JP2007017886A - Two-photon absorption recording material, two-photon absorption optical recording method and two-photon absorption optical recording and reproducing method - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a two-photon absorption recording material which performs recording by refractive index modulation, absorption index modulation or luminescence intensity modulation using two-photon absorption of a two-photon absorption compound, and which allows reproduction by illuminating light onto the recording material after the recording, and detecting difference in its reflectance, transmission or luminescence intensity. <P>SOLUTION: The two-photon absorption recording material contains at least the two-photon absorption compound which produces an excited state upon two-photon absorption, and a recording component which causes a coloring reaction or a decoloring reaction upon electron transfer or energy transfer from the excited state of the two-photon absorption compound, and can perform recording using modulation of refractive index, absorption index or luminescence intensity by the absorption change, wherein at least one of the two-photon absorption compound and the recording component is a polymer or an oligomer. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention relates to a two-photon absorption recording material and a two-photon absorption optical recording method applicable to a high-density optical recording medium such as a three-dimensional optical recording material and a three-dimensional volume display.

  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. In recent years, the third-order nonlinear optical effect has attracted attention, and non-resonant two-photon absorption is particularly attracting 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 non-resonant two-photon absorption is induced, a laser having a wavelength longer than that of a wavelength region in which a (linear) absorption band of a compound exists is often used. Since the laser in the transparent region is used, the laser beam can reach the inside of the sample without being absorbed or scattered, and one point inside the sample can be excited with extremely high spatial resolution due to the square characteristic of non-resonant two-photon absorption. This is a great advantage over ordinary one-photon (linear) absorption.

On the other hand, optical information recording media (optical discs) capable of recording information only once by laser light are known. 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 usually a light reflecting layer is formed on the recording layer, and a protective layer is further formed if necessary.
Information is recorded on the DVD-R by irradiating visible laser light (usually in a 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 (e.g., pit generation) occurs and changes its optical properties. On the other hand, reading (reproduction) of information is also performed by irradiating a laser beam having the same wavelength as the recording laser beam, and the portion where the optical characteristics of the recording layer have changed (recorded portion) and the portion that has not changed (unrecorded) Information is reproduced by detecting the difference in reflectance from the (part). This difference in reflectance is based on so-called “refractive index modulation”.

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, preferably 100 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 has a physical principle that even if the recording / reproducing wavelength is shortened, it is at most about 25 GB on one side and is sufficiently large to meet future requirements. It cannot be said that the recording 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 and reproduction (Levic, Eugene, Polis et al., Special Table 2001-524245 [Patent Document 1], Pavel, Eugene et al., Japanese Translation of PCT International Publication No. 2000-512061 [Patent Document 2]), a method of reading by absorption or fluorescence using a photochromic compound (Korotif, Nikolai Eye et al., Japanese Translation of PCT International Publication No. 2001-522119 [Patent Document 3], Arsenoff "Radimir et al., JP-T-2001-508221 [Patent Document 4]) and the like have been proposed, but none of the specific two-photon absorbing materials are presented, and two-photon absorbing compounds presented abstractly The two-photon absorption compound having a very low two-photon absorption efficiency is also used in the example of FIG. Since the romic compound is a reversible material, there are problems in nondestructive reading, long-term storage stability of recording, S / N ratio of reproduction, and the like, and it cannot be said that the system is practical as an optical recording medium.
In particular, in terms of non-destructive readout, long-term storage stability of recording, etc., it is preferable to reproduce by changing the reflectance or transmittance (refractive index or absorptivity) or emission intensity using an irreversible material. There was no example which specifically disclosed the two-photon absorption material having.
Also, three-dimensional recording by refractive index modulation is performed in Kawada Jun, Kawada Yoshimasa, JP-A-6-28672 [Patent Document 5], Kawada Kei, Kawada Yoshimasa et al. And JP-A-6-118306 [Patent Document 6]. However, there is no description on a method using a two-photon absorption three-dimensional optical recording material.
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

As described above, a reaction is caused by using the excitation energy obtained by non-resonant two-photon absorption, and as a result, the refractive index, absorption rate or emission intensity is changed in the laser focus (recording) part and the non-focus (non-recording) part. If it can be modulated, it can be recorded at an extremely high spatial resolution in an arbitrary place in a three-dimensional space, and can be applied to a three-dimensional optical recording medium that is considered to be the ultimate high-density recording medium.
However, the currently available two-photon absorption compounds have a low two-photon absorption capability, so that 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, in order to achieve a fast transfer rate, it is essential to construct a two-photon absorption three-dimensional optical recording material capable of recording with high sensitivity by two-photon absorption. For this purpose, a two-photon absorption compound that can absorb two-photons with high efficiency and generate an excited state, and a two-photon absorption compound excited state using a two-photon absorption compound excited state by any method. Alternatively, a material containing a recording component capable of efficiently forming a difference in light emission intensity is promising, but such a material has not been disclosed so far, and construction of such a material has been desired.

An object of the present invention is to record at least a two-photon absorption compound having a large two-photon absorption cross-sectional area by using refractive index modulation, absorptivity modulation, or emission intensity modulation using two-photon absorption of the two-photon absorption compound. Thereafter, the two-photon absorption optical recording / reproducing method and the recording / reproducing can be performed 2 by reproducing the light by irradiating the recording material with light and detecting the difference in reflectance, transmittance or emission intensity. A photon absorption recording material is provided.
The present invention also provides a two-photon absorption recording material having excellent storage stability. Furthermore, the present invention provides a two-photon absorption three-dimensional optical recording material, a two-photon absorption three-dimensional optical recording method and a reproducing method using them.

  As a result of intensive studies by the inventors, the above object of the present invention has been achieved by the following means.

(1) At least a two-photon absorption compound that generates an excited state by two-photon absorption, and a refractive index due to the absorption change by causing a color development reaction or a decoloring reaction by electron transfer or energy transfer from the two-photon absorption compound excitation state. A two-photon absorption recording material characterized in that at least one of the two-photon absorption compound or the recording component is a polymer or a recording component capable of recording using modulation of absorption rate or emission intensity. A two-photon absorption recording material which is an oligomer.
(2) The recording component includes at least an acid generator and an acid-color-forming dye precursor or an acid-erasable dye, and at least one of them is a polymer or an oligomer. The two-photon absorption recording material.
(3) The two-photon absorption recording material according to (2), wherein the acid color-forming dye precursor or the acid decolorizable dye is a polymer or an oligomer.
(4) In (2), (2) or (3), wherein the acid generator is a diaryliodonium salt, a sulfonium salt, a diazonium salt, a metal arene complex, a trihalomethyl-substituted triazine, or a sulfonic acid ester The two-photon absorption recording material.
(5) The two-photon absorption recording material according to (4), wherein, in (4), the acid generator is a diaryliodonium salt, a sulfonium salt, a trihalomethyl-substituted triazine, or a sulfonate ester.
(6) In (2), the recording is by refractive index modulation by a color development reaction, and the dye produced from the acid color development type dye precursor is a xanthene (fluorane) dye, triphenylmethane dye, or proton addition to a cyanine base The two-photon absorption recording material according to any one of (2) to (5), wherein the two-photon absorption recording material is a cyanine dye.
(7) In (2), the recording is by refractive index modulation by a decoloring reaction, and the acid decoloring dye is dissociated benzylidene dye, dissociable oxonol dye, dissociable xanthene dye, dissociable azo dye The two-photon absorption recording material according to any one of (2) to (5), which is a body.
(8) The recording component according to (1), wherein the recording component contains at least a base generator and a base coloring dye precursor or a base decoloring dye, and at least one of them is a polymer or an oligomer. Two-photon absorption recording material.
(9) The two-photon absorption recording material according to (8), wherein the base color-forming dye precursor or the base decolorizable dye according to (8) is a polymer or an oligomer.
(10) The two-photon absorption recording material according to (8) or (9), wherein the base generator is represented by the following general formulas (3-1) to (3-4) in (8): .

In general formulas (3-1) to (3-4), R ₁ , R ₂ , R ₁₃ , R ₁₄ and R ₁₅ are each independently a hydrogen atom, an alkyl group, an alkenyl group, a cycloalkyl group, an aryl group, hetero R ₁ or R ₂ may be linked to each other to form a ring, and R ₁₃ , R ₁₄ , or R ₁₅ may be linked to each other to form a ring. R ₃ , R ₆ , R ₇ and R ₉ each independently represent a substituent, R ₄ , R ₅ , R ₈ , R ₁₀ and R ₁₁ each independently represent a hydrogen atom or a substituent, and R ¹⁰ , R ¹¹ may be connected to each other to form a ring. R ₁₆ , R ₁₇ , R ₁₈ and R ₁₉ each independently represents an alkyl group or an aryl group, and R ₁₂ represents an aryl group or a heterocyclic group. n1 represents an integer of 0 or 1, and n2 to n4 each independently represents an integer of 0 to 5.
(11) The two-photon absorption recording material as described in (10), wherein n1 is 1 in the general formulas (3-1) and (3-2).
(12) In the general formula (3-1), R ₃ is either a nitro group substituted at the 2-position or 2,6-position, or an alkoxy group substituted at the 3,5-position ( The two-photon absorption recording material according to 10) or (11).
(13) The two-photon absorption recording material as described in (10) or (11), wherein in formula (3-2), R ₆ is an alkoxy group substituted at the 3,5-position.
(14) In (8), the recording is by refractive index modulation by a color development reaction, and the base color development type dye precursor is a dissociation azo dye, dissociation azomethine dye, dissociation benzylidene dye, dissociation oxonol dye, dissociation The two-photon absorption recording material according to any one of (8) to (13), wherein the two-photon absorption recording material is a non-dissociated product of a type xanthene (fluorane) dye and a dissociation type triphenylmethane dye.
(15) The recording in (8) is based on refractive index modulation by a decoloring reaction, and the base decoloring dye is a triphenylmethane dye, a xanthene dye, a fluorane dye, a cyanine dye formed by adding a proton to a cyanine base, etc. The two-photon absorption recording material according to any one of (8) to (13), which is an acid coloring dye coloring material.
(16) The two-photon according to any one of (1) to (15), wherein the recording component includes at least a color-forming dye precursor polymer or oligomer represented by the following general formula (1): Absorption recording material.
General formula (1)
(A1-PD) m1

In general formula (1), A1 and PD are covalently bonded, and A1 is a site having a function of breaking the covalent bond with PD by electron transfer or energy transfer with the excited state of the two-photon absorption compound. It represents a site that can cause a color reaction when the covalent bond with A1 is cleaved and released.
In the general formula (1), either A1 or PD is connected to each other through a covalent bond to form a polymer or oligomer, and m1 represents an integer of 3 to 1,000,000.
(17) In the general formula (1), PD is a group composed of any one of a dissociation azo dye, a dissociation azomethine dye, a dissociation benzylidene dye, a dissociation oxonol dye, a triphenylmethane dye, and a xanthene dye, The two-photon absorption recording material according to (16), which is covalently linked to A1 above.
(18) The two-photon absorption according to any one of (1) to (15), wherein the recording component contains at least a decolorizable dye polymer or oligomer represented by the following general formula (2): Recording material.
General formula (2)
(A2-DD) m2

In the general formula (2), A2 and DD are covalently bonded, and A2 is a site having a function of cleaving the covalent bond with DD by electron transfer or energy transfer with the excited state of the two-photon absorption compound. A site that is a dye when covalently bound to A2 is decolored when the covalent bond is cleaved and released.
In the general formula (2), either A2 or DD is connected to each other through a covalent bond to form a polymer or oligomer, and m2 represents an integer of 3 to 1,000,000.
(19) The two-photon absorption recording material as described in (18), wherein DD in the general formula (2) is a group comprising a cyanine base and is covalently linked to A1 on the chromophore.
(20) The molar extinction coefficient at a two-photon recording wavelength of a dye or a decolorizable dye developed from the color-forming dye precursor described in (1) to (19) is 1000 or less (1) to ( 19) The two-photon absorption recording material described.
(21) The two-photon absorption recording material according to (20), wherein the dye or decolorizable dye developed from the color-forming dye precursor in (20) has no absorption at the two-photon recording wavelength.
(22) The two-photon absorption compound contained in the two-photon absorption recording material described in (1) is represented by a cyanine dye, a merocyanine dye, an oxonol dye, a phthalocyanine dye, an azo dye, or the following general formula (21). The two-photon absorption recording material according to any one of (1) to (21).
Formula (21)

In the formula, R ₁₀₁ , R ₁₀₂ , R ₁₀₃ , and R ₁₀₄ each independently represent a hydrogen atom or a substituent, and some of R ₁₀₁ , R ₁₀₂ , R ₁₀₃ , and R ₁₀₄ are bonded to each other to form a ring. May be formed. n ₁₀₁ and m ₁₀₁ each independently represent an integer of 0 to 4, and when n ₁₀₁ and m ₁₀₁ are 2 or more, a plurality of R ₁₀₁ , R ₁₀₂ , R ₁₀₃ , and R ₁₀₄ may be the same or different. . However, n ₁₀₁ and m ₁₀₁ are not 0 simultaneously. X ₁₀₁ and X ₁₀₂ independently represent an aryl group, a heterocyclic group, or a group represented by General Formula (22).
General formula (22)

In the formula, R ₁₀₅ represents a hydrogen atom or a substituent, R ₁₀₆ represents a hydrogen atom, an alkyl group, an alkenyl group, an aryl group, or a heterocyclic group, and Z ₁₀₁ represents an atomic group forming a 5- or 6-membered ring. .
(23) In (22), the cyanine dye is represented by the following general formula (23), the merocyanine dye is represented by the following general formula (24), and the oxonol dye is represented by the general formula (25). The two-photon absorption recording material according to (22).

