JP2005100599A - Photon mode recording method and 3-dimensional optical recording method - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a photon mode recording method having a latent image amplifying function and high sensitivity. <P>SOLUTION: In the photon mode recording method, a photon mode recording material is used, containing at least a sensitizing dye and a dye precursor capable of becoming a coloring body having absorption in a wavelength region different from that of the sensitizing dye associated with transfer of absorption from an original state to a long wavelength side and having a recording component by which recording can be performed as difference between refractive indices or absorption indices through an electron transfer or energy transfer process from an exited state of the sensitizing dye or the coloring body. The photon mode recording method further has at least a first process for forming the coloring body as a latent image by irradiation with light and a second process for performing self-sensitization amplification of the coloring body latent image to perform recording as the difference between the refractive indices or the absorption indices. These steps are performed in a dry process. <P>COPYRIGHT: (C)2005,JPO&NCIPI

Description

At least a first step of forming a latent image by light irradiation and a second step of forming a difference in refractive index or absorptivity by amplifying the latent image, and performing them by dry processing The present invention relates to a photon mode recording method and a photon mode recording material capable of such recording.
In particular, it has at least a first step of forming a latent image by two-photon absorption caused by light irradiation and a second step of forming a difference in refractive index or absorptance by amplifying the latent image. The present invention relates to a two-photon absorption optical recording method and a two-photon absorption optical recording material capable of such recording.

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

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

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

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

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

Recently, networks such as the Internet and high-definition TV are rapidly spreading. In addition, HDTV (High Definition Television) will soon be broadcast, and there is an increasing demand for large-capacity recording media 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 is about 25 GB at most even if the recording / reproducing wavelength is shortened due to the physical principle, and is sufficiently large enough to meet future demands. It cannot be said that capacity can be expected.

Under such circumstances, a three-dimensional optical recording medium has attracted attention as an ultimate high-density, high-capacity recording medium. Three-dimensional optical recording media can be recorded in dozens or hundreds of layers in the three-dimensional (film thickness) direction, resulting in tens or hundreds of times the ultra-high density and ultra-high capacity recording of conventional two-dimensional recording media. That is what we are trying to achieve. In order to provide a three-dimensional optical recording medium, it is necessary to be able to access and write at an arbitrary place in the three-dimensional (film thickness) direction. As a means for this, a method using a two-photon absorption material and holography (interference) There is a method of using.
In a three-dimensional optical recording medium using a two-photon absorption material, so-called bit recording is possible over tens or hundreds of times based on the physical principle described above, and higher density recording is possible. It can be said to be the ultimate high-density, high-capacity optical recording medium.
As a three-dimensional optical recording medium using a two-photon absorption material, a method of reading with fluorescence using a fluorescent substance for recording / reproduction (Lewitch, Eugene, Polis et al., Special Table 2001-524245 [Patent Document 1], Pavel, Eugen et al., JP 2000-512061 [Patent Document 2]), a method of reading by absorption or fluorescence using a photochromic compound (Korotif, Nikolai Ai et al., JP 2001-522119 [Patent Document 3], Arsenoff U. Ladimir et al., JP 2001-508221 [Patent Document 4]) and the like have been proposed, but none of the specific two-photon absorption materials are presented, and two-photons presented abstractly. Examples of absorbing compounds also use two-photon absorbing compounds with extremely low two-photon absorption efficiency. Furthermore, non-destructive readout and long-term storage stability of recording There are problems such as the S / N ratio of the reproduction, it can not be said to be a method of utility as an optical recording medium.
In particular, in terms of non-destructive reading, long-term storage stability of recording, etc., it is preferable to reproduce by changing the reflectance (refractive index or absorptivity) using an irreversible material. A two-photon absorbing material having such a function is used. There were no specific examples disclosed.
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 about 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, if a reaction is caused by using the excitation energy obtained by non-resonant two-photon absorption, and as a result, the refractive index or the absorptance can be modulated between the laser focus part and the non-focus part, the three-dimensional space Light reflectivity or transmittance modulation by refractive index or absorptivity modulation can be generated at an arbitrary place with extremely high spatial resolution, and can be applied to a three-dimensional optical recording medium that is considered to be the ultimate high-density recording medium. Become. Furthermore, since non-destructive readout is possible and the material is an irreversible material, it can be expected to have good storage stability and is practical.
However, currently available two-photon absorption compounds have a low two-photon absorption capability, so 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, construction of a two-photon absorption three-dimensional optical recording material capable of performing refractive index or absorptivity modulation by two-photon absorption with high sensitivity to achieve a high writing speed. Is essential. For this purpose, a two-photon absorption compound capable of absorbing two-photons with high efficiency and generating an excited state reacts chemically by electron transfer or energy transfer from the two-photon absorption compound excited state, and a refractive index difference or absorption. Materials containing recording components capable of recording rate differences are prominent, and it is necessary to introduce an amplification function there to achieve further higher sensitivity, but such materials have never been disclosed so far. Therefore, the construction of such a material has been desired.

