetate, butyl acetate, ethylene glycol diacetate, ethyl lactate and cellosolve acetate, carbonization such as cyclohexane, toluene and xylene. Hydrogen solvents, ether solvents such as tetrahydrofuran, dioxane, diethyl ether, cellosolv solvents such as methyl cellosolve, ethyl cellosolve, butyl cellosolve, dimethyl cellosolve, methanol, ethanol, n-propanol, 2-propanol, n-butanol, diacetone Alcohol solvents such as alcohol, fluorine solvents such as 2,2,3,3-tetrafluoropropanol, dichloromethane, chloroform, 1,2-dichloro Halogenated hydrocarbon solvents such as Roetan, N, amide solvents such as N- dimethylformamide,
The two-photon absorption polymerizable composition can be applied directly onto the substrate, can be spin-coated, or can be cast as a film and laminated to the substrate by a conventional method. The solvent used can be removed by evaporation during drying.

  The two-photon absorption polymerization composition of the present invention is preferably subjected to refractive index recording by laser irradiation, and then irradiated with UV or visible light to cause one-photon absorption to perform fixing treatment. Further, it is also preferable to perform heating at 40 to 160 ° C.

  Hereinafter, specific embodiments of the present invention will be described based on experimental results. Of course, the present invention is not limited to these examples.

[Example 1]
Synthesis of the two-photon absorption compound of the present invention

(1) Synthesis of D-73

  The two-photon absorption compound D-73 of the present invention can be synthesized by the following method.

  14.3 g (40 mmol) of the quaternary salt [1] was dissolved in 50 ml of water, 1.6 g (40 mmol) of sodium hydroxide was added, and the mixture was stirred at room temperature for 30 minutes. The mixture was extracted three times with ethyl acetate, dried over magnesium sulfate and concentrated to obtain 9.2 g (yield 100%) of methylene-based [2] oil.

  3.97 g (40 mmol) of dimethylaminoacrolein [3] was dissolved in 50 ml of acetonitrile, and 6.75 g (44 mmol) of phosphorus oxychloride was added dropwise while cooling to 0 ° C., followed by stirring at 0 ° C. for 10 minutes. Subsequently, 9.2 g of acetonitrile solution of methylene base [2] was dropped, and the mixture was stirred at 35 ° C. for 4 hours. After pouring into 100 ml of ice water, 16 g of sodium hydroxide was added and refluxed for 10 minutes. After cooling, the mixture was extracted 3 times with ethyl acetate, dried over magnesium sulfate and concentrated. Purification by silica gel column chromatography (developing solvent: ethyl acetate: hexane = 1: 10 → 1: 3) gave 4.4 g (39% yield) of aldehyde [4] as an oil.

  0.126 g (1.5 mmol) of cyclopentanone and 0.85 g (3 mmol) of aldehyde 4 were dissolved in 30 ml of dehydrated methanol and refluxed in a dark place under a nitrogen atmosphere. After becoming uniform, 0.69 g (3.6 mmol) of a 28% sodium methoxide methanol solution was added, and the mixture was further refluxed for 6 hours. After cooling, the precipitated crystals were separated by filtration and washed with methanol to obtain 0.50 g (yield 54%) of D-73 dark green crystals. The structure was confirmed by NMR spectrum, MS spectrum and elemental analysis.

(2) Synthesis of D-84

  The two-photon absorption compound D-84 of the present invention can be synthesized by the following method.

  33.6 g (0.4 mol) of cyclopentanone, 2 ml of DBN, and 400 g of N, N-dimethylformamide dimethyl acetal were refluxed for 5 days. After concentration, acetone was added and cooled to separate the crystals, which were then washed with cold acetone to obtain 32.4 g of crystals [5] (yield 42%).

[5] 0.78 g (4 mmol), quaternary salt [6] 2.78 g (8 mmol), and 20 ml of pyridine were refluxed in a dark place under a nitrogen atmosphere for 4 hours. After cooling, ethyl acetate was added and the crystals were separated and washed with ethyl acetate. The crystals were dispersed in methanol and separated by filtration to obtain 2.14 g (yield 56%) of the desired deep blue crystals of D-84.
The structure was confirmed by NMR spectrum, MS spectrum and elemental analysis.

  In addition, other two-photon absorption compounds represented by the general formula (1) of the present invention can be synthesized by the synthesis methods of D-73 and D-84, Tetrahedron. Lett. 42, 6129, (2001) and the like.

(3) Synthesis of D-1

  The two-photon absorption compound D-1 of the present invention can be synthesized by the following method.

  Benzoxazole [7] 52.25 g (0.2 mol) and propane sultone [8] 45.75 g (0.375 mol) were heated and stirred at 140 ° C. for 4 hours. After cooling, acetone was added and the crystals were separated, and washed with acetone to obtain 70.42 g (yield 85%) of a quaternary salt [9].