In general formulas (23) to (25), Za ₁ , Za ₂ and Za ₃ each represent an atomic group forming a 5-membered or 6-membered nitrogen-containing heterocyclic ring, 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 represents an integer of 0 to 3. When ka ¹ is 2 or more, a 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 that neutralizes the electric charge, and y represents a number necessary for neutralizing the electric charge.
(24) The two-photon absorption recording material according to any one of (1) to (23), wherein the two-photon absorption compound is a polymer or an oligomer in (1).
(25) The electron-donating compound capable of donating an electron to the two-photon absorption compound radical cation after the electron transfer to the recording component is further included, according to any one of (1) to (24), The two-photon absorption recording material.
(26) In (25), the electron donating compound is an alkylamine, aniline, phenylenediamine, triphenylamine, carbazole, phenothiazine, phenoxazine, phenazine, hydroquinone, catechol, alkoxy The two-photon absorption recording material according to (25), which is any one of benzenes, aminophenols, imidazoles, pyridines, metallocenes, metal complexes, and semiconductor fine particles.
(27) The two-photon absorption recording material according to (25), wherein, in (25), the electron-donating compound is any one of triphenylamines, phenothiazines, phenoxazines, and phenazines.
(28) The two-photon absorption recording material according to (25), wherein, in (25), the electron donating compound is a phenothiazine.
(29) The two-photon absorption recording material according to any one of (25) to (28), wherein the electron donating compound according to (25) is a polymer or an oligomer.
(30) The two-photon absorption recording material according to (1) further comprises an electron-accepting compound capable of accepting electrons from the radical anion of the two-photon absorption compound after electron transfer from the recording component ( The two-photon absorption recording material according to any one of 1) to (29).
(31) In (30), the electron-accepting compound is an aromatic compound, a heterocyclic compound, or a heterocyclic compound having an electron-withdrawing group introduced, such as dinitrobenzene or dicyanobenzene. N-alkylpyridinium salts, benzoquinones, imides, metal complexes, and semiconductor fine particles, The two-photon absorption recording material according to (30).
(32) (1) to (31) characterized in that at least two of the two-photon absorption compounds, recording components, and electron donating compounds described in (1) to (31) contain a copolymerized polymer or oligomer. 2) The two-photon absorption recording material according to any one of the above.
(33) The two-photon absorption recording material described in (1) to (32) is 1) color development reaction, 2) latent image color development-color-former self-sensitized amplification color development reaction, 3) latent image color development-color-form-sensitized polymerization. Reaction 4) Dye decoloring reaction 5) Residual decoloring dye latent image-latent image sensitized polymerization reaction, A) Refractive index modulation, B) Absorption rate modulation, C) Luminescence ability modulation The two-photon absorption recording material according to any one of (1) to (32), wherein the recording can be carried out.
(34) In the method described in (33), in which 2) latent image color development-colored body self-sensitized amplification color development reaction is used for two-photon recording, at least a two-photon recording light having a different absorption form from the two-photon absorbing compound is used. Unlike the first step of generating a latent image by exposure and the two-photon recording light in the color body latent image, it is represented by any one of the general formulas (1) and (3-1) to (3-5). The two-photon absorption compound has a linear absorption molar extinction coefficient of 5000 or less, irradiates light with a wavelength range of less than 5000, generates a self-sensitized amplification, and forms a refractive index difference, an absorption difference, or a luminescence intensity difference. The two-photon absorption optical recording method according to (33), wherein the second step is performed by dry processing.
(35) As a compound group capable of two-photon recording by 1) color development reaction or 2) latent image color development-color former self-sensitized amplification color development reaction described in (33), at least
1) a two-photon absorption compound capable of absorbing two photons and generating an excited state;
2) A recording component capable of recording a color difference reaction by transferring electrons or energy from an excited state of a two-photon absorption compound and recording a difference in refractive index, difference in absorption rate, or difference in emission intensity,
A two-photon absorption optical recording method characterized by using:
(36) In the method described in (33), 3) latent image color development-coloring body sensitized polymerization reaction for two-photon recording, a first step of generating at least a color developing body as a latent image with two-photon recording light; A two-photon absorption optical recording method comprising a second step of forming a refractive index difference and recording by irradiating light on the color former latent image to cause polymerization based on linear absorption of the color former. .
(37) The compound group capable of the two-photon absorption optical recording method according to (36) is at least:
1) a two-photon absorption compound that generates an excited state by two-photon absorption in the first step;
Furthermore, as a recording component,
2) Absorption is increased in wavelength from the original state by transferring electrons or energy from the excited state of the two-photon absorption compound in the first step or from the excited state of the color former in the second step, and two-photon absorption. A group of dye precursors capable of becoming a color former having absorption in a wavelength range of 5000 or less in the linear absorption molar absorption coefficient of the compound;
3) a polymerization initiator capable of initiating polymerization of the polymerizable compound by transferring electrons or energy from the colored body excited state in the second step,
4) a polymerizable compound,
5) binder,
A two-photon absorption optical recording method characterized by using:
(38) In the compound group described in (33), 4) in a compound group capable of two-photon recording by a dye decoloring reaction,
1) a two-photon absorption compound that generates an excited state by two-photon absorption;
2) It has a decolorizable dye, or a decolorant precursor and a decolorable dye as a recording component, and after the two-photon absorbing dye generates an excited state by two-photon recording light, it directly gives energy to the decolorable dye. The decolorant is generated from the decolorant precursor by decoloring the decolorable dye by transfer or electron transfer, or by energy transfer or electron transfer to the decolorizer precursor, A recording component capable of recording a difference in refractive index, a difference in absorptivity or a difference in emission intensity by decolorizing the decolorizable dye;
A two-photon absorption optical recording method.
Here, the decolorizer precursor is any of a radical generator, an acid generator, a base generator, a nucleophile generator, an electrophile generator, and a triplet oxygen.
(39) The two-photon absorption compound that generates an excited state by two-photon recording light in a method of two-photon recording by a residual decolorizable dye latent image-latent image sensitized polymerization reaction is described in (33). After generating an excited state by recording light, energy transfer or electron transfer directly to the decolorizable dye described in (38) to erase the decolorable dye, or a decolorant precursor and energy transfer or electron The decoloring agent is generated from the decoloring agent precursor by moving, and the decoloring agent decolorizes the decoloring dye, whereby the first decoloring dye that has not been decolored is used as a latent image. And irradiating the residual decolorizable dye latent image with light having a wavelength different from that of the two-photon recording light, thereby activating the polymerization initiator by energy transfer or electron transfer to cause polymerization, thereby causing a difference in refractive index. A second step of forming and recording Two-photon absorbing optical recording method characterized by.
(40) The compound group capable of the two-photon absorption optical recording method according to (39) is at least:
1) a two-photon absorption compound that generates an excited state by two-photon absorption in the first step;
Furthermore, as a recording component,
2) As a result of direct energy transfer or electron transfer from the excited state of the two-photon absorption compound in the first step, or as a result of generating a decolorant by transferring energy or electron to the decolorizer precursor, decoloring A decolorizable dye having a molar extinction coefficient of 1000 or less at a two-photon recording light wavelength,
3) Polymerization of the polymerizable compound can be started by transferring electrons or energy from the excited state of the two-photon absorption compound in the first step and from the excited state of the decolorizable dye in the second step. A polymerization initiator (sometimes also serving as a decolorizer precursor of 2),
4) a polymerizable compound,
5) binder,
A two-photon absorption optical recording method characterized by using:
(41) In the two-photon absorption recording material described in (1) to (33) and the two-photon absorption optical recording method described in (34) to (40), the recording using the two-photon absorption of the two-photon absorption compound is rewritten. The two-photon absorption recording material according to any one of (1) to (40), which is a method that cannot be used.
(42) In the two-photon absorption recording material described in (1) to (33) and the two-photon absorption recording method described in (34) to (40), After performing recording by refractive index modulation or absorptance modulation using the two-photon absorption of the photon absorption compound, reproduction is performed by irradiating the recording material with light and detecting the difference in reflectance or transmittance. A two-photon absorption optical recording / reproducing method characterized in that
(43) In the two-photon absorption recording material described in (1) to (33) and the two-photon absorption recording method described in (34) to (40), Two-photon absorption light, wherein recording is performed by using two-photon absorption of a photon-absorbing compound, and then recording is performed by irradiating the recording material with light and detecting the difference in emission intensity. Recording and playback method.
(44) A two-photon absorption three-dimensional optical recording / reproducing method comprising the two-photon absorption optical recording / reproducing method according to (42) or (43).
(45) A two-photon absorption three-dimensional optical recording medium comprising the two-photon absorption recording material according to (1) to (33), (41).
(46) The two-photon absorption recording material described in (1) to (33), (41), (45) has a part of the wavelength range of ultraviolet light, visible light, and infrared light other than recording light and reproduction light. A two-photon absorption recording material comprising a light-shielding filter that can be cut on a front surface, a rear surface, or both surfaces of the two-photon absorption recording material.
(47) Two-photon absorption optical recording characterized in that the two-photon absorption recording material described in (1) to (33), (41), (45), (46) is stored in a light-shielding cartridge at the time of storage. Medium.
(48) The two-photon absorption recording material described in (1) to (33), (41), (45) to (47) has a longer wavelength than the linear absorption band of the two-photon absorption compound, and the molarity of linear absorption. A two-photon absorption optical recording method characterized in that recording is performed using two-photon absorption induced by irradiating a laser beam having an extinction coefficient of 10 or less.

The two-photon absorption compound of the present invention has a large two-photon absorption cross-sectional area (sensitivity). Further, by using the two-photon absorption recording material of the present invention using the compound, the refractive index modulation and absorption by two-photon absorption can be achieved with high sensitivity. Recording by rate modulation or emission intensity modulation can be performed. In particular, the storage stability after recording is also excellent.
Further, by using the two-photon absorption recording material of the present invention, two-photon absorption three-dimensional optical recording and reproduction are possible.

The two-photon absorption recording material, the two-photon absorption optical recording method, and the two-photon absorption optical recording / reproducing method of the present invention will be described in detail below.
The two-photon absorption recording material of the present invention causes at least a two-photon absorption compound that generates an excited state by two-photon absorption and a color reaction or a decoloring reaction by electron transfer or energy transfer from the two-photon absorption compound excited state. And a recording component capable of recording using modulation of the refractive index, absorption rate, or emission intensity due to the absorption change, and at least one of the two-photon absorption compound or the recording component is a polymer or an oligomer Is the feature.

Here, the polymer or oligomer of the present invention has a repeating unit of 2 or more and 1 million or less, preferably 3 or more and 1 million or less, more preferably 5 or more and 500,000 or less, and most preferably 10 or more and 100,000 or less. It is.
The molecular weight of the polymer or oligomer is preferably 500 or more and 10 million or less, more preferably 1000 or more and 5 million or less, further preferably 2000 or more and 1 million or less, and most preferably 3000 or more and 1 million or less. .

As a two-photon absorption optical recording / reproducing method of the present invention, recording by refractive index modulation or absorptance modulation was performed on a two-photon absorption recording material having a two-photon absorption compound by utilizing two-photon absorption of the two-photon absorption compound. Thereafter, a method of reproducing by irradiating the recording material with light and detecting a difference in reflectance is preferable.
On the other hand, after recording is performed on the two-photon absorption recording material having the two-photon absorption compound by using the two-photon absorption of the two-photon absorption compound, the emission intensity is irradiated by irradiating the recording material with light. A method of reproducing by detecting the difference is preferable.
In this case, the light emission may be fluorescence or phosphorescence, but fluorescence is preferable from the viewpoint of light emission efficiency.

The two-photon absorption recording material of the present invention is preferably not subjected to wet processing.
The two-photon absorption recording material of the present invention is preferably a system that cannot be rewritten. Here, the non-rewritable method is a method of recording by irreversible reaction, and indicates a method in which once recorded data can be stored without being rewritten even if it is overwritten and recorded. Therefore, it is suitable for storing important data that requires long-term storage. However, of course, it is possible to newly record in an area that has not been recorded yet. In that sense, it is generally called “write-once type” or “write-once type”.

  The two-photon absorption recording material of the present invention has a two-photon absorption compound and utilizes the two-photon absorption of the two-photon absorption compound, 1) color development reaction, 2) latent image color development-chromogen self-sensitized amplification color development A) Refractive index modulation by any of the following methods: reaction, 3) latent image color development-chromogen sensitized polymerization reaction, 4) decolorization reaction, 5) residual decolored dye latent image-latent image sensitization polymerization reaction, A two-photon absorption recording material characterized in that recording is performed by causing either B) absorption rate modulation or C) light emission ability modulation.

A laser is preferably used for recording of the two-photon absorption recording material of the present invention. The light used in the present invention is preferably ultraviolet light having a wavelength of 200 to 2000 nm, visible light, or infrared light, more preferably ultraviolet light having a wavelength of 300 to 1000 nm, visible light, or infrared light, and further preferably. Is visible light or infrared light of 400 to 800 nm.
The laser that can be used is not particularly limited, but specifically, it is also used in a solid laser such as Ti-sapphire having an oscillation wavelength near a central wavelength of 1000 nm, a fiber laser, a CD-R having an oscillation wavelength near 780 nm, or the like. Semiconductor lasers such as AlGaInP, which are also used in semiconductor lasers, solid lasers, fiber lasers, DVD-Rs having an oscillation wavelength in the range of 620-680 nm, solid lasers, GaN having an oscillation wavelength in the vicinity of 400-415 nm, A semiconductor laser such as InGaN can be preferably used.
In addition, a solid SHG laser such as a YAG / SHG laser having an oscillation wavelength in the visible light region, a semiconductor SHG laser, or the like can be preferably used.
The laser used in the present invention may be a pulsed laser or a CW laser.

  When recording on the two-photon absorption recording material of the present invention, laser light having a wavelength longer than the linear absorption band of the two-photon absorption compound and having a linear (one-photon) absorption molar absorption coefficient of 10 or less. It is preferable to cause recording using two-photon absorption induced by irradiation, more preferably 1 or less, further preferably 0.1 or less, and most preferably no linear absorption.

The light used for reproduction is preferably the above laser light, for example. Further, although the power or pulse shape is the same or different, it is more preferable to reproduce using a laser having the same wavelength as that used for recording.
Examples of the light used for reproduction include carbon arc, high-pressure mercury lamp, xenon lamp, metal halide lamp, fluorescent lamp, tungsten lamp, LED, and organic EL. In order to irradiate light in a specific wavelength range, it is also preferable to use a sharp cut filter, a band pass filter, a diffraction grating, or the like as necessary.

In the two-photon absorption recording material of the present invention, the size of the reaction part or coloring part produced by recording is preferably in the range of 10 nm to 100 μm, more preferably in the range of 50 nm to 5 μm, and 50 nm to More preferably, it is in the range of 2 μm.
Further, in order to enable the reproduction of the recording material, the size of the reaction part or the color development part is preferably 1/20 to 20 times the irradiation light wavelength, and is 1/10 to 10 times as large. It is more preferable that the size is 1/5 to 5 times.

In the two-photon absorption recording material of the present invention, after the two-photon recording, a fixing step may be performed by light (ordinary one-photon), heat, or both.
In particular, when an acid proliferating agent or a base proliferating agent is used in the two-photon absorption recording material of the present invention, it is preferable to use heating for fixing in order to make the acid proliferating agent or base proliferating agent function effectively.
In the case of photofixing, the entire surface of the two-photon absorption recording material is irradiated with ultraviolet light or visible light. Preferably, the light source used includes a visible light laser, an ultraviolet light laser, a carbon arc, a high-pressure mercury lamp, a xenon lamp, a metal halide lamp, a fluorescent lamp, a tungsten lamp, an LED, an organic EL, and the like.
It is also preferable to use a laser used for recording as a light source for light fixing as it is or by changing the power, pulse, condensing degree, wavelength and the like.
In the case of thermal fixing, the fixing step is preferably performed at 40 ° C to 160 ° C, more preferably 60 ° C to 130 ° C.
When both photofixing and heat fixing are performed, light and heat may be applied simultaneously, or light and heat may be added separately.

In the two-photon absorption recording material of the present invention, a chemical reaction, a color reaction, and the like that occur due to two-photon absorption are preferably reactions that do not involve thermal decomposition, that is, a photon mode, particularly from the viewpoint of increasing sensitivity. .
That is, it is preferable to record with a mechanism different from the method that is practically used in the existing CD-R and DVD-R, particularly when considering the writing transfer speed in the recording material.

The two-photon absorption optical recording / reproducing method of the present invention includes an optical recording / reproducing method such as DVD-R and DVD-BL (BD), a near-field optical recording / reproducing method, a three-dimensional optical recording / reproducing method, and a three-dimensional volume display recording / reproducing method. It is preferably used for a method or the like, but more preferably used for a three-dimensional optical recording / reproducing method. That is, the two-photon absorption optical recording / reproducing method of the present invention is preferably used for a two-photon absorption three-dimensional optical recording / reproducing method or a two-photon absorption three-dimensional volume display recording / reproducing method.
Similarly, the two-photon absorption recording material of the present invention can be applied to optical recording media such as DVD-R and DVD-BL (BD), near-field optical recording media, three-dimensional optical recording media, and three-dimensional volume display recording materials. It is preferably used, but more preferably used for a three-dimensional optical recording material or medium. That is, the two-photon absorption recording material of the present invention is preferably used for a two-photon absorption three-dimensional optical recording medium or a two-photon absorption three-dimensional volume display recording material.

  When the two-photon absorption recording material of the present invention is used for an optical recording medium, it is preferable that the two-photon absorption recording material is stored in a light shielding cartridge during storage. Further, a light-shielding filter capable of cutting a part of the wavelength range of ultraviolet light, visible light, and infrared light other than the recording light and reproduction light wavelengths is provided on the front surface, back surface, or both surfaces of the two-photon absorption recording material. It is also preferable.

  When the two-photon absorption recording material of the present invention is used for an optical recording medium, the optical recording medium may be disk-shaped, card-shaped, tape-shaped, or any shape.

  Further, the two-photon absorption compound and the two-photon absorption recording material of the present invention may perform multiphoton absorption of three or more photons.

  The two-photon absorption recording material of the present invention contains a two-photon absorption compound. First, the two-photon absorption compound used in the two-photon absorption recording material of the present invention will be described in detail.

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 absorbed and excited in an energy region where there is no (linear) absorption band of the compound).
When applied to a two-photon absorption recording material, especially a two-photon absorption three-dimensional optical recording material, to achieve a high transfer (recording) speed, two-photon absorption is performed with high sensitivity to efficiently generate an excited state. There is a need for a two-photon absorption compound capable of
The efficiency with which the two-photon absorption compound performs two-photon absorption is represented by a two-photon absorption cross section δ and is defined by 1GM = 1 × 10 ⁻⁵⁰ cm ⁴ s / photon. The two-photon absorption cross-sectional area δ of the two-photon absorption compound in the two-photon absorption recording material of the present invention is preferably 100 GM or more from the viewpoint of improving the writing speed, reducing the size of the laser and reducing the cost, and more preferably 1000 GM or more. More preferably, it is 5000 GM or more, most preferably 10,000 GM or more.

The two-photon absorption compound of the present invention is preferably an organic compound.
The two-photon absorption compound is preferably one that absorbs two photons of ultraviolet light, visible light, or infrared light having a wavelength of 200 to 2000 nm to generate an excited state, and more preferably visible light having a wavelength of 400 to 1100 nm. It absorbs light or infrared light to generate an excited state, and more preferably absorbs visible light or infrared light of 400 to 800 nm to generate an excited state.

  The two-photon absorption compound of the present invention preferably has linear absorption in any of ultraviolet light, visible light, and infrared light having a wavelength of 200 to 1000 nm, that is, a dye, and is preferably ultraviolet light having a wavelength of 200 to 700 nm. More preferably, it has linear absorption in any of the light.

In the present invention, when a specific portion is referred to as “group”, unless otherwise specified, it may be substituted with one or more substituents (up to the maximum possible number). 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 “ring” is included in “group”, 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.