  An object of the present invention is to provide a highly sensitive photon mode recording material having a latent image amplification function and a recording method, and more particularly to a two-photon absorption optical recording material and a two-photon absorption optical recording / reproducing method capable of recording with a difference in refractive index or an absorption difference. Is to provide. Furthermore, it is to provide a two-photon absorption three-dimensional optical recording medium or a three-dimensional volume display 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) 1) a sensitizing dye, and 2) a sensitizing dye that includes a dye precursor capable of becoming a color former having a longer wavelength than the original state and having absorption in a wavelength region different from that of the sensitizing dye. Or a photon mode recording method having a recording component that can be recorded as a difference in refractive index or a difference in absorption rate by electron transfer or energy transfer from the excited state of the chromophore, wherein the latent image of the chromogen is at least irradiated with light. And a second step of amplifying and generating the latent image and recording it as a difference in refractive index or a difference in absorption rate.
(2) The photon mode recording method according to (1), wherein, in (1), the second step is any one of light irradiation, heat application, electric field application, and magnetic field application (preferably light irradiation). .
(3) (1) or (2), wherein the sensitizing dye is a two-photon absorption compound, and the first step generates a latent image by at least two-photon absorption caused by light irradiation. Photon mode recording method.
(4) at least 1) a sensitizing dye, and 2) a dye precursor that can be a color former that has a wavelength longer than that of the sensitizing dye and has absorption in a wavelength range different from that of the sensitizing dye, and A recording component capable of recording as a refractive index difference or an absorption difference through an electron transfer or energy transfer process from an excited state of a sensitizing dye or the color former, and a recording method of a photon mode recording material, A first step of generating the color former as a latent image by light irradiation; and the color former latent image obtained by irradiating the color former latent image with light having a wavelength range of a molar absorption coefficient of sensitizing dye linear absorption of 5000 or less. And a second step of recording the color body as a difference in refractive index or a difference in absorption rate by performing linear absorption, and performing these steps by dry processing. (1) to ( Photon-mode recording method according to any one of).
(5) The photon mode recording according to any one of (1) to (4), wherein the molar absorption coefficient of the sensitizing dye is 1000 or less in the wavelength range of the light irradiated in the second step. Method.
(6) The photon mode recording method according to any one of (1) to (5), wherein a molar extinction coefficient of the color former is 5000 or more in the wavelength range of the light irradiated in the second step. .
(7) The photon mode recording method according to (2), wherein the second step is either light irradiation or heat application.
(8) In (3), a first step of generating a color image having a different absorption form from the linear absorption of at least the two-photon absorption compound as a latent image by two-photon absorption exposure; Absorption compound linear (single photon) absorption molar absorption coefficient of 5000 or less irradiates light in the wavelength range to cause linear absorption of the color former to produce self-sensitized amplification to produce a refractive index difference or an absorption difference The photon mode recording method according to any one of (3) to (7), further comprising a second step of recording as:
(9) The photon mode according to (8), wherein the molar absorption coefficient of linear absorption of the two-photon absorption compound is 1000 or less in the wavelength range of the light irradiated in the second step according to (8) Recording method.
(10) The photon mode according to (8) or (9), wherein the molar extinction coefficient of the color former is 5000 or more in the wavelength range of the light irradiated in the second step according to (8) Recording method.
(11) The wavelength of light for forming a latent image in the first step is the same as the wavelength of light for amplifying the latent image in the second step to form a refractive index difference or an absorptance difference. The photon mode recording method according to any one of (1) to (10).
(12) The wavelength of light that amplifies the latent image in the second step to form a difference in refractive index or absorptivity than the wavelength of light that forms the latent image by two-photon absorption recording in the first step. The photon mode recording method according to any one of (1) to (10), wherein
(13) The photon mode recording method according to any one of (1) to (12), wherein the recording cannot be rewritten in (1) to (12).
(14) Using the photon mode recording material recorded by the method described in any one of (1) to (13), irradiating the recording material with light, An optical recording / reproducing method, wherein reproduction is performed by detecting a difference in transmittance.
(15) In (14), the wavelength of the light irradiated when recording is the same as the wavelength of the light irradiated for detecting a difference in reflectance or transmittance during reproduction (characterized in that 14) The two-photon absorption optical recording / reproducing method described in 14).
(16) In (14), the latent image is amplified in the second step to a difference in refractive index or absorptivity than the wavelength of the light that forms the latent image by the two-photon absorption recording in the first step. The wavelength of the light forming the light is a short wavelength, the molar absorption coefficient of the two-photon absorption compound linear (one-photon) absorption is in the wavelength range of 5000 or less, and the light irradiated when recording by two-photon absorption is performed The two-photon absorption optical recording / reproducing method according to (14), wherein the wavelength of the light and the wavelength of light irradiated for detecting a difference in reflectance or transmittance during reproduction are the same.
(17) The photon mode recording method according to any one of (1) to (13), wherein the recording component contains at least an acid-color-forming dye precursor as a dye precursor and an acid generator.
(18) The photon mode recording according to (17), 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. Method.
(19) The two-photon absorption optical recording material according to (17) or (18), wherein the acid generator is a diaryliodonium salt, a sulfonium salt, or a sulfonic acid ester.
(20) In any one of (17) to (19), the dye produced from the acid-color-formable dye precursor is a xanthene (preferably fluorane) dye or a triphenylmethane dye The photon mode recording method according to claim 1.
(21) Any one of (17) to (20), wherein the recording component of (17) comprises at least an acid color-forming dye precursor as a dye precursor, an acid generator, and an acid multiplier. The photon mode recording method described in 1.
(22) The photon mode recording method as described in (21), wherein the acid proliferating agent is represented by the following general formulas (34-1) to (34-6) in (21):