Quaternary salt [9] 66.2 g (0.2 mol), triethyl orthopropionate [10] 200 ml, pyridine 200 ml and acetic acid 80 ml were heated and stirred at 120 ° C. for 1 hour. After cooling, decantation washing was performed 3 times with ethyl acetate. When dissolved in 100 ml of methanol and stirred, a solution of sodium acetate 4.0 g (50 mmol) / methanol 20 ml was added, and the resulting crystals were separated. Furthermore, it disperse | distributed to methanol and separated and obtained the target D-1 vermilion crystal 31.36g (yield 43.4%).
The structure was confirmed by NMR spectrum, MS spectrum and elemental analysis.

(4) Synthesis of D-42

  The two-photon absorption compound D-42 of the present invention can be synthesized by the following method.

Quaternary salt [11] 2.81 g (10 mmol), [12] 6.67 g (30 mmol), acetic anhydride 10 g, and acetonitrile 50 ml were refluxed for 30 minutes. After concentration, decantation with ethyl acetate was performed to obtain a crude product of anil form [13].
To the crude product of anil [13], 2.00 g (10 mmol) of thiobarbituric acid [14], 3.0 g (30 mmol) of triethylamine and 100 ml of ethanol were added and refluxed for 1 hour. After concentration, the residue was purified by silica gel column chromatography (developing solvent: chloroform: methanol = 20: 1 → 10: 1), and further recrystallized from methanol-isopropyl alcohol to obtain 2.55 g of the target D-42 crystal. (Total yield 41.3%) was obtained.
The structure was confirmed by NMR spectrum, MS spectrum and elemental analysis.

(5) Synthesis of D-56

  The two-photon absorption compound D-56 of the present invention can be synthesized by the following method.

Barbituric acid [15] 3.12 g (20 mmol), [16] 2.85 g (10 mmol) and triethylamine 4.1 g (40 mmol) were dissolved in DMF 30 ml, and the mixture was stirred at room temperature for 2 hours. Crystals produced by adding dilute hydrochloric acid were filtered, washed with water and dried to obtain 2.99 g (yield: 80.0%) of the desired D-56 crystals.
The structure was confirmed by NMR spectrum, MS spectrum and elemental analysis.

  Further, other cyanine dyes, merocyanine dyes, oxonol dyes and the like are also described in F.I. M.M. By Harmer, Heterocyclic Compounds-Cyanine Dies and Related Compounds, John & Wiley & Sons, New York, London, 1964, D.C. M.M. According to Sturmer, Heterocyclic Compounds-Special Topics in Heterocyclic Chemistry, Chapter 18, Section 14, pages 482-515, John & Wiley & Son et al., New Yor et al.

  However, the synthesis method of the two-photon absorption compound of the present invention is not limited to this.

  Most of the polymerization initiator, polymerizable compound, binder, chain transfer agent, heat stabilizer, plasticizer, solvent and the like of the present invention are commercially available, and commercially available products can be used as they are.

[Example 2]
[Three-dimensional refractive index modulation evaluation by two-photon absorption polymerizable composition]

  Next, a three-dimensional refractive index modulation method by photopolymerization caused by non-resonant two-photon absorption of the two-photon absorption polymerization composition of the present invention will be described. As the laser light source to be used, laser light having a wavelength longer than the linear absorption band of the two-photon absorption compound of the present invention and having no linear absorption is used. Specifically, a solid-state laser or fiber laser having an oscillation wavelength around 1000 nm, a semiconductor laser having an oscillation wavelength around 780 nm, a solid-state laser, a fiber laser, a semiconductor laser or a solid laser having an oscillation wavelength in the range of 620 to 680 nm. A laser or the like can be used.

A sample 101 of the two-photon absorption polymerizable composition of the present invention was prepared with the following composition. Furthermore, as described in Table 1, samples 102 to 111 were prepared by replacing an equivalent mass of a two-photon absorption compound, a polymerization initiator, a polymerizable monomer, and a binder. The chain transfer agent was added only to the sample 106 except for the sample 101. Samples 102, 103, and 108 are reference examples.
The sample was bar-coated on a prepared glass plate, dried with a solvent, and then put on a PET film to give an evaluation sample. The film thickness was in the range of 5-10 μm.

<Sample 101: Two-photon absorption polymerizable composition of the present invention>
Two-photon absorption compound: D-77 0.02 g
Polymerization initiator: 0.03 g of I-54
Polymerizable compound (polymerizable monomer): M-1 1.15 g
Binder: CAB 1.25g
Chain transfer agent: I-57 0.045 g
Solvent: 7.8 g of dichloromethane

For the performance evaluation of the two-photon absorption polymerizable composition of the present invention, a Ti: sapphire pulse laser (pulse width: 100 fs, repetition: 80 MHz, average output: 1 W, peak power: 100 kW) that can be measured in the wavelength range of 700 nm to 1000 nm. ), The two-photon absorption polymerizable composition of the present invention was irradiated with the laser beam condensed by a lens with NA of 0.6.
The irradiation wavelength used was a wavelength that maximizes the two-photon absorption cross section δ in a 10 ⁻⁴ M solution of the two-photon absorption compound.