  Any two-photon absorption compound in the present invention may be used. For example, cyanine dye, hemicyanine dye, streptocyanine dye, styryl dye, pyrylium dye, merocyanine dye, trinuclear merocyanine dye, tetranuclear merocyanine dye, rhodacyanine dye, complex Cyanine dye, complex merocyanine dye, allopolar dye, arylidene dye, oxonol dye, hemioxonol dye, squalium dye, croconium dye, azurenium dye, coumarin dye, ketocoumarin dye, styrylcoumarin dye, pyran dye, anthraquinone dye, quinone dye, tri Phenylmethane dye, diphenylmethane dye, xanthene dye, thioxanthene dye, phenothiazine dye, phenoxazine dye, phenazine dye, azo Element, azomethine dye, fluorenone dye, diarylethene dye, spiropyran dye, fulgide dye, perylene dye, phthaloperylene dye, indigo dye, polyene dye, acridine dye, acridinone dye, diphenylamine dye, quinacridone dye, quinophthalone dye, porphyrin dye, azaporphyrin dye Chlorophyll dyes, phthalocyanine dyes, fused aromatic dyes, styrenic dyes, metallocene dyes, metal complex dyes, phenylene vinylene dyes, stilbazolium dyes, more preferably cyanine dyes, hemicyanine dyes, streptocyanine dyes, styryl dyes , Pyrylium dye, merocyanine dye, arylidene dye, oxonol dye, squalium dye, ketocoumarin dye, styrylcoumarin dye, pyran dye Thioxanthene dye, phenothiazine dye, phenoxazine dye, phenazine dye, azo dye, polyene dye, azaporphyrin dye, chlorophyll dye, phthalocyanine dye, metal complex dye, more preferably cyanine dye, merocyanine dye, oxonol dye, azo dye Phthalocyanine dyes, more preferably cyanine dyes, merocyanine dyes, and oxonol dyes, and most preferably cyanine dyes.

  When the two-photon absorption compound of the present invention is a cyanine dye, it is preferably represented by the general formula (23).

  In the general formula (23), Za1 and Za2 each represent an atomic group forming a 5-membered or 6-membered nitrogen-containing heterocycle. The 5- 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-ethyloxazolyl, 2-3-sulfopropyloxa Zolyl, 2-3-sulfopropylbenzoxazolyl, 2-3-ethylbenzoxazolyl, 2-3-sulfopropyl-γ-naphthoxazolyl, 2-3-ethyl-α-naphthoxazolyl , 2-3-methyl-β-naphthoxazolyl, 2-3-sulfopropyl-β-naphthoxazolyl, 2-5-chloro-3-ethyl-α-naphthoxazolyl, 2-5-chloro -3-ethylbenzoxazolyl, 2-5-chloro-3-sulfopropylbenzoxazolyl, 2-5,6-dichloro-3-sulfopropylbenzoxazolyl, 2-5-bromo-3-sulfo Propylbenzoxazolyl, 2-3-ethyl-5-phenylbenzoxazolyl, 2-5-phenyl-3-sulfopropylbenzoxazolyl, 2-5- (4-bromophenyl) -3-sulfobutyl Benzoxazolyl, 2-5- (1-pyrrolyl) -3-sulfopropylbenzoxazolyl, 2-5,6-dimethyl-3-sulfopropylbenzoxazolyl, 2-3-ethyl-5-methoxy Benzoxazolyl, 2-3-ethyl-5-sulfobenzoxazolyl, etc.), thiazole nucleus having 3 to 25 carbon atoms (for example, 2-3-ethylthiazolyl, 2-3-sulfopropylthiazolyl) , 2-3-ethylbenzothiazolyl, 2-3-sulfopropylbenzothiazolyl, 2-3-methyl-β-naphthothiazolyl, 2-3-sulfopropyl-γ Naphthothiazolyl, 2-3,5-dimethylbenzothiazolyl, 2-5-chloro-3-ethylbenzothiazolyl, 2-5-chloro-3-sulfopropylbenzothiazolyl, 2-3-ethyl-5 -Iodobenzothiazolyl, 2-5-bromo-3-methylbenzothiazolyl, 2-3-ethyl-5-methoxybenzothiazolyl, 2-5-phenyl-3-sulfopropylbenzothiazolyl An imidazole nucleus having 3 to 25 carbon atoms (for example, 2-1,3-diethylimidazolyl, 2-5,6-dichloro-1,3-diethylbenzimidazolyl, 2-5,6-dichloro-3- Ethyl-1-sulfopropylbenzimidazolyl, 2-5-chloro-6-cyano-1,3-diethylbenzimidazolyl, 2-5-chloro-1,3-diethyl-6-tri Fluoromethylbenzimidazolyl, etc.), C10-30 indolenine nucleus (for example, 3,3-dimethyl-1-pentylindolenine, 3,3, -dimethyl-1-sulfopropylindolenine, 5-carboxy -1,3,3-trimethylindolenine, 5-carbamoyl-1,3,3-trimethylindolenine, 1,3,3, -trimethyl-4,5-benzoindolenine), C number 9 -25 quinoline nuclei (e.g., 2-1 -ethylquinolyl, 2-1 -sulfobutylquinolyl, 4-1 -pentylquinolyl, 4-1 -sulfoethylquinolyl, 4-1 -methyl-7-chloroquinolyl, Selenazole nucleus having 3 to 25 carbon atoms (for example, 2-3-methylbenzoselenazolyl etc.), 5 to 2 carbon atoms Pyridine nucleus (for example, 2-pyridyl etc.) and the like, and in addition, thiazoline nucleus, oxazoline nucleus, selenazoline nucleus, tellurazoline nucleus, tellurazole nucleus, benzotelrazole nucleus, imidazoline nucleus, imidazo [4,5 -Quinoxaline] nucleus, oxadiazole nucleus, thiadiazole nucleus, tetrazole nucleus, pyrimidine nucleus.

  These may be substituted, and for example, an alkyl group, an alkenyl group, a cycloalkyl group, an aryl group, a heterocyclic group, an alkynyl group, a halogen atom, an amino group, a cyano group, a nitro group, a hydroxyl group, Mercapto group, carboxyl group, sulfo group, phosphonic acid group, acyl group, alkoxy group, aryloxy group, alkylthio group, arylthio group, alkylsulfonyl group, arylsulfonyl group, sulfamoyl group, carbamoyl group, acylamino group, imino group, acyloxy Group, alkoxycarbonyl group, carbamoylamino group, more preferably alkyl group, aryl group, heterocyclic group, halogen atom, cyano group, carboxyl group, sulfo group, alkoxy group, sulfamoyl group, carbamoyl group, alkoxycarbonyl group. A 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 Za1 and Za2 is an oxazole nucleus, an imidazole nucleus, a thiazole nucleus, an indolenine ring, and more preferably an oxazole nucleus, an imidazole nucleus, or an indolenine ring. Yes, most preferred is an oxazole nucleus, and a benzoxazole ring is particularly preferred.

  Ra1 and Ra2 each independently represent a hydrogen atom or an alkyl group (preferably having 1 to 20 carbon atoms, 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 C2-20, 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), and 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.

Ma1 to Ma7 each represents a methine group and may have a substituent (examples of preferred substituents are the same as those of the substituents on Za1 and Za2), and the substituents are preferably alkyl groups, halogen atoms, A nitro group, an alkoxy group, an aryl group, a nitro group, a heterocyclic group, an aryloxy group, an acylamino group, a carbamoyl group, a sulfo group, a hydroxy group, a carboxy group, an alkylthio group, a cyano group and the like are preferable, and a substituent is more preferable. Is an alkyl group.
Ma1 to Ma7 are preferably an unsubstituted methine group or an alkyl group (preferably a C number of 1 to 6) substituted methine group, and more preferably an unsubstituted, ethyl group-substituted, or methyl group-substituted methine group.
Ma1 to Ma7 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.

na1 and na2 are 0 or 1, preferably both 0.
ka1 represents an integer of 0 to 3, more preferably ka1 represents 0 to 2, and further preferably ka1 represents 1 or 2.
When ka1 is 2 or more, the plurality of Ma3 and Ma4 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 (24).

In the general formula (24), Za ₃ represents a group of atoms forming a 5-membered or 6-membered nitrogen-containing heterocycle (preferred examples are the same as Za ₁ and Za ₂ ), and these may be substituted (preferred substitution) Examples of the group are the same as those of the substituents on Za ₁ and Za ₂ )), and these heterocyclic rings may be further condensed.

More preferably, the 5- or 6-membered nitrogen-containing heterocycle formed by Za ₃ is an oxazole nucleus, an imidazole nucleus, a thiazole nucleus, or an indolenine nucleus, and more preferably a benzoxazole nucleus, a benzothiazole nucleus, or India. The renin nucleus.

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 ed., The Theory of the Photographic Process, 4th edition, Macmillan, 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 the examples of the substituent on Za ₃ ). More preferably, the substituent is preferably an alkyl group, aryl group, heterocyclic group, 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 the 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 an unsubstituted methine group or an alkyl group (preferably having a C number of 1 to 6) substituted methine group, more preferably an unsubstituted, ethyl group-substituted, or methyl group-substituted methine group.
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 1 to 3.
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 (25).

In general formula (25), Za ₅ and Za ₆ each represent an atomic group forming a 5-membered or 6-membered ring (preferred examples are the same as Za ₄ ), and these may be substituted (examples of preferred substituents). Is the same as the example of the substituent on Za ₄ ), and these heterocyclic rings 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, and more preferably represents 1 or 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 (21).

In the general formula (21), R ₁₀₁ , R ₁₀₂ , R ₁₀₃ , and R ₁₀₄ each independently represent a hydrogen atom or a substituent, and the substituent is preferably an alkyl group, an alkenyl group, a cycloalkyl group, an aryl group, It is a heterocyclic group. R ₁₀₁ , R ₁₀₂ , R ₁₀₃ and R ₁₀₄ are preferably a hydrogen atom or an alkyl group, and some (preferably two) of R ₁₀₁ , R ₁₀₂ , R ₁₀₃ and R ₁₀₄ are bonded to each other to form a ring. May be formed. 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 the general formula (21), n ₁₀₁ and m ₁₀₁ each independently represent an integer of 0 to 4, preferably an integer of 1 to 4. However, n ₁₀₁ and m ₁₀₁ are not 0 simultaneously. When n ₁₀₁ and m ₁₀₁ are 2 or more, a plurality of R ₁₀₁ , R ₁₀₂ , R ₁₀₃ , and R ₁₀₄ may be the same or different.

X ₁₀₁ and X ₁₀₂ are independently an aryl group [preferably having a C number of 6 to 20, preferably a substituted aryl group (for example, a substituted phenyl group, a substituted naphthyl group, and preferably a substituent of Ma ₁ to Ma ₇ 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 by 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 (22) Represents a group represented by

In General Formula (22), R ₁₀₅ represents a hydrogen atom or a substituent (preferred examples are the same as R _{101 to} R ₁₀₄ ), preferably a hydrogen atom or an alkyl group, and more preferably a hydrogen atom.
R ₁₀₆ 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 R _{101 to} R ₁₀₄ ), preferably an alkyl group (preferably having a C number of 1 to 6 alkyl groups).

Z ₁₀₁ 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 ₁₀₁ may have a substituent (examples of preferred substituents are the same as the examples of substituents on Za ₁ and Za ₂ ), and more preferably alkyl groups and aryls. 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 ₁₀₁ and X ₁₀₂ are each preferably an aryl group or a group represented by the general formula (22), more preferably an aryl group substituted with a dialkylamino group or a diarylamino group at the 4-position, or a general formula (22) 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. As the hydrogen bonding group of the present invention, either —COOH or —CONH ₂ is preferable.

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. From the viewpoint of the absorption wavelength of the aggregate, the aggregate whose absorption shifts to a short wavelength with respect to monomer absorption is defined as an H aggregate (the dimer is specially called a dimer), and the aggregate whose shift is shifted to a long wavelength. Called coalescence.
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.

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 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.

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 a polymer dispersion system, an amorphous system, a crystal system, and an LB film system.
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.

  Specific examples of the case where the two-photon absorption compound of the present invention is not a polymer or oligomer will be given below, but the present invention is not limited thereto.

  Preferred examples of other two-photon absorption compounds include synthesis examples of the two-photon absorption compounds, such as JP-A-2004-123668, JP-A-2004-224864, JP-A-2003-183213, JP-A-2005-25152, JP-A-2005-25152. 2004-279795, JP-A-2004-279794, JP-A-2004-250545, JP-A-2004-279646, JP-A-2004-339435, JP-A-2004-341425, JP-A-2004-126440, JP-A-2004 -149517, JP-A-2005-71570, and the like.

  In the two-photon absorption recording material of the present invention, when the two-photon absorption compound is a polymer or oligomer, the two-photon absorption compound is included in the side chain even if the main chain contains the two-photon absorption compound. The polymer or oligomer may be a polymer or oligomer that contains a two-photon absorption compound in the side chain. In the case of a polymer or oligomer containing a two-photon absorption compound in the side chain, even if it is a homopolymerization or a two-photon absorption compound is a copolymer of two or more monomers contained in the side chain, a two-photon A copolymer of a monomer in which the absorbing compound is contained in the side chain and a monomer in which the two-photon absorption compound is not contained in the side chain may be used.

  When the two-photon absorption compound in the two-photon absorption recording material of the present invention is a polymer or oligomer, it is preferable that the two-photon absorption compound mentioned above as a specific example is a polymer or oligomer contained in the main chain or side chain. .

  In the following, particularly preferred two-photon absorption compound polymers or oligomers are listed, but the present invention is not limited thereto.

As described above, the two-photon absorption recording material of the present invention has a two-photon absorption compound and uses the two-photon absorption of the two-photon absorption compound to 1) color development reaction, 2) latent image color development-coloring body. Self-sensitized amplification color reaction, 3) latent image color development-colored body sensitization polymerization reaction, 4) decolorization reaction, 5) residual decolored dye latent image-latent image sensitization polymerization reaction, Recording is preferably performed by causing any one of (1) refractive index modulation, (B) absorption coefficient modulation, and (C) emission intensity modulation.
Then, next, the preferable recording methods 1) to 5) for causing any one of A) refractive index modulation, B) absorption rate modulation, and C) emission intensity modulation will be described.
Here, A) recording by refractive index modulation can be performed by any of the above methods 1) to 5). Recording by B) absorption rate modulation and C) emission intensity can be performed by the methods 1), 2) and 4).
A) Regarding the two-photon absorption recording material and the two-photon absorption recording method by refractive index modulation, JP-A-2005-71570, JP-A-2005-100599, JP-A-2005-97538, JP-A-2005-55875, Examples described in Japanese Patent Application No. 2004-264202 are preferably used, and B) two-photon absorption recording material and two-photon absorption optical recording method by absorptance modulation are disclosed in JP-A-2005-71570 and JP-A-2005-2005. Examples described in Japanese Patent Application No. 100599, Japanese Patent Application Laid-Open No. 2005-55875, and Japanese Patent Application No. 2004-264202 are preferably used, and C) a two-photon absorption recording material and a two-photon absorption optical recording method using emission intensity modulation. Examples described in Kaikai 2005-100606 are preferably used.

  The above recording methods will be described below.

1) Recording by color reaction

  In the present invention, the color development reaction refers to a reaction in which the shape of the absorption spectrum changes in the ultraviolet light, visible light, and infrared light regions of 200 to 2000 nm, and more preferably λmax has a longer wavelength in the absorption spectrum. , Indicates a reaction in which either increase in ε occurs, and more preferably indicates a reaction in which both occur. Moreover, it is more preferable that the color development reaction occurs in a wavelength region of 200 to 1000 nm, and it is more preferable that the color development reaction occurs in a wavelength region of 300 to 900 nm.

If the recording is due to a color reaction, preferably
at least,
1) a two-photon absorption compound capable of absorbing two photons and generating an excited state;
2) A recording component capable of recording a color difference reaction by transferring electrons or energy from an excited state of a two-photon absorption compound and recording a difference in refractive index, difference in absorption rate, or difference in emission intensity,
It is preferable to contain.
Further, it is more preferable that the recording component contains a dye precursor capable of becoming a color former whose absorption has been extended from the original state by electron transfer or energy transfer from the excited state of the two-photon absorption compound.
Furthermore, it is more preferable that a binder polymer is included. Preferable examples of the binder polymer include those described in JP-A Nos. 2005-71570 and 2005-99751.

Here, the refractive index of the dye generally takes a high value from the vicinity of the linear absorption maximum wavelength (λmax) in a region having a longer wavelength than that, and particularly takes a very high value in a region having a wavelength as long as 200 nm from λmax to λmax, Some dyes have high values exceeding 1.8, and in some cases exceeding 2. On the other hand, organic compounds that are not pigments such as binder polymers usually have a refractive index of about 1.4 to 1.6.
Therefore, it can be seen that coloring the dye precursor by two-photon absorption of the two-photon absorption compound can preferably form not only an absorption difference but also a large refractive index difference.
When recording using the difference in refractive index in the two-photon absorption recording material of the present invention, the refractive index of the dye formed from the recording component is preferably maximized in the vicinity of the laser wavelength used for reproduction.
In the case of recording using the difference in emission intensity, it is preferable that there is a difference in emission intensity when the color former and the dye precursor are irradiated with light having a certain wavelength during reproduction.