In the general formulas (34-1) to (34-6), R ₁₀₁ represents a group in which R ₁₀₁ OH becomes an acid having a pKa of 5 or less. R ₁₀₂ represents a 2-alkyl-2-propyl, 2-aryl-2-propyl group, a cyclohexyl group, a tetrahydropyranyl group, either of bis (p- alkoxyphenyl) methyl group. R ₁₀₃ , R ₁₀₄ , R ₁₁₅ and R ₁₁₇ each independently represent a substituent, and R ₁₀₅ , R ₁₀₆ , R ₁₀₇ , R ₁₁₀ , R ₁₁₃ and R ₁₁₆ each independently represent a hydrogen atom or a substituent. R ₁₁₈ and R ₁₁₉ each represents an alkyl group, and may be linked to each other to form a ring. R ₁₁₁ and R ₁₁₂ represent an alkyl group that is linked to each other to form a ring, and R ₁₁₄ represents a hydrogen atom or a nitro group. n101 represents an integer of 0 to 3.
(23) In the general formulas (34-1) to (34-6), R ₁₀₁ is a group in which R ₁₀₁ OH is either a sulfonic acid or an electron-withdrawing group-substituted carboxylic acid. (23) The photon mode recording method according to (23).
(24) The photon mode recording method according to any one of (1) to (13), wherein the recording component contains at least a base color-forming dye precursor as a dye precursor and a base generator.
(25) The photon mode recording method as described in (24), wherein the base generator is represented by the following general formulas (31-1) to (31-4) in (24).