As a result, in any sample of the present invention, it was possible to confirm refractive index modulation (0.005 or more) at the laser focus portion and the non-focus portion after photopolymerization.
Further, the refractive index modulation could be confirmed in the same manner after being left in a light place and a dark place for 1 week.
Further, it was confirmed that the refractive index modulation can be performed in any depth direction, that is, in a three-dimensional direction, by scanning the laser focal position in the depth direction in any sample.

Claims (8)

A non-resonant two-photon having at least a non-resonant two-photon absorption compound, a polymerization initiator, a polymerizable compound, and a binder, and capable of three-dimensional refractive index modulation by photopolymerization caused by non-resonant two-photon absorption Composition for absorption polymerization.
However, non-resonant two-photon absorption compound is a cyanine dye, a merocyanine dye, oxonol dye, Ri compound der represented by phthalocyanine dyes or the following general formula (1), polymerizable compound, at least one aryl group, It contains an aromatic heterocyclic group, chlorine atom, bromine atom, iodine atom, or sulfur atom, and the binder does not contain them .

In the formula, each of R ¹ , R ² , R ³ and R ⁴ independently represents a hydrogen atom or a substituent, and some of R ¹ , R ² , R ³ and R ⁴ are bonded to each other to form a ring. May be formed. n and m each independently represent an integer of 0 to 4, and when n and m are 2 or more, a plurality of R ¹ , R ² , R ³ and R ⁴ may be the same or different. However, n and m are not 0 simultaneously. X ¹ and X ² independently represent an aryl group, a heterocyclic group, or a group represented by the following general formula (2).

In the formula, R ⁵ represents a hydrogen atom or a substituent, R ⁶ represents a hydrogen atom, an alkyl group, an alkenyl group, an aryl group, or a heterocyclic group, and Z ¹ represents an atomic group forming a 5- or 6-membered ring. . The non-cyan compound according to claim 1, wherein the cyanine dye is represented by the following general formula (3), the merocyanine dye is represented by the following general formula (4), and the oxonol dye is represented by the general formula (5). Resonant two-photon absorption polymerization composition.

In the general formulas (3) to (5), Za ₁ , Za ₂ and Za ₃ each represent an atomic group forming a 5-membered or 6-membered nitrogen-containing heterocycle, and Za ₄ , Za ₅ and Za ₆ are each 5 A group of atoms forming a member or six-membered ring is represented. Ra ₁ , Ra ₂ and Ra ₃ each independently represent a hydrogen atom, an alkyl group, an alkenyl group, an aryl group or a heterocyclic group.
Ma _{1 to} Ma ₁₄ each independently represent a methine group, may have a substituent, and may form a ring with another methine group. na ¹ , na ² and na ³ are each 0 or 1, and ka ¹ and ka ³ each represent an integer of 0 to 3. When ka ¹ is 2 or more, the plurality of Ma ₃ and Ma ₄ may be the same or different, and when ka ³ is 2 or more, the plurality of Ma ₁₂ and Ma ₁₃ may be the same or different. ka ² represents an integer of 0 to 8, and when ka ² is 2 or more, a plurality of Ma ₁₀ and Ma ₁₁ may be the same or different.
CI represents an ion for neutralizing the electric charge, and y represents a number necessary for neutralizing the electric charge.   In the composition for non-resonant two-photon absorption polymerization, the polymerizable compound and the binder have different refractive indexes, and the polymerizable compound is formed in the laser focal part and the non-focus part by photopolymerization caused by non-resonant two-photon absorption using laser light. 3. The composition for non-resonant two-photon absorption polymerization according to claim 1, wherein the composition ratio of the polymerization reaction product and the binder becomes non-uniform so that three-dimensional refractive index modulation is possible. object. The composition for nonresonant two-photon absorption polymerization according to any one of claims 1 to 3 , wherein at least one of the polymerizable compounds is a liquid having a boiling point of 100 ° C or higher. The binder has a lower refractive index than the polymerizable compound, and the binder is at least one polymer selected from polymers containing cellulose ester, polyvinyl alcohol, polyvinyl acetate, polyvinyl butyral, polyvinyl formal, and fluorine. The composition for nonresonant two-photon absorption polymerization according to any one of claims 1 to 4 . The said polymerization initiator contains the polymerization initiator which generate | occur | produces at least 1 sort (s) of radical, The polymerizable compound contains the radical polymerizable compound which superposes | polymerizes by at least 1 type of radical, The one of Claims 1-5 characterized by the above-mentioned. The composition for non-resonant two-photon absorption polymerization according to one item. Includes a polymerization initiator polymerization initiator that generates at least one acid, claim 1-6 polymerizable compound, characterized by containing a cationic polymerizable compound that undergoes polymerization when irradiated with at least one acid The composition for non-resonant two-photon absorption polymerization according to one item. A three-dimensional optical recording medium comprising the composition for nonresonant two-photon absorption polymerization according to any one of claims 1 to 7 .