  As the recording component, the following combinations are preferable. About these, the example described in Unexamined-Japanese-Patent No. 2005-71570 is mentioned as a specific example preferably.

i) A combination comprising at least an acid color-forming dye precursor as a dye precursor and an acid generator. A combination further containing an acid proliferating agent if necessary.

  In this case, as the two-photon absorption recording material of the present invention, either the acid coloring dye precursor or the acid generator is preferably a polymer or oligomer. Both the acid coloring dye precursor and the acid generator may be polymers or oligomers, and may be copolymers.

An acid generator is a compound capable of generating an acid by energy transfer or electron transfer from an excited state of a two-photon absorption compound. The acid generator is preferably stable in the dark. The acid generator in the present invention is preferably a compound capable of generating an acid by electron transfer from the excited state of the two-photon absorption compound.
The acid generator is preferably a trihalomethyl-substituted triazine, diazonium salt, diaryliodonium salt, sulfonium salt, metal arene complex, or sulfonate ester, trihalomethyl-substituted triazine or diaryliodonium salt , Sulfonium salts and sulfonic acid esters are more preferable. Specific examples of preferred acid generators include those described in JP-A-2005-71570.

  When the acid generator is a polymer or oligomer, it may be a polymer or oligomer containing an acid generator in the main chain, or a polymer or oligomer containing an acid generator in the side chain. It is preferable that the polymer or oligomer contains an acid generator. In the case of a polymer or oligomer containing an acid generator in the side chain, the acid generator is contained in the side chain even if the acid generator is a copolymer of two or more monomers contained in the side chain. It may be a copolymer of monomers and monomers that do not contain an acid generator.

  Although the preferable specific example in case the acid generator in this invention is not a polymer or an oligomer is given to the following, this invention is not necessarily limited to this.

  Next, when the acid generator in the two-photon absorption recording material of the present invention is a polymer or oligomer, the acid generator is preferably a polymer or oligomer contained in the main chain or side chain.

  Among them, particularly preferred acid generator polymers or oligomers are listed below, but the present invention is not limited thereto.

  It is also preferable to use an acid proliferating agent from the viewpoint of increasing sensitivity. Specific examples of preferred acid proliferating agents include those described in JP-A-2005-17730.

Next, the acid coloring dye precursor will be described.
When the acid coloring dye precursor is a polymer or oligomer, the polymer or oligomer containing the acid coloring dye precursor in the side chain, even if the acid coloring dye precursor is included in the main chain However, it is preferably a polymer or oligomer containing an acid coloring dye precursor in the side chain. In the case of a polymer or oligomer containing an acid coloring dye precursor in the side chain, even if the acid coloring dye precursor is a copolymer of two or more monomers contained in the side chain, the acid coloring dye precursor The copolymer may be a copolymer of a monomer that is contained in a side chain and a monomer that does not contain an acid coloring dye precursor.

  The color former generated from the acid color-formable dye precursor is preferably a xanthene dye, a fluorane dye or a triphenylmethane dye. Particularly preferred specific examples when the acid-color-forming dye precursor of the present invention is not a polymer or oligomer are given below, but the present invention is not limited thereto.

  In addition, as the acid color-forming dye precursor of the present invention, a cyanine base (leucocyanine dye) that develops color by adding an acid (proton) is also preferably used. Preferred specific examples of the cyanine base when not a polymer or oligomer are shown below, but the present invention is not limited thereto.

  Next, when the acid coloring dye precursor in the two-photon absorption recording material of the present invention is a polymer or oligomer, the acid coloring dye precursor may be a polymer or oligomer contained in the main chain or side chain. preferable.

  In the following, particularly preferred acid coloring dye precursor polymers or oligomers are listed, but the present invention is not limited thereto.

  Furthermore, the two-photon absorption recording material of the present invention may contain a polymer or oligomer which is a copolymer of a monomer containing an acid generator as described below in its side chain and a monomer containing an acid coloring dye precursor in its side chain. More preferred.

ii) A combination including at least a base color-forming dye precursor as a dye precursor, a base generator, and, if necessary, a base proliferating agent.

  In this case, as the two-photon absorption recording material of the present invention, either the base coloring dye precursor or the base generator is preferably a polymer or oligomer. Both the base coloring dye precursor and the base generator may be polymers or oligomers, and may be copolymers.

In this case, the base generator is a compound capable of generating a base by energy transfer or electron transfer from the excited state of the two-photon absorption compound. The base generator is preferably stable in the dark. The base generator in the present invention is preferably a compound capable of generating a base by electron transfer from the excited state of the two-photon absorption compound.
The base generator of the present invention preferably generates a Bronsted base by light, more preferably generates an organic base, and particularly preferably generates an amine as the organic base.

  The base generator of the present invention is preferably represented by the general formulas (3-1) to (3-4). In addition, you may use these base generators as 2 or more types of mixtures by arbitrary ratios as needed.

In the general formula (3-1) or (3-2), R ₁ and R ₂ 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, n-octadecyl, benzyl, 3-sulfopropyl, 4-sulfobutyl, carboxymethyl, 5-carboxypentyl), an alkenyl group (preferably having 2 to 20 carbon atoms) , For example, vinyl, allyl, 2-butenyl, 1,3-butadienyl), a cycloalkyl group (preferably having 3 to 20 carbon atoms such as cyclopentyl, cyclohexyl), an aryl group (preferably having 6 to 20 carbon atoms such as phenyl 2-chlorophenyl, 4-methoxyphenyl, 3-methylphenyl, 1-naphthyl, 2-naphthyl), heterocyclic group (preferably Or C 1-20, for example, pyridyl, thienyl, furyl, thiazolyl, imidazolyl, pyrazolyl, pyrrolidino, piperidino, morpholino), more preferably a hydrogen atom, an alkyl group, or a cycloalkyl group, More preferably, it represents a hydrogen atom, a methyl group, an ethyl group, a cyclohexyl group, or a cyclopentyl group.
R ₁ and R ₂ may be linked to each other to form a ring, and the heterocycle formed is preferably a piperidine ring, a pyrrolidine ring, a piperazine ring, a morphophorin ring, a pyridine ring, a quinoline ring, or an imidazole ring, More preferred is a piperidine ring, pyrrolidine ring, or imidazole ring, and most preferred is a piperidine ring.
R _1, A more preferable combination of _{R 2, R 1} is substituted by _{R 2} is a hydrogen atom also a good cyclohexyl group, _{R 2} is a hydrogen atom in the alkyl group which may be _{R 1} is _{substituted, R} 1, R ₂ may be linked to form a piperidine ring or an imidazole ring.

  In the general formula (3-1) or (3-2), n1 is 0 or 1, preferably 1.

In General Formula (3-1), each R ₃ independently represents a substituent, and preferred examples of the substituent include 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, carboxymethyl, 5-carboxypentyl), alkenyl group (preferably having 2 to 20 carbon atoms, for example, vinyl, allyl, 2-butenyl) 1,3-butadienyl), a cycloalkyl group (preferably having 3 to 20 carbon atoms, such as cyclopentyl, cyclohexyl), an aryl group (preferably having 6 to 20 carbon atoms, such as phenyl, 2-chlorophenyl, 4-methoxyphenyl, 3-methylphenyl, 1-naphthyl), heterocyclic group (preferably having 1 to 20 carbon atoms such as pyridyl, thie Nyl, furyl, thiazolyl, imidazolyl, 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 (including alkylamino group and arylamino group, preferably C 0-20, for example, amino, dimethylamino, diethylamino, dibutylamino, anilino), cyano group , A nitro group, a hydroxyl group, a mercapto group, a carboxyl group, a sulfo group, a phosphonic acid group, an acyl group (preferably having a C number of 1 to 20, for example, acetyl, benzoyl, salicyloyl, pivaloyl), an alkoxy group (preferably having a C number of 1 -20, for example, methoxy, butoxy, cyclohexyl Xyl), an aryloxy group (preferably C 6-26, such as phenoxy, 1-naphthoxy), an alkylthio group (preferably C 1-20, such as methylthio, ethylthio), an arylthio group (preferably C 6) To 20, for example, phenylthio, 4-chlorophenylthio), an alkylsulfonyl group (preferably having 1 to 20 carbon atoms, for example, methanesulfonyl, butanesulfonyl), an arylsulfonyl group (preferably having 6 to 20 carbon atoms, for example, benzenesulfonyl) , Paratoluenesulfonyl), sulfamoyl group (preferably C 0-20, such as sulfamoyl, N-methylsulfamoyl, N-phenylsulfamoyl), carbamoyl group (preferably C 1-20, such as carbamoyl) N-methylcarbamoyl, N, N-dimethyl Carbamoyl, N-phenylcarbamoyl), acylamino group (preferably C number 1-20, such as acetylamino, benzoylamino), imino group (preferably C number 2-20, such as phthalimino), acyloxy group (preferably C number 1) -20, such as acetyloxy, benzoyloxy), alkoxycarbonyl groups (preferably C 2-20, such as methoxycarbonyl, phenoxycarbonyl), carbamoylamino groups (preferably C 1-20, such as carbamoylamino, N- Methylcarbamoylamino, N-phenylcarbamoylamino), more preferably alkyl group, aryl group, heterocyclic group, halogen atom, amino group, cyano group, nitro group, carboxyl group, sulfo group, alkoxy group, alkylthio. Group, aryl A sulfonyl group, a sulfamoyl group, a carbamoyl group, and an alkoxycarbonyl group.

In the general formula (3-1), R ₃ is preferably a nitro group or an alkoxy group, more preferably a nitro group or a methoxy group, and most preferably a nitro group.
In general formula (3-1), n2 is an integer of 0-5, Preferably it is an integer of 0-3, More preferably, it is 1 or 2. When n2 is 2 or more, the plurality of R ₃ may be the same or different, and may be linked to form a ring. Preferred rings include a benzene ring and a naphthalene ring.
In the general formula (3-1), when R ₃ is a nitro group, it is preferably substituted at the 2-position or 2,6-position, and when R ₃ is an alkoxy group, it is substituted at the 3, 5-position. Is preferred.

In the formula _{(3-1), R 4, R} 5 ( preferably the same as the substituents exemplified in R ₃ as a substituent) Preferred examples each independently represent a hydrogen atom or a substituent R ₃ The hydrogen atom, an alkyl group, or an aryl group, and more preferably any one of a hydrogen atom, a methyl group, and a 2-nitrophenyl group.
R _4, a more preferable combination of _{R 5,} R 4, _{R 5} both hydrogen atoms, _{R 5} is a hydrogen atom in _{R 4} is a methyl _group, R 4, _{R 5} both methyl, _{R 4} is 2-nitrophenyl group R ₅ is a hydrogen atom, and the like, more preferably R ₄ and R _{5 are both} hydrogen atoms.

In the formula _{(3-2), R 6, R} 7 represents a substituent (preferred substituents are the same as the substituents exemplified in R _3), preferably, an alkoxy group, an alkylthio group, a nitro Group and an alkyl group, more preferably a methoxy group.
In General Formula (3-2), n3 and n4 each independently represent an integer of 0 to 5, preferably an integer of 0 to 2. When n3 and n4 are 2 or more, a plurality of R ₆ and R ₇ may be the same or different, and may be linked to form a ring. Preferred examples of the ring formed include a benzene ring and a naphthalene ring. .
In general formula (3-2), R ₆ is more preferably an alkoxy group substituted at the 3,5-position, and even more preferably a methoxy group substituted at the 3,5-position.

In the general formula (3-2), R ₈ represents a hydrogen atom or a substituent (preferably the same as the substituents exemplified in R ₃ as the substituent), preferably a hydrogen atom or an aryl group, More preferably, it is a hydrogen atom.

In the formula (3-3), R ₉ represents a substituent (preferred substituents are the same as the substituents exemplified in R _3), preferably an alkyl group, an aryl group, a benzyl group, an amino group And more preferably an alkyl group which may be substituted, a t-butyl group, a phenyl group, a benzyl group, an anilino group which may be substituted, or a cyclohexylamino group. The compound represented by the general formula (3-3) may be a compound connected from R ₉ in the polymer chain.

In the general formula (3-3), R ₁₀ and R ₁₁ each independently represents a hydrogen atom or a substituent (preferably the same as the substituents exemplified for R ₃ as a substituent), preferably an alkyl group. Or an aryl group is represented, More preferably, a methyl group, a phenyl group, and 2-naphthyl group are represented.
R ₁₀ and R ₁₁ may be connected to each other to form a ring. As the ring to be formed, for example, a fluorene ring is preferable.

In General Formula (3-4), R ₁₂ represents an aryl group or a heterocyclic group, and more preferably the following aryl group or heterocyclic group.

In General Formula (3-4), R ₁₃ , R ₁₄ , and R ₁₅ are each independently a hydrogen atom, an alkyl group, an alkenyl group, a cycloalkyl group, an aryl group, or a heterocyclic group (above preferred examples are R ₁ , R _The same as ₂ ), preferably an alkyl group, more preferably a butyl group. R ₁₃ , R ₁₄ and R ₁₅ may be linked to each other to form a ring, and preferably a hetero ring formed is preferably a piperidine ring, a pyrrolidine ring, a piperazine ring, a morphophore ring, a pyridine ring, a quinoline ring, an imidazole. A ring, more preferably a piperidine ring, a pyrrolidine ring, and an imidazole ring.

In the general formula (3-4), R ₁₆ , R ₁₇ , R ₁₈ and R ₁₉ each independently represents an alkyl group or an aryl group, R ₁₆ , R ₁₇ and R ₁₈ are phenyl groups, and R ₁₉ is It is more preferably an n-butyl group or a phenyl group.

  The base generator of the present invention is preferably represented by the general formula (3-1) or (3-3), and more preferably represented by the general formula (3-1).

  When the base generator is a polymer or oligomer, it may be a polymer or oligomer containing a base generator in the main chain, or a polymer or oligomer containing a base generator in the side chain. It is preferable that the polymer is a polymer or oligomer containing a base generator. In the case of a polymer or oligomer containing a base generator in the side chain, even if the base generator is a copolymer of two or more monomers contained in the side chain, the monomer in which the base generator is contained in the side chain And a copolymer of monomers not containing a base generator.

  Although the preferable specific example in case the base generator of this invention is not a polymer or an oligomer is shown below, this invention is not limited to this.

  Preferable examples of the base generator include those described in Japanese Patent Application No. 2003-178083.

  Next, when the base generator in the two-photon absorption recording material of the present invention is a polymer or oligomer, the base generator is preferably a polymer or oligomer contained in the main chain or side chain.

  Among them, particularly preferred base generator polymers or oligomers are listed below, but the present invention is not limited thereto.

  It is also preferable to use a base proliferating agent from the viewpoint of increasing sensitivity. Specific examples of preferred base proliferating agents include those described in JP-A-2005-177354.

Next, the base color-forming dye precursor will be described.
When the base coloring dye precursor is a polymer or oligomer, the polymer or oligomer containing the base coloring dye precursor in the side chain even if it is a polymer or oligomer containing the base coloring dye precursor in the main chain However, it is preferably a polymer or oligomer containing a base color-forming dye precursor in the side chain. In the case of a polymer or oligomer containing a base coloring dye precursor in the side chain, the base coloring dye precursor is on the side even if the base coloring dye precursor is two or more types of polymers contained in the side chain. It may be a copolymer of monomers contained in the chain and monomers not containing the base color-forming dye precursor.

Base coloring dye precursors include dissociated azo dyes, dissociated azomethine dyes, dissociated benzylidene dyes, dissociated oxonol dyes, dissociated xanthene dyes, dissociated fluorane dyes, and dissociated triphenylmethane dyes. Preferably, non-dissociated forms of dissociable azo dyes, dissociable oxonol dyes, and dissociable benzylidene dyes are used.
Preferable specific examples when the base color developing dye precursor is not a polymer or oligomer are given below, but the present invention is not limited thereto.

  Next, when the base color-forming dye precursor in the two-photon absorption recording material of the present invention is a polymer or oligomer, the base color-forming dye precursor may be a polymer or oligomer contained in the main chain or side chain. preferable.

  In the following, particularly preferred base color-forming dye precursor polymers or oligomers are listed, but the present invention is not limited thereto.

  Further, the two-photon absorption recording material of the present invention may contain a polymer or oligomer which is a copolymer of a monomer containing a base generator as described below in its side chain and a monomer containing a base coloring dye precursor in its side chain. More preferred.

iii) an organic compound portion having a function of breaking a covalent bond by electron transfer or energy transfer with an excited state of a two-photon absorption compound, and an organic compound having a feature that becomes a color former when covalently bonded and released Including compounds where the moiety is covalently bonded. A combination further containing a base if necessary. Particularly preferred specific examples are listed below, but the present invention is not limited thereto.

Further, the compound is preferably a coloring pigment precursor polymer or oligomer represented by the following general formula (1).
General formula (1)
(A1-PD) m1

In general formula (1), A1 and PD are covalently bonded, and A1 is a site having a function of breaking the covalent bond with PD by electron transfer or energy transfer with the excited state of the two-photon absorption compound. It represents a site that can cause a color reaction when the covalent bond with A1 is cleaved and released.
In the general formula (1), either A1 or PD is connected to each other through a covalent bond to form a polymer or oligomer, and m1 represents an integer of 3 to 1,000,000.