In formula (31-1) ~ (31-4), R 201, R 202, R 213, R 214, R 215 are each independently a hydrogen atom, an alkyl group, an alkenyl group, a cycloalkyl group, an aryl group, a hetero R ₂₀₁ , R ₂₀₂ may be connected to each other to form a ring, and R ₂₁₃ , R ₂₁₄ , R ₂₁₅ may be connected to each other to form a ring. R ₂₀₃ , R ₂₀₆ , R ₂₀₇ and R ₂₀₉ each independently represent a substituent, and R ₂₀₄ , R ₂₀₅ , R ₂₀₈ , R ₂₁₀ and R ₂₁₁ each independently represents a hydrogen atom or a substituent, R ₂₁₀ , R ₂₁₁ may be linked to each other to form a ring. R ₂₁₆ , R ₂₁₇ , R ₂₁₈ and R ₂₁₉ each independently represents an alkyl group or an aryl group, and R ₂₁₂ represents an aryl group or a heterocyclic group. n201 represents an integer of 0 or 1, and n202 to n204 each independently represents an integer of 0 to 5.
(26) The two-photon absorption optical recording material as described in (25), wherein in formulas (31-1) and (31-2), n201 is 1.
(27) In the general formula (31-1), R ₂₀₃ is any one of a nitro group substituted at the 2-position or the 2,6-position, or an alkoxy group substituted at the 3,5-position ( 25) or the photon mode recording method according to (26).
(28) The photon mode recording method as described in (25) or (26), wherein in formula (31-2), R ₂₀₆ is an alkoxy group substituted at the 3,5-position.
(29) The base color-forming dye precursor is a dissociated azo dye, dissociated azomethine dye, dissociable oxonol dye, dissociable xanthene (fluorane) dye, or dissociated triphenylmethane dye, The photon mode recording method according to (24) to (28).
(30) The photon according to any one of (24) to (29), wherein the recording component of (24) comprises at least a base color-forming dye precursor as a dye precursor, a base generator, and further a base proliferating agent. Mode recording method.
(31) The photon mode recording method as described in (33), wherein the base proliferating agent is represented by the following general formula (35) in (30).

In the general formula (35), R ₁₂₁ and R ₁₂₂ each independently represents any of a hydrogen atom, an alkyl group, an alkenyl group, a cycloalkyl group, an aryl group, and a heterocyclic group, and R ₁₂₁ and R ₁₂₂ are connected to each other. R ₁₂₃ and R ₁₂₄ each independently represent a substituent, R ₁₂₃ and R ₁₂₄ may be linked together to form a ring, and R ₁₂₅ and R ₁₂₆ are each independently Represents a hydrogen atom or a substituent. n102 represents an integer of 0 or 1.
(32) The photon mode recording method as described in (31), wherein n102 is 1 in the general formula (35).
(33) The photon mode recording method according to (31) or (32), wherein the base proliferating agent of the general formula (35) is represented by the general formula (36-1) or (36-2).

In general formulas (36-1) and (36-2), R ₁₂₁ and R ₁₂₂ have the same meanings as in general formula (35).
(34) The photon mode recording method according to any one of (1) to (16), wherein the recording component contains at least a dye precursor represented by the following general formula (32).

In the general formula (32), A1 and PD are covalently bonded, and A1 is an organic compound site having a function of cutting the covalent bond with PD by electron transfer or energy transfer with the excited state of the two-photon absorption compound, PD represents an organic compound moiety having a feature that becomes a color former when covalently bonded to A1 and when the covalent bond with A1 is cleaved and released.
(35) The photon mode recording method described in (34), wherein the dye precursor of the general formula (32) is represented by any one of the general formulas (33-1) to (33-6).

In the general formulas (33-1) to (33-6), PD is as defined in the general formula (32), R ₇₁ , R ₈₀ and R ₈₁ represent a hydrogen atom or a substituent, and R ₇₂ , R ₇₃ , R ₇₈ , R ₇₉ , R ₈₂ and R ₈₃ each represents a substituent, a71, a72, a74 and a75 each independently represents an integer of 0 to 5, and a73 and a76 each independently represent 0 or 1. a71, a72, a74, a75 is 2 or more, plural _{R 72, R 73, R 78} , R 79 may be the same or different, may form a ring. R ₈₀ and R ₈₁ , R ₈₂ and R ₈₃ may be connected to each other to form a ring.
(36) In the general formula (32) or (33-1) to (33-6), PD is any one of dissociable azo dye, dissociable azomethine dye, dissociable oxonol dye, triphenylmethane dye, and xanthene dye. The photon mode recording method according to (34) or (35), wherein the photon mode recording method is characterized in that it is covalently linked to A1 on the chromophore.
(37) The photon mode recording method described in (1) to (3), wherein the recording component described in (1) is represented by the recording component described in (17) to (36).
(38) The photon mode recording method described in (1) to (37), wherein the sensitizing dye is an organic dye.
(39) The photon mode recording method as described in any one of (1) to (38), wherein the sensitizing dye is a methine dye or a phthalocyanine dye.
(40) The photon mode recording method according to (38), wherein the sensitizing dye is a cyanine dye, merocyanine dye, oxonol dye, phthalocyanine dye or a compound represented by the following general formula (1).
General formula (1)

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

In the formula, R ⁵ represents a hydrogen atom or a substituent, R ⁶ represents a hydrogen atom, an alkyl group, an alkenyl group, an aryl group, or a heterocyclic group, and Z ¹ represents an atomic group forming a 5- or 6-membered ring. .
(41) The photon mode recording method described in (40), wherein in the compound represented by the general formula (1), R ¹ and R ³ are linked to form a ring.
(42) The photon mode recording method described in (41), wherein in the compound represented by the general formula (1), R ¹ and R ³ are linked to form a cyclopentanone ring together with a carbonyl group.
(43) The photon mode recording method described in (40) to (42), wherein X ¹ and X ² of the compound represented by the general formula (1) are represented by the general formula (2).
(44) In the compound represented by the general formula (1), X ¹ and X ² are represented by the general formula (2), R ⁶ is an alkyl group, and the ring formed by Z ¹ is an indolenine ring , An azindolenin ring, pyrazoline ring, benzothiazole ring, thiazole ring, thiazoline ring, benzoxazole ring, oxazole ring, oxazoline ring, benzimidazole ring, thiadiazole ring, quinoline ring (46) The two-photon absorption optical recording material according to (46).
(48) In the compound represented by the general formula (1), X ¹ and X ² are represented by the general formula (2), R ⁶ is an alkyl group, and the ring formed by Z ¹ is an indolenine ring The photon mode recording method according to any one of (40) to (43), wherein the photon mode recording method is represented by any one of: azaindolenin ring, benzothiazole ring, benzoxazole ring, and benzimidazole ring.
(46) In (40), the cyanine dye is represented by the following general formula (3), the merocyanine dye is represented by the following general formula (4), and the oxonol dye is represented by the general formula (5). The photon mode recording method according to (40).

In the general formulas (3) to (5), Za ₁ , Za ₂ and Za ₃ each represent an atomic group forming a 5-membered or 6-membered nitrogen-containing heterocycle, and Za ₄ , Za ₅ and Za ₆ are each 5 A group of atoms forming a member or six-membered ring is represented. Ra ₁ , Ra ₂ and Ra ₃ each independently represent a hydrogen atom, an alkyl group, an alkenyl group, an aryl group or a heterocyclic group.
Ma _{1 to} Ma ₁₄ each independently represent a methine group, may have a substituent, and may form a ring with another methine group. na ¹ , na ² and na ³ are each 0 or 1, and ka ¹ and ka ³ each represents an integer of 0 to 3. When ka ¹ is 2 or more, the plurality of Ma ₃ and Ma ₄ may be the same or different. 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.
(47) The photon mode recording method according to any one of (1) to (46), wherein the sensitizing dye has at least one hydrogen bonding group in (1) to (46).
(48) The photon mode recording method as described in (47), wherein the hydrogen bonding group is a —COOH group or a —CONH ₂ group in (47).
(49) The photon according to any one of (1) to (48), wherein the sensitizing dye is a two-photon absorption compound and functions as a sensitizing dye by performing linear (one-photon) absorption. Mode recording method.
(50) Coloring produced by a photon mode recording material (preferably a two-photon absorption optical recording material) used in the photon mode recording method described in (1) to (49) from a sensitizing dye, a two-photon absorption compound or a dye precursor. An electron-donating compound having the ability to reduce the radical cation of the body, or an electron-accepting compound having the ability to oxidize the radical anion of the chromophore generated from the sensitizing dye, the two-photon absorption compound or the dye precursor The photon mode recording method described in any one of (1) to (49).
(51) In (50), the photon mode recording material contains an electron donating compound, and the electron donating compound is an alkylamine, aniline, phenylenediamine, triphenylamine, carbazole, phenothiazine, or phenoxazine. Photon according to (50), characterized in that the photon is any one of benzene, phenazines, hydroquinones, catechols, alkoxybenzenes, aminophenols, imidazoles, pyridines, metallocenes, metal complexes, and semiconductor fine particles Mode recording method.
(52) The photon mode recording method as described in (50) or (51), wherein the electron donating compound is a phenothiazine.
(53) In (50), the photon mode recording material contains an electron-accepting compound, and the electron-accepting compound is an aromatic compound, a heterocyclic compound or the like having an electron-attracting group introduced, such as dinitrobenzene or dicyanobenzene. The photon mode recording method as described in (50), which is any one of a heterocyclic compound having an electron withdrawing group introduced, an N-alkylpyridinium salt, a benzoquinone, an imide, a metal complex, or a semiconductor fine particle .
(54) Two-photon absorption induced by irradiating the two-photon absorption optical recording material with a laser beam having a wavelength longer than the linear absorption band of the two-photon absorption compound and having no linear absorption in the first step A photon mode recording method comprising forming a latent image using
(55) A photon mode recording material (preferably a two-photon absorption optical recording material) which performs the photon mode recording method described in (1) to (54).
(56) A two-photon absorption three-dimensional optical recording medium, a two-photon absorption three-dimensional optical recording method and a reproducing method comprising the two-photon absorption optical recording material described above.
(57) The photon mode optical recording medium described above, wherein the photon mode optical recording material, the two-photon absorption optical recording material or the two-photon absorption three-dimensional optical recording material is stored in a light-shielding cartridge at the time of storage; Photon absorption recording medium or two-photon absorption three-dimensional optical recording medium.
(58) A three-dimensional volume display comprising the two-photon absorption optical recording material and a three-dimensional volume display manufacturing method.
(59) An optical recording medium, an optical recording method and a reproducing method using the photon mode recording material or the two-photon absorption optical recording material described above.
(60) A near-field optical recording medium, a near-field recording method, and a reproducing method using the optical recording medium according to (59).