  In the general formula (1), PD is a group composed of any one of a dissociation azo dye, a dissociation azomethine dye, a dissociation oxonol dye, a dissociation benzylidene dye, a triphenylmethane dye, and a xanthene dye. And PD is preferably a dissociable azo dye or dissociable benzylidene dye.

  Preferable examples of the color-forming dye precursor polymer or oligomer of the present invention represented by the general formula (1) are shown below, but the present invention is not limited thereto.

iv) When a compound that reacts by electron transfer with an excited state of a two-photon absorption compound and can change the absorption form is included. So-called electrochromic compounds can be preferably used. The electrochromic compound is preferably a polymer or an oligomer.

  In the method of recording by 1) coloring method of the present invention, it is more preferable that a binder polymer is further included in addition to the two-photon absorption compound and the recording component. Preferable examples include binder polymers described later in the description of the polymerization-sensitive reaction and examples described in JP-A Nos. 2005-99751 and 2005-71570.

3) Latent image color development—Recording by color former self-sensitized amplification color development reaction

  Preferably, at least a first step of generating a color body having an absorption form different from that of the two-photon absorption compound as a latent image by two-photon absorption exposure, and two-photon absorption compound linear (one-photon) absorption in the color body latent image The color developing body is self-sensitized and amplified by irradiating light in the wavelength range where the molar extinction coefficient is 5000 or less to cause linear absorption of the color forming body, and formed as a difference in refractive index, difference in absorption rate or difference in emission intensity. A two-photon absorption optical recording method, which is preferable in terms of high-speed writing, high S / N ratio reproduction, and the like.

  Here, the “latent image” means “a refractive index difference, an absorptivity difference, or a luminescence intensity difference that is preferably half or less of a difference in refractive index, an absorptivity difference, or a luminescence intensity difference formed after the second step”. "Difference" (that is, preferably an amplification step of 2 times or more is performed in the second step), more preferably 1/5 or less, further preferably 1/10 or less, and most preferably 30. An image having a refractive index, absorptivity or emission intensity difference image of 1 or less (that is, an amplification step of preferably 5 times or more, more preferably 10 times or more, most preferably 30 times or more in the second step). To be done).

Here, the second step is preferably light irradiation, heat application, or both, more preferably light irradiation, and the light to be irradiated is the entire surface exposure (so-called solid exposure, blanket exposure, non-image). Wise exposure) is preferable.
Preferred examples of the light source to be used include a visible light laser, an ultraviolet light laser, an infrared light laser, a carbon arc, a high pressure mercury lamp, a xenon lamp, a metal halide lamp, a fluorescent lamp, a tungsten lamp, an LED, and an organic EL. In order to irradiate light in a specific wavelength range, it is also preferable to use a sharp cut filter, a band pass filter, a diffraction grating, or the like as necessary.

Furthermore, as a two-photon absorption recording material capable of such a two-photon recording method,
at least,
1) a two-photon absorption compound capable of absorbing two photons and generating an excited state in the first step;
2) including a dye precursor that can be a color former that has a longer wavelength than the original state and has absorption in a wavelength range different from the linear absorption of the two-photon absorption compound; Recording component that can be recorded as a difference in refractive index, a difference in absorption rate or a difference in emission intensity by electron transfer or energy transfer
It is preferable to contain.
Furthermore, it is more preferable that a binder polymer is included. Preferable examples of the binder polymer include those described in JP-A Nos. 2005-71570 and 2005-99751.
Preferred examples of the recording component are the same as those described in 2) Color development reaction.
In the wavelength range of the light irradiated in the second step, the molar absorption coefficient of linear absorption of the two-photon absorption compound is more preferably 1000 or less, and further preferably 500 or less.
In the wavelength range of the light irradiated in the second step, it is more preferable that the molar extinction coefficient of the color former is 1000 or more.

The concept of “latent image color development—colored body self-sensitized amplification color reaction system” will be described below.
For example, a two-photon absorption recording material is irradiated with a 780 nm laser, and a two-photon absorption compound is absorbed two-photons to generate an excited state. By transferring energy or electrons from the excited state of the two-photon absorption compound to the recording component, the dye precursor contained in the recording component is changed to a color former to form a latent image by color development (the first step). Next, light in a wavelength range of 680 to 740 nm is irradiated to cause linear absorption of the color former, and the color former is amplified and generated by self-sensitization of the color former (the second step). In the first process, a latent image is not generated in an unrecorded part that is not a laser focal part, so that a self-sensitized color development reaction hardly occurs in the second process. Absorption rate modulation or emission intensity modulation can be formed. For example, by using a 780 nm laser again and irradiating the recorded two-photon absorption recording material, it becomes possible to reproduce the light based on the difference in reflectance or transmittance of light based on a large difference in refractive index between the recording part and the non-recording part. A two-photon absorption (three-dimensional) optical recording medium by 780 nm optical recording / reproduction can be provided.

  Specific examples of the latent image color development-chromogen self-sensitized amplification color development reaction are preferably the examples described in JP-A-2005-100599.

4) Latent image color development—Recording by color development sensitized polymerization reaction

Preferably, at least the first step of generating a color former as a latent image by two-photon absorption and the polymerization based on the linear absorption of the color former by irradiating light to the color former latent image It is a two-photon absorption optical recording method characterized by having a second step of recording by forming a difference, and is excellent in high-speed writing, storability and the like.
In the second step, a method in which polymerization is caused while self-sensitizing amplification production is performed is also preferable.

Furthermore, as a group of compounds for which such a two-photon absorption recording method is possible,
at least,
1) a two-photon absorption compound capable of absorbing two photons and generating an excited state in the first step;
2) Absorption is increased in wavelength from the original state by transferring electrons or energy from the excited state of the two-photon absorption compound in the first step or from the excited state of the color former in the second step, and two-photon absorption. A group of dye precursors capable of becoming a color former having absorption in a wavelength range of 5000 or less in the linear absorption molar absorption coefficient of the compound;
3) a polymerization initiator capable of initiating polymerization of the polymerizable compound by transferring electrons or energy from the colored body excited state in the second step,
4) a polymerizable compound,
5) binder,
It is preferable to contain.
Preferred examples of the recording component are the same as those described in 2) Color development reaction.
Preferred examples of the polymerization initiator, the polymerizable compound and the binder are the same as those described in 1) polymerization reaction.
In the wavelength range of the light irradiated in the second step, the molar absorption coefficient of linear absorption of the two-photon absorption compound is more preferably 1000 or less, and further preferably 500 or less.
In the wavelength range of the light irradiated in the second step, it is more preferable that the molar extinction coefficient of the color former is 1000 or more.

  Hereinafter, preferable examples of the polymerization initiator, the polymerizable compound, and the binder will be described.

The binder preferably has a refractive index different from that of the polymerizable compound. 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, and the refractive index difference is preferably 0.01 or more, more preferably 0.05 or more. Preferably, it is 0.1 or more.
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. It is preferable. It does not matter whether the polymerizable compound has a higher refractive index or the binder has a higher refractive index.

The polymerizable compound of the present invention is a radical, acid (Bronsted acid or Lewis acid) or base (Bronsted base or Lewis acid) generated by irradiating light to a two-photon absorption compound (or color former) and a polymerization initiator. It is a compound that can be oligomerized or polymerized by addition polymerization with a base.
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 or anionic polymerization.
In the following, for each of the polymerizable compound capable of radical polymerization and the polymerizable compound capable of cationic or anion polymerization, A) refractive index: polymerizable compound> binder, and B) refractive index: binder> polymerizable compound. In particular, examples of preferred 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, 2- (p-chlorophenoxy) ethyl acrylate, benzyl acrylate, 2- (1-naphthyloxy) ethyl acrylate, 2,2-di (p-hydroxyphenyl) propane diacrylate or di Methacrylate, di (2-methacryloxyethyl) ether of bisphenol-A, di (2-acryloxyethyl) ether of bisphenol-A, di (2-methacryloxyethyl) ether of tetrachloro-bisphenol-A, tetrabromo-bisphenol Di- (2-methacryloxyethyl) ether of Ru-A, 1,4-benzenediol dimethacrylate, 1,4-diisopropenylbenzene, and the like, more preferably 2-phenoxyethyl acrylate, methacrylic acid 2 -Phenoxyethyl, 2- (p-chlorophenoxy) ethyl acrylate, p-chlorophenyl acrylate, phenyl acrylate, 2-phenylethyl acrylate, bisphenol-A di (2-acryloxyethyl) ether, acrylic acid 2 -(1-naphthyloxy) ethyl and the like can be mentioned.

  Preferred polymerizable compounds are liquids, but they are N-vinylcarbazole, 2-naphthyl acrylate, pentachlorophenyl acrylate, 2,4,6-tribromophenyl acrylate, bisphenol-A diacrylate, 2-acrylate. It may be used in admixture with (2-naphthyloxy) ethyl and a second solid polymerizable compound such as N-phenylmaleimide.

B) Refractive index: Preferable example of radically 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, 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, glycerol diacrylate, trimethylol Propane diacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, triethylene glycol diacrylate, triethylene Recall dimethacrylate, ethylene glycol dimethacrylate, 1,3-propanediol dimethacrylate, 1,2,4-butanetriol trimethacrylate, 2,2,4-trimethyl-1,3-propanediol dimethacrylate, pentaerythritol trimethacrylate , Pentaerythritol tetramethacrylate, trimethylolpropane trimethacrylate, 1,5-pentanediol dimethacrylate, diallyl fumarate, acrylic acid 1H, 1H-perfluorooctyl, methacrylic acid 1H, 1H, 2H, 2H-perfluorooctyl, acrylic Acids 1H, 1H, 2H, 2H-perfluorooctyl, 1-vinyl-2-pyrrolidinone and the like, more preferably decanediol diacrylate, iso-bornyl acrylate, triethylene group Examples thereof include coal diacrylate, diethylene glycol diacrylate, triethylene glycol dimethacrylate, ethoxyethoxyethyl acrylate, triacrylate ester of ethoxylated trimethylolpropane, and 1-vinyl-2-pyrrolidine. Acrylate, iso-bornyl acrylate, triethylene glycol diacrylate, diethylene glycol diacrylate, triethylene glycol dimethacrylate, ethoxyethoxyethyl acrylate, 1H, 1H-perfluorooctyl acrylate, 1H, 1H, 2H, 2H-methacrylic acid Examples include perfluorooctyl, acrylic acid 1H, 1H, 2H, 2H-perfluorooctyl, and 1-vinyl-2-pyrrolidine.

  The preferred 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 irradiating the two-photon absorbing compound and the cationic polymerization initiator with light, and the anionic polymerizable compound of the present invention is a two-photon absorbing compound and It is a compound in which polymerization is initiated by a base generated by irradiating an anionic polymerization initiator with light.

The cation polymerizable compound of the present invention is preferably a compound having at least one oxirane ring, oxetane ring, vinyl ether group, styrene group or N-vinyl carbazole moiety in the molecule, more preferably a compound having an oxirane ring moiety. is there.
The anionic polymerizable compound of the present invention is preferably an oxirane ring, an oxetane ring, a vinyl ether group, a styrene group, an N-vinylcarbazole moiety, an ethylenic double bond moiety having an electron-withdrawing substituent, a lactone moiety, a lactam moiety, A compound having at least one cyclic urethane moiety, cyclic urea moiety, or cyclic siloxane moiety in the molecule, and more preferably a compound having an oxirane ring moiety.

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

  In this case, the cation or anion polymerizable compound preferably has a high refractive index, and the high refractive index cation or anion polymerizable compound of the present invention includes at least one oxirane ring, oxetane ring, vinyl ether group, N-vinylcarbazole. A compound having a moiety in the molecule and further containing at least one aryl group, aromatic heterocyclic group, chlorine atom, bromine atom, iodine atom or 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 cation or anion polymerizable monomer having an oxirane ring is phenyl glycidyl ether, phthalic acid diglycidyl ester, trimellitic acid triglycidyl 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-diglycidyl Ether, 1,3-bis (3 ′, 4′-epoxycyclohexyl) ethyl) -1,3, -diphenyl-1,3-dimethyldisiloxane, and the like. I can get lost.

  Specific examples of the high refractive index cation or anion polymerizable monomer having an oxetane ring include compounds in which the oxirane ring in the specific examples of the high refractive index cation or anion polymerizable monomer having an oxirane ring is replaced with an oxetane ring. It is done.

  Specific examples of the high refractive index cation or anion 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, and tetrabromobisphenol A. Examples thereof include divinyl ether, bisphenol F divinyl ether, phenoxyethylene vinyl ether, and p-bromophenoxyethylene vinyl ether.

  In addition, styrenes such as N-vinylcarbazole, styrene, 2-chlorostyrene, 2-bromostyrene, and methoxystyrene are also preferable as the high refractive index cation or anion polymerizable monomer.

B) Refractive index: Preferable example of cationic or anionic polymerizable compound in the case of binder> polymerizable compound

  In this case, the cation or anion polymerizable compound preferably has a low refractive index, and the low refractive index cation or anion polymerizable compound of the present invention includes at least one oxirane ring, oxetane ring, vinyl ether group, N-vinylcarbazole. A compound having a moiety in the molecule and further containing no aryl group, aromatic heterocyclic group, chlorine atom, bromine atom, iodine atom or 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 cation or anion polymerizable monomer having an oxirane ring include glycerol diglycidyl ether, glycerol triglycidyl ether, pentaerythritol polyglycidyl ether, trimethylolpropane triglycidyl ether, 1,6-hexanediol. Diglycidyl ether, ethylene glycol diglycidyl ether, ethylene glycol monoglycidyl ether, propylene glycol diglycidyl ether, neopentyl glycol diglycidyl ether, adipic acid diglycidyl ester, 1,2,7,8-diepoxyoctane, 1, 6-dimethylol perfluorohexane diglycidyl ether, vinylcyclohexene dioxide, 3,4-epoxycyclohexylmethyl-3 ', 4'-epoxy Chlohexanecarboxylate, 3,4-epoxycyclohexyloxirane, bis (3,4-epoxycyclohexyl) adipate, 2,2-bis [4- (2,3-epoxypropoxy) cyclohexyl] propane, 2,2-bis [ 4- (2,3-epoxypropoxy) cyclohexyl] hexafluoropropane, 2- (3,4-epoxycyclohexyl) -3 ′, 4′-epoxy-1,3-dioxane-5-spirocyclohexane, 1,2- Ethylenedioxy-bis (3,4-epoxycyclohexylmethane), ethylene glycol-bis (3,4-epoxycyclohexanecarboxylate), bis- (3,4-epoxycyclohexylmethyl) adipate, di-2,3-epoxy Cyclopentyl ether, vinyl glycidyl ether, allyl glycidyl ether , 2-ethylhexyl glycidyl ether, 1,3-bis (3 ', 4'-epoxycyclohexyl) ethyl) -1,1,3,3, - tetramethyl disiloxane and the like.

  Specific examples of the low refractive index cation or anion polymerizable monomer having an oxetane ring include compounds in which the oxirane ring in the specific examples of the low refractive index cation or anion polymerizable monomer having an oxirane ring is replaced with an oxetane ring. It is done.

  Specific examples of the low refractive index cationic or anionic 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, neo Pentyl glycol divinyl glycol, glycerol divinyl ether, glycerol trivinyl ether, triethylene glycol divinyl ether, trimethylolpropane monovinyl ether, trimethylolpropane divinyl ether, trimethylolpropane trivinyl ether, allyl vinyl ether, 2,2-bis (4-cyclohexanol ) Propane divinyl ether, 2,2-bis (4-cyclohexanol) trifluoro Examples thereof include propane divinyl ether.

  Next, examples of preferred binders in the present invention at the time of recording by polymerization reaction include A) refractive index: polymerizable compound> binder and B) refractive index: binder> polymerizable compound. explain.

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

In this case, the binder preferably has a low refractive index, and is preferably a binder containing no aryl group, aromatic heterocyclic group, chlorine atom, bromine atom, iodine atom, or sulfur atom.
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 an average molecular weight of approximately 4,000 to 1,000,000 (for example, epoxides having acrylate or methacrylate groups) Polyamide (for example, N-methoxymethyl polyhexamethylene adipamide), cellulose ester (for example, cellulose acetate, cellulose acetate succinate and cellulose acetate butyrate), cellulose ether (for example, methyl cellulose, ethyl cellulose, ethyl benzyl cellulose), polycarbonate , Polyvinyl acetal (for example, polyvinyl butyral and polyvinyl formal), polyvinyl alcohol, polyvinyl pyrrolidone, and the like.

  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.

  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.

Also, preferred examples include silicon compounds such as poly (dimethylsiloxane) and silicon oils that do not contain aromatics.
In addition, an epoxy oligomer compound containing no aromatic can also be used as a low refractive index reactive binder.