By using the photon mode recording material and recording method of the present invention, recording and reproduction based on a difference in refractive index or an absorption rate can be performed with very high sensitivity.
Further, by using the two-photon absorption optical recording material of the present invention, the refractive index or the absorptance is three-dimensionally with very high sensitivity at the laser focal point (recording part) and the non-focusing part (non-recording part). It can be modulated, and can be applied to a three-dimensional optical recording medium and its high-speed recording / reproducing method.

  The photon mode recording material of the present invention will be described in detail below.

The photon mode recording material of the present invention is at least
1) sensitizing dye,
2) It contains a dye precursor which can be a color former that has a longer absorption wavelength than the sensitizing dye and has an absorption in a wavelength range different from that of the sensitizing dye, and electron transfer or energy from the excited state of the sensitizing dye or color former. A recording component that can be recorded as a difference in refractive index or absorptance by moving,
Have
Here, the sensitizing dye may function as a two-photon absorption sensitizing dye by performing two-photon absorption by non-resonant two-photon absorption, or may function as a sensitizing dye by normal linear (one-photon) absorption.

Furthermore, in the photon mode recording method of the present invention, at least a first step of generating a color former having an absorption form different from that of the sensitizing dye as a latent image by light irradiation, and a molar of sensitizing dye linear absorption in the color former latent image. A second step of irradiating light in a wavelength region having an extinction coefficient of 5000 or less to cause linear absorption of the color former and generating the color former by self-sensitizing amplification and recording it as a refractive index difference or an absorption difference; These are performed by dry processing.
In addition, in the wavelength range of the light irradiated at a 2nd process, it is more preferable that the molar absorption coefficient of a sensitizing dye linear absorption is 1000 or less, and it is further more preferable that it is 500 or less.
Further, in the wavelength range of the light irradiated in the second step, the molar extinction coefficient of the color former is more preferably 5000 or more, and further preferably 10,000 or more.
It is preferable that the light irradiated in the first step and the second step have different wavelengths. Moreover, it is preferable that the light irradiated at a 2nd process is whole surface exposure (what is called solid exposure, blanket exposure, non-imagewise exposure).

  Here, the “latent image” in the first step of the present invention means “a refractive index difference or an absorptance preferably equal to or less than a half of a refractive index difference or an absorptivity difference formed after the second step”. "Difference image" (that is, preferably an amplification step of 2 times or more is performed in the second step), more preferably 1/5 or less, more preferably 1/10 or less, and still more preferably An image having a difference in refractive index or absorptivity difference of 1/30 or less (that is, an amplification step of 5 times or more, more preferably 10 times or more, more preferably 30 times or more is performed in the second step). ).

  The photon mode recording material of the present invention includes an optical recording medium such as DVD-R and DVD-BL (BR), a near-field optical recording medium, a three-dimensional optical recording medium, an imaging material, and a three-dimensional imaging material (three-dimensional volume display). It is preferably used for a three-dimensional optical recording medium and a three-dimensional imaging material (three-dimensional volume display material).