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

In this case, the binder preferably has a high refractive index, and is preferably a binder containing at least one aryl group, aromatic heterocyclic group, chlorine atom, bromine atom, iodine atom, or sulfur atom. More preferably, the binder is included.
Specific examples of preferred high refractive index binders include polystyrene polymers and copolymers such as acrylonitrile, maleic anhydride, acrylic acid, methacrylic acid and esters thereof, vinylidene chloride copolymers (eg, vinylidene chloride / acrylonitrile copolymer). Polymers, vinylidene chloride / methacrylate copolymers, vinylidene chloride / vinyl acetate copolymers), polyvinyl chloride and copolymers (eg, polyvinyl chloride / acetate, vinyl chloride / acrylonitrile copolymers), 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 copolymers), copolyesters (eg, polymethylene glycols of the formula HO (CH ₂ ) nOH (where n is an integer from 2 to 10), and ( 1) manufactured 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 a copolymer thereof, a polycarbonate composed of carbonate ester and bisphenol, and the like.

Preferable examples include poly (methylphenylsiloxane), silicon compounds such as 1,3,5-trimethyl-1,1,3,5,5-pentaphenyltrisiloxane, silicon oil containing a large amount of aromatics, and the like. .
In addition, an epoxy oligomer compound containing a large amount of aromatics can also be used as a high refractive index reactive binder.

  The polymerization initiator used for recording by the polymerization reaction of the present invention is preferably a ketone, an organic peroxide, a trihalomethyl-substituted triazine, a diazonium salt, a diaryliodonium salt, a sulfonium salt, a borate, or a diaryl. Radical polymerization of any of iodonium organic boron complex, sulfonium organic boron complex, cationic two-photon absorption compound, organic boron complex, anionic two-photon absorption compound, onium salt complex, metal arene complex, or sulfonate ester An agent (radical generator) or a cationic polymerization initiator (acid generator), or a compound having both functions.

  At that time, it is also preferable to use an acid proliferating agent from the viewpoint of high sensitivity. Specific examples of the acid proliferating agent include, for example, JP-A-2005-17730.

  Further, it is also preferable to use anionic polymerization and an anionic polymerization initiator (base generator). In that case, it is also preferable to use a base proliferating agent from the viewpoint of high sensitivity. In these cases, specific examples of the anionic polymerization initiator and the base proliferating agent include those described in JP-A-2005-17354.

  Specific examples of preferred polymerization initiators, polymerizable compounds and binders according to the present invention include those described in JP-A-2005-97538.

  Specific examples of preferred radical polymerization initiators in the present invention are listed below, but the present invention is not limited thereto.

Further, preferred specific examples of the cationic polymerization initiator or the cationic polymerization initiator / radical polymerization initiator of the present invention include 1) the above-mentioned acid generators in the color development reaction.
Further, preferred specific examples of the anionic polymerization initiator of the present invention include 1) the aforementioned base generator in the color development reaction.

  In the two-photon absorption optical recording method of the present invention and the two-photon absorption recording material capable of such recording, fixing by the first step, the second step, or subsequent light irradiation, heat application, or both. It is preferable in terms of storage stability and nondestructive regeneration to decompose and fix the two-photon absorption compound by any of the steps, and further, in the first step, the second step, or subsequent light irradiation, heat application, Alternatively, the two-photon absorbing compound can be decomposed and fixed by either the second step, or the fixing step by the subsequent light irradiation, heat application, or both by the fixing step by both of them. More preferred.

The concept of “latent image color development-colored material sensitized polymerization reaction system” will be described below.
For example, a two-photon absorption recording material is irradiated with a 780 nm laser, and the two-photon absorption compound absorbs the two-photon absorption recording material to generate an excited state. By transferring energy or electrons from the excited state of the two-photon absorption compound to the dye precursor group, the dye precursor contained in the dye precursor group is changed to a color former to form a latent image by color development (the first is described above). Process). Next, light in the wavelength region of 680-740 nm is irradiated to cause linear absorption of the color former, and the polymerization initiator is activated by electron transfer or energy transfer to initiate polymerization. For example, when the polymerizable compound has a higher refractive index than the binder, the refractive index increases because the polymerizable compound collects in the portion where the polymerization occurs (second step). In the first step, a latent image is not generated in an unrecorded portion that is not a laser focus portion, so that polymerization does not occur so much in the second step, and the abundance ratio of the binder is increased. As a result, the recorded portion and the non-recorded portion Refractive index modulation can be formed at. Provided is a colorless and transparent two-photon absorption recording material excellent in nondestructive reproduction and storability if the two-photon absorption compound and the colored body can be decomposed and decolored by the first and second steps or further fixing step. be able to.
For example, when a 780 nm laser is used again and the recorded two-photon absorption recording material is irradiated, reproduction based on the difference in the reflectance or transmittance of light based on the difference in refractive index between the recording portion and the non-recording portion becomes possible. A photon absorption (three-dimensional) optical recording medium can be provided.

  Specific examples of the latent image color development-colored material sensitization polymerization reaction preferably include those described in JP-A-2005-97538.

4) Recording by decoloring reaction

Preferably, the recording method has at least one or more decolorable dyes, and the decolorant dyes are decolored by two-photon absorption, and recording is performed by refractive index or absorptance modulation, or emission intensity difference.
When recording is performed using a difference in refractive index, the refractive index of the decolorizable dye is preferably maximized in the vicinity of the laser wavelength used for reproduction.
In the case of recording using a difference in emission intensity, it is preferable that there is a difference in emission intensity between the decolorizable dye and its decolored body when light having a certain wavelength is irradiated during reproduction.

  The decolorizable dye in the present invention has absorption in the ultraviolet, visible and infrared regions of 200 to 2000 nm, and λmax is shortened directly or indirectly by light irradiation. The generic name of the dye that causes any decrease in the coefficient is shown, and more preferably, the dye causes both. Moreover, it is more preferable that the decoloring reaction occurs in a wavelength region of 200 to 1000 nm, and it is further preferable that the decoloring reaction occurs in a wavelength region of 300 to 900 nm.

As a preferred recording method,
(A) A recording method using the decolorizable dye itself being a two-photon absorption compound and decoloring itself by two-photon absorption.
(B) At least a two-photon absorption compound and a two-photon absorption compound, and a two-photon recording wavelength molar extinction coefficient of 1000 or less, preferably 100 or less, have a decolorizable dye, and are generated during two-photon absorption. A recording method using decolorization of a decolorizable dye by electron transfer or energy transfer from an excited state of a two-photon absorption compound.
Is mentioned.

  Furthermore, after having a decoloring agent precursor different from the decoloring dye and the two-photon absorption compound, the decoloring agent precursor after the two-photon absorption compound or the decoloring dye generates an excited state by two-photon absorption Also preferred is a recording method in which a decoloring agent is generated from the decoloring agent precursor by energy transfer or electron transfer, and the decoloring agent decolorizes the decolorable dye. In that case, the decolorizer is preferably any one of radical, acid, base, nucleophile, electrophile, and singlet oxygen. Therefore, the decolorizer precursor is a radical generator, acid generator, base. It is preferably any of a generator, a nucleophile generator, an electrophile generator, and triplet oxygen. The decoloring precursor is more preferably any of a radical generator, an acid generator and a base generator.

  In the recording method using the decoloring method 4) of the present invention, at least one of the two-photon absorption compound, the decoloring dye, and the decoloring agent precursor is a polymer or an oligomer. More preferably, at least one of the colorant precursors is a polymer or oligomer, and both the decolorizable dye and the decolorizer precursor may be a polymer or oligomer, and may be a copolymer.

  In any case, it is more preferable to further include a binder polymer. Examples of the binder polymer include 1) the examples described above in the description of the polymerization reaction, and JP-A-2005-71570 and JP-A-2005-99751. Preferred examples are given.

  Next, in the “dye decolorization reaction method”, a decolorizable dye for forming a difference in refractive index, a difference in absorptivity, or a difference in light emission intensity between the laser focus portion and the non-focus portion is described in detail.

In the above-described method (A), since the two-photon absorbing compound serves as a decolorizable dye, a preferable example of the decolorable dye includes the two-photon absorbing compound described above.
Λmax of the decolorizable dye is preferably between the two-photon recording light wavelength and the wavelength region shorter by 300 nm from the two-photon recording wavelength.

On the other hand, in the above-described method (B), a decolorizable dye is used separately from the two-photon absorption compound. In that case, the decolorizable dye preferably has a molar extinction coefficient of two-photon recording light wavelength of 1000 or less, more preferably 100 or less, and most preferably 0.
Λmax of the decolorizable dye is preferably between the two-photon recording light wavelength and a wavelength region shorter by 300 nm from the two-photon recording wavelength.

In the method (B), the decolorizable dye is preferably a cyanine dye, squarylium cyanine dye, styryl dye, pyrylium dye, merocyanine dye, benzylidene dye, oxonol dye, coumarin dye, pyran dye, xanthene dye, thiol. Xanthene dye, phenothiazine dye, phenoxazine dye, phenazine dye, phthalocyanine dye, azaporphyrin dye, porphyrin dye, condensed ring aromatic dye, perylene dye, azomethine dye, azo dye, anthraquinone dye, metal complex dye More preferably, any of a cyanine dye, a styryl dye, a merocyanine dye, a benzylidene dye, an oxonol dye, a coumarin dye, a xanthene dye, an azomethine dye, an azo dye, and a metal complex dye.

In the two-photon absorption optical recording material capable of recording by the decoloring method of B), it is preferable that the following components are included in addition to the two-photon absorption compound and the binder.
i) A combination comprising at least an acid decolorizable dye and an acid generator.
ii) A combination comprising at least a base decolorizable dye and a base generator.
iii) The following decolorizable dyes which can be decolored as a result of bond breakage due to electron transfer or energy transfer with the excited state of the two-photon absorption compound.
Each will be described in detail below.

i) A combination comprising at least an acid decolorizable dye and an acid generator.

When the decolorizer is an acid, that is, when the decolorizer precursor is an acid generator, the decolorizable dye is a dissociable benzylidene dye, dissociable oxonol dye, dissociable xanthene dye as an acid decolorizable dye. It is preferably a dissociated form of a dissociable azo dye, and more preferably a dissociated form of a dissociable benzylidene dye, dissociated oxonol dye, or dissociable azo dye. Here, the dissociative dye has an active hydrogen having a pKa in the range of about 2 to 14, such as —OH group, —SH group, —COOH group, —NHSO ₂ R group, —CONHSO ₂ R group, etc. Is a general term for dyes whose absorption becomes longer in wavelength or higher in ε due to dissociation. Therefore, if the dissociation type dye is treated with a base in advance to obtain a dissociation type, it is possible to prepare a dye having a long wavelength or a high ε in advance, and it is changed to a non-dissociation type by photoacid generation and is decolored (short wavelength Or low ε).

  In that case, it is preferable that at least one of the acid generators as the acid decolorizable dye or the decolorizer precursor is a polymer or oligomer, and both the acid decolorizable dye and the acid generator are polymers or oligomers. It may be preferable, and may be a copolymer.

  Preferred examples when the acid generator is a polymer or an oligomer include those described in 1) Coloring reaction.

  Next, when the acid decolorizable dye is a polymer or oligomer, even if it is a polymer or oligomer containing an acid decolorable dye in the main chain, it is a polymer or oligomer containing an acid decolorable dye in the side chain. Although it may be present, it is preferably a polymer or oligomer containing an acid decoloring dye in the side chain. In the case of a polymer or oligomer containing an acid decoloring dye in the side chain, the acid decoloring dye even if the acid decoloring dye is a copolymer of two or more monomers contained in the side chain May be a copolymer of a monomer contained in the side chain and a monomer containing no acid decolorizable dye.

  Specific examples when the acid decolorizable dye of the present invention is not a polymer or oligomer are given below, but the present invention is not limited thereto.

  Next, when the acid decolorizable dye in the two-photon absorption recording material of the present invention is a polymer or oligomer, the acid decolorable dye is preferably a polymer or oligomer contained in the main chain or side chain.

  Particularly preferred acid decolorizable dye polymers or oligomers are listed below, but the present invention is not limited thereto.

  Further, the two-photon absorption recording material of the present invention may further comprise a polymer or oligomer which is a copolymer of a monomer containing an acid generator as described below in the side chain and a monomer containing an acid decoloring dye in the side chain. preferable.

ii) A combination comprising at least a base decolorizable dye and a base generator.

  When the decolorizer is a base, that is, when the decolorizer precursor is a base generator, triphenylmethane dye, xanthene dye, fluorane dye, and protonation to cyanine base that have been treated with acid in advance to form a color former If an acid color-developing color developing material such as a cyanine dye is used as a base decoloring color, it can be changed to an aprotic adduct by photobase generation and decolored (short wavelength or low ε).

  At that time, it is preferable that at least one of the base decoloring dye or the base generator as a decoloring agent precursor is a polymer or oligomer, and both the base decoloring dye and the base generator are polymers or oligomers. It may be preferable, and may be a copolymer.

  Preferred examples when the base generator is a polymer or an oligomer include those described in 1) Coloring reaction.

  Next, when the base decoloring dye is a polymer or oligomer, even if it is a polymer or oligomer containing a base decoloring dye in the main chain, it is a polymer or oligomer containing a base decoloring dye in the side chain. Although it may be, it is preferably a polymer or oligomer containing a base decolorizable dye in the side chain. When the side chain is a polymer or oligomer containing a base decoloring dye, even if the base decoloring dye is a copolymer of two or more monomers contained in the side chain, the base decoloring dye May be a copolymer of a monomer contained in the side chain and a monomer containing no base decolorizable dye.

  Specific examples when the base decolorizable dye of the present invention is not a polymer or oligomer are given below, but the present invention is not limited thereto.

  Next, when the base decolorizable dye in the two-photon absorption recording material of the present invention is a polymer or oligomer, the base decolorable dye is preferably a polymer or oligomer contained in the main chain or side chain.

  In the following, particularly preferred base decolorizable dye polymers or oligomers are listed, but the present invention is not limited thereto.

  Furthermore, the two-photon absorption recording material of the present invention may contain a polymer or oligomer which is a copolymer of a monomer containing a base generator as described below in the side chain and a monomer containing a base decoloring dye in the side chain. preferable.

iii) The following decolorizable dyes which can be decolored as a result of bond breakage due to electron transfer or energy transfer with the excited state of the two-photon absorption compound.

As the decolorizable dye of the present invention, the decolorization that can be decolored as a result of electron transfer or energy transfer from the excited state of the two-photon absorption compound generated by two-photon recording, preferably by electron transfer. The example of a sex pigment can also be mentioned preferably.
The following examples are preferred as such decolorizable dyes. However, the decolorizable dye of the present invention is not limited to this.
These decolorizable dyes are originally cyanine dyes, but they are changed to cyanine bases (leucocyanine dyes) due to bond breakage by electron transfer, and absorption decolorization or shortening of wavelengths occurs.

Further, the compound is preferably a decolorizable dye polymer or oligomer represented by the following general formula (2).
General formula (1)
(A2-DD) m1

In the general formula (2), A2 and DD are covalently bonded, and A2 is a site having a function of cleaving the covalent bond with DD by electron transfer or energy transfer with the excited state of the two-photon absorption compound. A site that is a dye when covalently bound to A2 is decolored when the covalent bond is cleaved and released.
In the general formula (2), either A2 or DD is connected to each other through a covalent bond to form a polymer or oligomer, and m2 represents an integer of 3 to 1,000,000.
In the general formula (2), DD is a group comprising a cyanine base, and is preferably covalently linked to A1 on the chromophore.
Although the preferable example of the decolorizable pigment | dye polymer or oligomer of this invention represented by General formula (2) below is given, this invention is not necessarily limited to this.

  Specific examples of the color erasing method, color erasable colorant, color erasing agent and the like preferably include the examples described in JP-A-2005-55875 as the type (A), and the type (B). Is preferably an example described in Japanese Patent Application No. 2004-264202.

5) Residual color erasable dye latent image-latent image sensitized polymerization reaction

Preferably, after the two-photon absorption compound generates an excited state by two-photon absorption, the molar absorption coefficient of the two-photon recording wavelength is 1000 or less, preferably 100 or less, and most preferably 0, using the excitation energy. A first step of decolorizing the dye and using the remaining decolorizable dye that has not been decolored as a latent image, and irradiating the remaining decolorizable dye latent image with light having a wavelength different from the two-photon recording wavelength Is a recording method characterized in that it has a second step of recording as a refractive index modulation, and is excellent in high-speed recording, suitability for multiple recording, storability after recording, and the like.
Further, after the two-photon absorption compound generates an excited state by two-photon absorption, the decolorizer is generated from the decolorizer precursor by energy transfer or electron transfer with the decolorizer precursor described in 6), A first step in which the decolorizable dye decolorizes the decolorizable dye to form a residual decolorable dye that has not been decolored as a latent image; and the two-photon absorption compound in the residual decolorizable dye latent image By irradiating light by irradiating light with a wavelength range where the molar absorption coefficient of linear absorption is 5000 or less and causing linear absorption of the color former, the polymerization initiator is activated by energy transfer or electron transfer to perform polymerization. Also preferred is a recording method characterized by having a second step of waking up and recording as refractive index modulation.

Furthermore, as a group of compounds capable of such a two-photon recording method,
at least,
1) a two-photon absorption compound capable of absorbing two photons and generating an excited state in the first step;
2) As a result of direct energy transfer or electron transfer from the excited state of the two-photon absorption compound in the first step, or as a result of generating a decolorant by transferring energy or electron to the decolorizer precursor, decoloring A decolorizable dye having a two-photon recording wavelength molar extinction coefficient of 1000 or less,
3) Polymerization of the polymerizable compound can be started by transferring electrons or energy from the excited state of the two-photon absorption compound in the first step and from the excited state of the decolorizable dye in the second step. A polymerization initiator (sometimes also serving as a decolorizer precursor of 2),
4) a polymerizable compound,
5) binder,
It is preferable to contain.
In addition, when energy transfer or electron transfer to the decolorizer precursor in 2),
6) A decolorizer precursor capable of generating a decolorizer by electron transfer or energy transfer from the excited state of the two-photon absorption compound in the first step,
Is also preferably included.

  Among them, it is preferable that at least one of the two-photon absorption compound, the decoloring dye, and the decoloring agent precursor is a polymer or an oligomer, and at least one of the decoloring dye or the decoloring agent precursor is a polymer or an oligomer. More preferably, it is an oligomer, and both the decolorizable dye and the decolorizer precursor may be a polymer or an oligomer, and may be a copolymer.

Preferred examples of the two-photon absorption compound are the same as those described in 2) Color development reaction.
Preferred examples of the polymerization initiator, the polymerizable compound and the binder are the same as those described in 1) polymerization reaction.
Preferable examples of the color erasable dye and the color erasing agent precursor are the same as the examples described in 6) Color erasing reaction.
In the wavelength range of the light irradiated in the second step, the molar absorption coefficient of linear absorption of the two-photon absorption compound is more preferably 1000 or less, and further preferably 500 or less.
Moreover, it is preferable that the molar extinction coefficient of the decolorizable dye is 1000 or more in the wavelength range of the light irradiated in the second step.

Here, in the “residual decoloring dye latent image-latent image sensitization polymerization method” of the present invention, it is also preferable that the decoloring agent precursor and the polymerization initiator are partially or entirely the same and serve both functions.
When a decolorizable dye is added separately from the two-photon absorption compound, and the decolorizer precursor and the polymerization initiator are different (for example, the decolorizer precursor is an acid generator or a base generator, the polymerization initiator is Radical polymerization initiator or decolorizer precursor is radical generator or nucleophile generator, polymerization initiator is acid generator or base generator), two-photon absorption compound is decolorizer precursor It is preferable that only electron transfer sensitization is possible, and the polymerization initiator can be electron transfer sensitized only by a decolorizable dye.

  In the two-photon absorption optical recording method of the present invention and the two-photon absorption recording material capable of such recording, fixing by the first step, the second step, or subsequent light irradiation, heat application, or both. It is preferable in terms of storage stability and nondestructive regeneration to decompose and fix the two-photon absorption compound by any of the steps, and further, in the first step, the second step, or subsequent light irradiation, heat application, Either the two-photon absorbing compound is decomposed by either the fixing step by the both, or the decolorizable dye remaining by the fixing step by the second step or the subsequent light irradiation, heat application, or both is decomposed. It is more preferable to fix it.

The concept of “residual decoloring dye latent image-latent image sensitized polymerization reaction method” will be described below.
For example, a two-photon absorption recording material is irradiated with a 780 nm laser, and the two-photon absorption compound absorbs the two-photon absorption recording material to generate an excited state.
The decoloring agent is generated by transferring energy or electrons from the excited state of the two-photon absorption compound to the decoloring agent precursor to decolorize the decoloring dye. As a result, a latent image can be formed by the remaining decolorizable dye (first step). Next, light in the wavelength region of 680 to 740 nm is irradiated to cause absorption of the residual decolorizable dye latent image, and the polymerization initiator is activated by electron transfer or energy transfer to initiate polymerization. For example, when the polymerizable compound has a refractive index lower than that of the binder, the refractive index is lowered because the polymerizable compound is collected at the portion where the polymerization occurs (second step). In the recording part that becomes the laser focal part in the first step, there is little residual decolorizable dye that becomes a latent image, so that polymerization does not occur much in the second process and the abundance ratio of the binder becomes high. As a result, the recording part A large refractive index modulation can be formed in the unrecorded portion, and a refractive index modulation can be formed. If the two-photon absorption compound and the remaining decolorizable dye can be decomposed and decolored by the first and second steps or further fixing step, the two-photon absorption recording material is excellent in nondestructive reproduction and storage and is colorless and transparent. Can be provided.
For example, when a 780 nm laser is used again and the recorded two-photon absorption recording material is irradiated, reproduction based on the difference in the reflectance or transmittance of light based on the difference in refractive index between the recording portion and the non-recording portion becomes possible. A photon absorption (three-dimensional) optical recording medium can be provided.

  Preferable examples of the residual decolorizable dye latent image-latent image sensitizing polymerization reaction include those described in Japanese Patent Application No. 2004-264202.

  The two-photon absorption recording material of the present invention is further required in addition to the two-photon absorption compound, the recording component, the polymerization initiator, the polymerizable compound, the binder, the decoloring dye, the decoloring agent precursor, and the like. Accordingly, additives such as an electron donating compound, an electron accepting compound, a chain transfer agent, a crosslinking agent, a heat stabilizer, a plasticizer, and a solvent can be used.

The electron-donating compound has the ability to reduce the radical cation of the two-photon absorption compound or chromophore, and the electron-accepting compound has the ability to oxidize the radical anion of the two-photon absorption compound or chromogen, both of which absorb two-photons It has a function of regenerating a compound or color former. Specifically, for example, an example described in JP-A-2005-71570 can be given as a preferable example.
In particular, the electron donating compound is useful for high sensitivity because it can quickly regenerate the two-photon absorption compound or the color former radical cation after the electron transfer to the dye precursor group. As the electron donating compound, those having an oxidation potential lower than those of the two-photon absorption compound and the color former are preferable.
The electron donating compounds are preferably alkylamines, anilines, phenylenediamines, triphenylamines, carbazoles, phenothiazines, phenoxazines, phenazines, hydroquinones, catechols, alkoxybenzenes, aminophenols. , Imidazoles, pyridines, metallocenes, metal complexes, semiconductor fine particles, more preferably triphenylamines, phenothiazines, phenoxazines, phenazines, especially phenothiazine compounds. (For example, 10-methylphenothiazine, 10- (4′-methoxyphenyl) phenothiazine), triphenylamine compounds (for example, triphenylamine, tri (4′-methoxyphenyl) amine, TPD compounds (for example, TPD), etc. Preferably, more preferably phenothiazine compound, N- methyl phenothiazine is most preferred.
Specific examples of preferable electron donating compounds are listed below, but the present invention is not limited thereto.

In the two-photon absorption recording material of the present invention, the electron donating compound is preferably a polymer or an oligomer.
When the electron donating compound is a polymer or an oligomer, it may be a polymer or an oligomer containing an electron donating compound in the main chain or a polymer or an oligomer containing an electron donating compound in the side chain. The polymer is preferably a polymer or oligomer containing an electron donating compound in the side chain. When the polymer or oligomer contains an electron donating compound in the side chain, the electron donating compound is contained in the side chain even if the electron donating compound is a copolymer of two or more monomers contained in the side chain. It may be a copolymer of a monomer that does not contain an electron-donating compound.
Next, when the electron donating compound in the two-photon absorption recording material of the present invention is a polymer or oligomer, the electron donating compound is preferably a polymer or oligomer contained in the main chain or side chain.

  Particularly preferable electron donating compound polymers or oligomers are listed below, but the present invention is not limited thereto.

  Further, the two-photon absorption recording material of the present invention is a copolymer of a monomer containing an electron donating compound in the side chain as described below and a monomer containing either the two-photon absorption compound or the recording component in the side chain. It is also preferred to include a polymer or oligomer.

The electron-accepting compound is useful for high sensitivity because it can quickly regenerate the two-photon absorption compound or color former radical anion after electron transfer from the dye precursor group. As the electron-accepting compound, those having a reduction potential nobler than the reduction potential of the two-photon absorption compound and the color former are preferable.
The electron accepting compound is preferably an aromatic compound into which an electron withdrawing group is introduced, such as dinitrobenzene or dicyanobenzene, a heterocyclic compound, a heterocyclic compound into which an electron withdrawing group is introduced, or an N-alkylpyridinium salt Benzoquinones, imides, metal complexes, semiconductor fine particles and the like.

  Specific examples of chain transfer agents, crosslinking agents, heat stabilizers, plasticizers, solvents, and the like are preferably described in JP-A No. 2004-346238.

Preferred chain transfer agents are thiols, such as 2-mercaptobenzoxazole, 2-mercaptobenzthiazole, 2-mercaptobenzimidazole, 4-methyl-4H-1,2,4-triazole-3-thiol, Examples include p-bromobenzenethiol, thiocyanuric acid, 1,4-bis (mercaptomethyl) benzene, p-toluenethiol and the like.
In particular, when the polymerization initiator is 2,4,5-triphenylimidazolyl dimer, it is preferable to use a chain transfer agent.

A heat stabilizer can be added to the two-photon absorption recording material of the present invention in order to improve the storage stability during storage.
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.

  Plasticizers are used to change the adhesion, flexibility, hardness, and other mechanical properties of the two-photon absorption recording material. 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, dibutyl phthalate, alcohols, and phenols.

The two-photon absorption recording material of the present invention may be prepared by a usual method.
For example, as a method for forming a two-photon absorption recording material of the present invention, the above binder and each component may be dissolved in a solvent and applied using a spin coater or a bar coater.
In that case, preferably as a solvent, for example, ketone solvents such as methyl ethyl ketone, methyl isobutyl ketone, acetone, cyclohexanone, ester solvents such as ethyl acetate, butyl acetate, ethylene glycol diacetate, ethyl lactate, cellosolve acetate, cyclohexane, toluene, Hydrocarbon solvents such as xylene, 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- Alcohol solvents such as butanol and diacetone alcohol, fluorine solvents such as 2,2,3,3-tetrafluoropropanol, dichloromethane, chloroform , 1,2-halogenated hydrocarbon solvents such as dichloroethane, N, amide solvents such as N- dimethylformamide, acetonitrile, and nitrile-based solvents such as propionitrile.

The two-photon absorption recording material of the present invention can be applied directly on the substrate by using a spin coater, roll coater, bar coater or the like, or can be cast as a film and laminated on the substrate by an ordinary method. Accordingly, a two-photon absorption recording material can be obtained.
Here, “substrate” means any natural or synthetic support, preferably one that can exist in the form of a flexible or rigid film, sheet or plate.
Preferred examples of the substrate include polyethylene terephthalate, resin-primed polyethylene terephthalate, polyethylene terephthalate subjected to flame or electrostatic discharge treatment, cellulose acetate, polycarbonate, polymethyl methacrylate, polyester, polyvinyl alcohol, and glass.
The solvent used can be removed by evaporation during drying. Heating or reduced pressure may be used for evaporation removal.

The two-photon absorption optical recording material of the present invention may be formed by melting a binder containing each component at a temperature equal to or higher than the glass transition temperature or the melting point of the binder, and melt-extrusion or injection molding. At that time, a reactive cross-linking binder may be used as the binder, and the film may be cured by cross-linking after extrusion or molding to increase the film strength. In that case, radical polymerization reaction, cationic polymerization reaction, condensation polymerization reaction, addition polymerization reaction, etc. can be used for the crosslinking reaction. In addition, methods described in JP-A Nos. 2000-250382 and 2000-172154 can also be preferably used.
In addition, a method in which each component is dissolved in a monomer solution forming a binder and then the monomer is thermally polymerized or photopolymerized to form a polymer, which is preferably used as a binder. As a polymerization method at that time, a radical polymerization reaction, a cationic polymerization reaction, a condensation polymerization reaction, an addition polymerization reaction, or the like can be used.

  Further, a protective layer for blocking oxygen may be formed on the two-photon absorption recording material. The protective layer is made of a plastic film or plate such as polyolefin such as polypropylene or polyethylene, polyvinyl chloride, polyvinylidene chloride, polyvinyl alcohol, polyethylene terephthalate or cellophane film by electrostatic adhesion or lamination using an extruder. Alternatively, the polymer solution may be applied. Further, a glass plate may be bonded. Further, an adhesive or a liquid substance may be present between the protective layer and the photosensitive film and / or between the base material and the photosensitive film in order to improve airtightness.

When the two-photon absorption recording material of the present invention is used for a two-photon absorption three-dimensional optical memory, the two-photon absorption recording material is less likely to shrink before and after the two-photon recording in terms of improving the S / N ratio at the time of signal reproduction. More preferred.
Therefore, for example, the two-photon absorption recording material of the present invention uses an expanding agent described in JP-A No. 2000-86914, or has shrink resistance as described in JP-A Nos. 2000-250382, 2000-172154, and JP-A No. 11-344917. It is also preferable to use a binder.

  As described above, the two-photon absorption recording material of the present invention provides a completely new recording method that can solve both of the above-mentioned problems, and can achieve both high sensitivity, good storage stability, dry processing, and high recording density. In particular, it is preferably used for an optical recording medium.

  Furthermore, the two-photon absorption recording material of the present invention can be preferably used for a three-dimensional volume display, an optical material, a lens, a security application and the like in addition to the optical recording medium.

[Example]
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.

[Three-dimensional refractive index, absorptance, and emission intensity modulation method by two-photon absorption coloring method]

First, a method for reproducing the two-photon absorption recording material of the present invention by modulating the refractive index, the absorptivity or the emission intensity by the method of generating a color former from a dye precursor by two-photon absorption will be described.
In a dark room, the two-photon absorption compound, electron donating compound, recording component, additive, binder PMMA-EA (poly (methyl methacrylate-5% ethyl acrylate) copolymer, Mw 101000) shown in Table 1 Dissolve in ˜4-fold mass of methylene chloride (with acetone or acetonitrile if necessary), prepare novel compositions for two-photon absorption recording materials 101 to 104 using the polymer component of the present invention, and cope with it Comparative sample compositions 11-14 that do not use the polymer component to be prepared were prepared. In addition, all% represents the mass% with respect to binder PMMA-EA.

* However, PL-2 is n68: n69 = 1: 2, PL-7 is n68: n69 = 1: 2, PDD-2 is n79: n80 = 1: 2, PE-11 is n84: n85 = 1: 2. , PED-2 is n101: n102 = 1: 1.

  Samples 101 to 104 and comparative samples 1 to 4 were bar-coated on a preparation glass plate, dried with a solvent, and then prepared with the preparation glass as an evaluation sample. The film thickness was about 10 μm.

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.
Samples 101 to 104 and comparative samples 1 to 4 were irradiated with 740 nm laser light to cause two-photon absorption. As a result, in Samples 101 to 104 and Comparative Samples 11 to 14, color development was confirmed at the laser focal point (recording unit) of the light irradiation unit. The change in the absorptance between the recording part and the non-recording part could be confirmed visually using an optical microscope or the like. When the refractive index of the color developing part (recording part) was measured with an ellipsometer, it increased compared to the laser non-focusing part (non-recording part). When the samples 101 to 104 and the comparative samples 11 to 14 were irradiated with 740 nm laser light using a reflective confocal microscope, the difference in reflectance due to the difference in refractive index could be confirmed between the recording part and the non-recording part.
In addition, when the recorded samples 101 to 104 and the comparative samples 11 to 14 were irradiated with a 660 nm laser using a transmission confocal microscope, the difference in transmittance due to the difference in the absorptance was recorded between the recorded portion and the non-recorded portion. It could be confirmed. Moreover, the difference in emitted light intensity was also confirmed.

  In addition, by scanning the laser focal position in the horizontal and depth directions, it was possible to develop a color at an arbitrary place in the three-dimensional direction. It can be confirmed that three-dimensional reflectance modulation by refractive index modulation can be performed by 740 nm laser irradiation, and three-dimensional reflectance modulation or three-dimensional emission intensity modulation by absorption modulation can be performed by laser irradiation of 660 nm. It was.

  Here, since the two-photon absorption recording materials 101 to 104 using the polymer component of the present invention use a polymer as a refractive index modulator such as a recording component, the disappearance of the recording and the resolution decrease due to the movement of the substance after recording. As a result, the reflectance, the absorptivity, and the modulation rate of the emission intensity are higher than those of the comparative samples 11 to 14. In addition, even when left for one month at room temperature in the dark, no decrease in the reflectance, absorption rate, or modulation rate of the emission intensity is observed, which is promising in terms of storage stability.

[Two-dimensional refractive index, absorptance and emission intensity modulation method by two-photon absorption latent image coloring-coloring material self-sensitized amplification coloring method]

Next, the two-photon absorption was caused by irradiating the samples 101 to 104 and the comparative samples 11 to 14 of Example 1 with a laser beam of 740 nm by 1/30 of the light amount of Example 1 (first step, Hereinafter, in Samples 201 to 204 and Comparative Samples 21 to 24) and Samples 201 to 204, the color development (latent image) was slightly confirmed at the laser focal point (recording unit) of the light irradiation unit.
Furthermore, as a result of exposing the entire surface of light in the wavelength range of 680 to 720 nm using a xenon lamp and a band pass filter (second step), color development can be clearly confirmed in the recording portion of the first step. Color development did not occur in the recording part, and the change in the absorptance between the recording part and the non-recording part could be visually confirmed using an optical microscope or the like. When the refractive index of the color developing part (recording part) was measured with an ellipsometer, it increased compared to the laser non-focusing part (non-recording part). When a 740 nm laser was irradiated using a reflective confocal microscope, a difference in reflectance due to a difference in refractive index could be confirmed between the colored recording portion and the non-recording portion.
Also, when the recorded samples 201 to 204 and the comparative samples 21 to 24 were irradiated with a 660 nm laser using a transmission confocal microscope, the difference in transmittance due to the difference in the absorption rate was confirmed between the recording portion and the non-recording portion. did it. Moreover, the difference in emitted light intensity was also confirmed.

In addition, by scanning the laser focal position in the horizontal and depth directions, it was possible to develop a color at an arbitrary place in the three-dimensional direction. It can be confirmed that three-dimensional reflectance modulation by refractive index modulation is possible by laser irradiation at 740 nm, and three-dimensional reflectance modulation or three-dimensional emission intensity modulation by absorption modulation is possible by laser irradiation at 660 nm. It was.
As described above, the two-photon absorption latent image coloring-coloring body self-sensitized amplification coloring method of the present invention shows that about 30 times amplification is possible in the second step. It can also be confirmed that further amplification is possible by increasing the irradiation time of the second step.

  Here, since the two-photon absorption recording materials 201 to 204 using the polymer component of the present invention use a polymer as a refractive index modulator such as a recording component, the disappearance of the recording and the reduction in the resolution due to the movement of the substance after the recording are caused. As a result, the reflectance, the absorptivity, and the modulation rate of the emission intensity are higher than those of the comparative samples 21 to 24. In addition, even when left for one month at room temperature in the dark, no decrease in the reflectance, absorption rate, or modulation rate of the emission intensity is observed, which is promising in terms of storage stability.

In Examples 1 and 2, the two-photon absorption compounds are D-2, D-5, D-8, D-10, D-12, D-13, D-14, D-15, D-20. , D-22, D-24, D-25, D-28, D-32, D-35, D-36, D-47, D-50, D-52, D-64, D-65, D -66, D-73, D-76, D-78, D-80, D-81, D-86, D-88, D-89, D-90, D-119 Moreover, even if it changed into any of PS-1-PS-8, PS-10, PS-11-PS-14, the same effect was acquired.
In Samples 101 and 102 and Samples 201 and 202, the recording component acid generators are AI-1 to AI-5, AI-7 to AI-9, AI-11 to AI-13, AI-17 to AI-. 19, changed to tris (4-methylphenyl) sulfonium tetra (pentafluorophenyl) borate, triphenylsulfonium perfluoropentanoate, bis (1- (4-diphenylsulfonium) phenyl sulfide ditriflate, or benzoin tosylate Even in Samples 101 and 102 and Samples 201 and 202, the acid coloring dye precursor polymer of the recording component is changed to any of PL-1, PL-3, PL-5 to PL-8, and PL-9. However, the same effect was obtained.
Further, even when the base generator of the recording component is changed to any of PB-1, PB-3 to PB-9 in the samples 103 and 203, the base coloring type dye precursor (dissociation type) is used in the samples 103 and 203. The same effect was obtained even when the polymer was changed to any one of PDD-1, PDD-3 to PDD-8, PDD-11, and PDD-12.
In addition, the same effect was obtained when the recording components of Samples 104 and 204 were changed to any of PE-2 to PE-8, PE-13, and PE-14.
Even if the electron-donating compound is changed to any one of A-2 to A-6 and A-9 to A-11 in Samples 101 to 104 and 201 to 204, the polymer electron-donating compound PED-3 The same effect was obtained even when changed to -PED-7.
In Samples 101 to 104 and Samples 201 to 204, the binder was polymethyl methacrylate (Mw 996000, 350,000, 120,000), poly (methyl methacrylate-butyl acrylate copolymer (Mw 75000), polyvinyl acetal (Mw 83000), polycarbonate, cellulose acetate. The same effect was obtained even if it was changed to either butyrate.

  In addition, in the case of the above, the solvent at the time of preparing the sample, the laser wavelength and the light amount at the time of causing the two-photon absorption, the wavelength and the light amount of the light irradiated for the second step, the change in the reflectance and the emission intensity are observed. Therefore, the optimum wavelength is used for each system.

[Three-dimensional refractive index, absorptance and emission intensity modulation method by two-photon absorption decolorization method]

  Next, a method for regenerating by modulating the refractive index, the absorptivity, or the emission intensity by the decoloring reaction of the decolorizable dye caused by the two-photon absorption of the two-photon absorption decoloring material of the present invention will be described.

  Under a dark room, the two-photon absorption compound, electron donating compound, decolorant precursor, decolorizable dye, binder PMMA-EA (poly (methyl methacrylate-5% ethyl acrylate) copolymer shown in Table 2 Mw 101000) is dissolved in 2 to 4 times the mass of methylene chloride (with acetone or acetonitrile if necessary), and a novel composition for two-photon absorption recording material 301 to 304 using the polymer component of the present invention is prepared. Further, comparative sample compositions 31 to 34 were prepared without using the corresponding polymer component. In addition, all% represents the mass% with respect to binder PMMA-EA.

  * However, PG-5 is n86: n87 = 1: 2, PG-13 is n86: n87 = 1: 2, PG-21 is n93: n94 = 1: 2, PG-29 is n98: n99 = 1: 2. It is.

  Samples 301 to 304 and comparative samples 31 to 34 were bar-coated on a preparation glass plate, dried with a solvent, and then prepared with the preparation glass as an evaluation sample. The film thickness was about 10 μm.

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.
Samples 301 to 304 and comparative samples 31 to 34 were irradiated with a laser beam of 740 nm to cause two-photon absorption. As a result, in Samples 301 to 304 and Comparative Samples 31 to 34, decoloration could be confirmed at the laser focal point (recording unit) of the light irradiation unit. The change in the absorptance between the recording part and the non-recording part could be confirmed visually using an optical microscope or the like. When the refractive index of the decolored portion (recording portion) was measured with an ellipsometer, it decreased compared to the laser non-focused portion (non-recording portion). When the samples 301 to 304 and the comparative samples 31 to 34 were irradiated with 740 nm laser light using a reflective confocal microscope, the difference in reflectance due to the difference in refractive index between the recording part and the non-recording part could be confirmed.
In addition, when the recorded samples 301 to 304 and the comparative samples 31 to 34 were irradiated with a 660 nm laser using a transmission confocal microscope, the difference in transmittance due to the difference in the absorptance was confirmed in the recording portion and the non-recording portion. did it. Moreover, the difference in emitted light intensity was also confirmed.

  In addition, by scanning the laser focal position in the horizontal and depth directions, it was possible to develop a color at an arbitrary place in the three-dimensional direction. It can be confirmed that three-dimensional reflectance modulation by refractive index modulation is possible by laser irradiation at 740 nm, and three-dimensional reflectance modulation or three-dimensional emission intensity modulation by absorption modulation is possible by laser irradiation at 660 nm. It was.

  Here, since the two-photon absorption recording materials 301 to 304 using the polymer component of the present invention use a polymer as a refractive index modulation agent such as a recording component, the disappearance of the recording and the reduction of the resolution due to the movement of the substance after recording are caused. As a result, the reflectance, the absorptance, and the modulation rate of the emission intensity are higher than those of the comparative samples 31 to 34. In addition, even when left for one month at room temperature in the dark, no decrease in the reflectance, absorption rate, or modulation rate of the emission intensity is observed, which is promising in terms of storage stability.

In Example 3, the two-photon absorption compound is D-2, D-5, D-8, D-10, D-12, D-13, D-14, D-15, D-20, D -22, D-24, D-25, D-28, D-32, D-35, D-36, D-47, D-50, D-52, D-64, D-65, D-66 , D-73, D-76, D-78, D-80, D-81, D-86, D-88, D-89, D-90, D-119, The same effect was obtained even if PS-1 to PS-8, PS-10, or PS-11 to PS-14 was changed.
In Samples 301 and 302, the acid generators of recording components are AI-1 to AI-5, AI-7 to AI-9, AI-11 to AI-13, AI-17 to AI-19, Tris (4 -Methylphenyl) sulfonium tetra (pentafluorophenyl) borate, triphenylsulfonium perfluoropentanoate, bis (1- (4-diphenylsulfonium) phenyl sulfide ditriflate, benzoin tosylate In 301 and 302, the same effect was obtained even when the acid decolorizable dye polymer of the recording component was changed to any one of PG-1, PG-9, and PG-13.
Further, even if the base generator of the recording component is changed to any of PB-1, PB-3 to PB-9 in the sample 303, the base decolorizable dye polymer in the sample 303 is changed to PG-16, PG- The same effect was obtained even when changed to any one of 17, PG-19, PG-20, and PG-22.
In addition, the same effect was obtained when the decolorizable dye of the recording component was changed to any one of PG-28, PG-30, and PG-31 in Sample 304.
Even if the electron donating compound is changed to any one of A-2 to A-6 and A-9 to A-11 in the samples 301 to 304, the polymer electron donating compounds PED-1, PED-3, The same effect was obtained even if it changed to any of PED-7.
In Samples 301 to 304, the binder is any one of polymethyl methacrylate (Mw 996000, 350,000, 120,000), poly (methyl methacrylate-butyl acrylate copolymer (Mw 75000), polyvinyl acetal (Mw 83000), polycarbonate, and cellulose acetate butyrate. The same effect was obtained even when changed to.
In the above case, the solvent used for preparing the sample, the laser wavelength and the light quantity when causing the two-photon absorption, the wavelength of the light to be irradiated in order to see changes in the reflectance and the emission intensity are optimal for each system. Condition is used.

Claims (20)

  At least a two-photon absorption compound that generates an excited state by two-photon absorption and a color reaction or decoloring reaction caused by electron transfer or energy transfer from the excited state of the two-photon absorption compound, and the refractive index and absorptance due to the absorption change Or a recording component capable of recording using modulation of light emission intensity, wherein at least one of the two-photon absorption compound or the recording component is a polymer or an oligomer A two-photon absorption recording material.   2. The two-photon according to claim 1, wherein the recording component includes at least an acid generator and an acid coloring dye precursor or an acid decoloring dye, and at least one of them is a polymer or an oligomer. Absorption recording material.   3. The two-photon absorption recording material according to claim 2, wherein the acid coloring dye precursor or the acid decolorizable dye is a polymer or an oligomer.   2. The two-photon according to claim 1, wherein the recording component includes at least a base generator and a base color-forming dye precursor or a base decolorizable dye, and at least one of them is a polymer or an oligomer. Absorption recording material.   5. The two-photon absorption recording material according to claim 4, wherein the base color-forming dye precursor or the base decolorizable dye is a polymer or an oligomer. The two-photon absorption recording material according to any one of claims 1 to 5, wherein the recording component contains at least a color-forming dye precursor polymer or oligomer represented by the following general formula (1).
General formula (1)
(A1-PD) m1
In general formula (1), A1 and PD are covalently bonded, and A1 is a site having a function of breaking the covalent bond with PD by electron transfer or energy transfer with the excited state of the two-photon absorption compound. It represents a site that can cause a color reaction when the covalent bond with A1 is cleaved and released.
In the general formula (1), either A1 or PD is connected to each other through a covalent bond to form a polymer or oligomer, and m1 represents an integer of 3 to 1,000,000. The two-photon absorption recording material according to any one of claims 1 to 5, wherein the recording component contains at least a decolorizable dye polymer or oligomer represented by the following general formula (2).
General formula (2)
(A2-DD) m2
In the general formula (2), A2 and DD are covalently bonded, and A2 is a site having a function of cleaving the covalent bond with DD by electron transfer or energy transfer with the excited state of the two-photon absorption compound. A site that is a dye when covalently bound to A2 is decolored when the covalent bond is cleaved and released.
In the general formula (2), either A2 or DD is connected to each other through a covalent bond to form a polymer or oligomer, and m2 represents an integer of 3 to 1,000,000. The two-photon absorption compound contained in the two-photon absorption recording material according to claim 1 is represented by a cyanine dye, a merocyanine dye, an oxonol dye, a phthalocyanine dye, an azo dye, or the following general formula (21): The two-photon absorption recording material according to claim 1.
Formula (21)

In the formula, R ₁₀₁ , R ₁₀₂ , R ₁₀₃ , and R ₁₀₄ each independently represent a hydrogen atom or a substituent, and some of R ₁₀₁ , R ₁₀₂ , R ₁₀₃ , and R ₁₀₄ are bonded to each other to form a ring. May be formed. n ₁₀₁ and m ₁₀₁ each independently represent an integer of 0 to 4, and when n ₁₀₁ and m ₁₀₁ are 2 or more, a plurality of R ₁₀₁ , R ₁₀₂ , R ₁₀₃ , and R ₁₀₄ may be the same or different. . However, n ₁₀₁ and m ₁₀₁ are not 0 simultaneously. X ₁₀₁ and X ₁₀₂ independently represent an aryl group, a heterocyclic group, or a group represented by General Formula (22).
General formula (22)

In the formula, R ₁₀₅ represents a hydrogen atom or a substituent, R ₁₀₆ represents a hydrogen atom, an alkyl group, an alkenyl group, an aryl group, or a heterocyclic group, and Z ₁₀₁ represents an atomic group forming a 5- or 6-membered ring. To express. The cyanine dye may be represented by the following general formula (23), the merocyanine dye may be represented by the following general formula (24), and the oxonol dye may be represented by the general formula (25). Item 9. The two-photon absorption recording material according to Item 8.

In general formulas (23) to (25), Za ₁ , Za ₂ and Za ₃ each represent an atomic group forming a 5-membered or 6-membered nitrogen-containing heterocyclic ring, 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 represents an integer of 0 to 3. When ka ¹ is 2 or more, a 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 that neutralizes the electric charge, and y represents a number necessary for neutralizing the electric charge.   The two-photon absorption recording material according to any one of claims 1 to 9, wherein the two-photon absorption compound is a polymer or an oligomer.   The two-photon absorption recording according to any one of claims 1 to 10, further comprising an electron donating compound capable of donating an electron to the radical cation after the electron transfer to the recording component. material.   12. The two-photon absorption recording material according to claim 11, wherein the electron donating compound according to claim 11 is a polymer or an oligomer.   13. The polymer or oligomer according to claim 1, wherein at least two of the two-photon absorption compound, the recording component, and the electron donating compound according to claim 1 comprise a copolymerized polymer or oligomer. Two-photon absorption recording material.   The two-photon absorption recording material according to any one of claims 1 to 13, comprising: 1) color development reaction, 2) latent image color development-color-former self-sensitized amplification color development reaction, 3) latent image color development-color-form-sensitized polymerization reaction, 4) dye Recording by causing any one of A) refractive index modulation, B) absorptance modulation, and C) light emission ability modulation by any one of the decoloring reaction, 5) residual decoloring dye latent image-latent image sensitization polymerization reaction The two-photon absorption recording material according to claim 1, wherein the two-photon absorption recording material can be used.   The two-photon absorption recording material having the two-photon absorption compound according to claim 1 to 14 is subjected to recording by refractive index modulation or absorptivity modulation using two-photon absorption of the two-photon absorption compound, and then the light is recorded. A two-photon absorption optical recording / reproducing method characterized in that reproduction is performed by irradiating and detecting a difference in reflectance or transmittance.   The two-photon absorption recording material having the two-photon absorption compound according to claim 1 to 14 is recorded by light emission modulation using two-photon absorption of the two-photon absorption compound, and then the recording material is irradiated with light. A two-photon absorption optical recording / reproducing method, wherein reproduction is performed by detecting a difference in the emission intensity.   A two-photon absorption three-dimensional optical recording / reproducing method comprising the two-photon absorption optical recording / reproducing method according to claim 15 or 16.   A two-photon absorption three-dimensional optical recording medium comprising the two-photon absorption recording material according to claim 1.   19. A two-photon absorption optical recording medium, wherein the two-photon absorption recording material according to claim 1 is stored in a light-shielding cartridge at the time of storage.   The two-photon absorption recording material according to any one of claims 1 to 14, 18, and 19 is irradiated with a laser beam having a wavelength longer than the linear absorption band of the two-photon absorption compound and having a linear absorption molar absorption coefficient of 10 or less. And a two-photon absorption optical recording method, wherein recording is caused by utilizing two-photon absorption induced in this manner.