Further, the photon mode recording method of the present invention and the photon mode recording material capable of such recording include at least a first step of forming a latent image by two-photon absorption caused by light irradiation, and the latent image. A two-photon absorption optical recording method characterized by having a second step of forming a refractive index difference or an absorption difference by amplification, and a two-photon absorption optical recording material capable of such recording preferable.
In that case, it is preferably used for optical recording media such as DVD-R and DVD-BL (BR), near-field optical recording media, three-dimensional optical recording media, three-dimensional imaging materials (three-dimensional volume display materials), and the like. .
The photon mode recording method of the present invention and the photon mode recording material capable of such recording are more preferably the two-photon absorption three-dimensional optical recording method having the above characteristics and the two-photon absorption capable of such recording. A three-dimensional optical recording material is preferable, and in that case, it is more preferably used for a three-dimensional optical recording medium, a three-dimensional imaging material (three-dimensional volume display material), and the like.

  Here, the “latent image” in the first step of the present invention also means “a refractive index difference or an absorptance preferably equal to or less than a half of a difference in refractive index or an absorption difference formed after the second step. "Difference image" (that is, preferably an amplification step of 2 times or more is performed in the second step), more preferably 1/5 or less, more preferably 1/10 or less, and still more preferably An image having a difference in refractive index or absorptivity difference of 1/30 or less (that is, an amplification step of 5 times or more, more preferably 10 times or more, more preferably 30 times or more is performed in the second step). ).

Here, the second step is preferably any one of light irradiation, heat application, electric field application, and magnetic field application. These are preferably performed over the entire surface of the recording material.
The second step is more preferably any one of light irradiation, heat application, and electric field application, more preferably either light irradiation or heat application, and most preferably light irradiation.
Further, when the second step is light irradiation, the light to be irradiated is preferably full-surface exposure (so-called solid exposure, blanket exposure, non-imagewise exposure).
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.

Further, as the two-photon absorption optical recording method of the present invention and the two-photon absorption optical recording material capable of such recording, a color image having an absorption shape different from that of at least the two-photon absorption compound is obtained by two-photon absorption exposure. And a linear absorption of the color former by irradiating the color former latent image with light having a wavelength range of 5000 or less of the two-photon absorption compound linear (1-photon) absorption. It is preferable to have a second step of generating a color former by self-sensitizing amplification and recording it as a difference in refractive index or a difference in absorbance.
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.
Further, in the wavelength range of the light irradiated in the second step, the molar extinction coefficient of the color former is more preferably 5000 or more, and further preferably 10,000 or more.

Furthermore, as a two-photon absorption optical recording method of the present invention and a two-photon absorption optical recording material capable of such recording, preferably a compound group capable of recording a difference in refractive index or an absorption difference by two-photon absorption is used. ,
1) a two-photon absorption compound capable of absorbing two photons and generating an excited state in the first step;
2) 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, and from the excited state of the two-photon absorption compound or the color former A recording component that can be recorded as a difference in refractive index or a difference in absorption rate by electron transfer or energy transfer,
A two-photon absorption optical recording method characterized by having a two-photon absorption optical recording material capable of such recording is preferable.

At that time,
B) The wavelength of light for forming a latent image by two-photon absorption recording in the first step is the same as the wavelength of light for amplifying the latent image in the second step to form a difference in refractive index or absorptivity. If it is,
B) The wavelength of light that amplifies the latent image in the second step to form a difference in refractive index or absorptivity than the wavelength of light that forms the latent image by two-photon absorption recording in the first step. When the short wavelength and the molar absorption coefficient of the two-photon absorption compound linear (one-photon) absorption is in the wavelength range of 5000 or less,
It is preferable that it is either.
In the case of the above (a), the molar extinction coefficient of linear (one-photon) absorption of the two-photon absorption compound is preferably 10 or less at the wavelength of light irradiated in the first step and the second step. It is more preferably 1 or less, further preferably 0.1 or less, and most preferably no linear absorption.
In the case of (b) above, the molar absorption coefficient of linear absorption of the two-photon absorption compound is more preferably 1000 or less, and even more preferably 500 or less in the wavelength range of the light irradiated in the second step. .
Further, in both of the above a) and b), the molar extinction coefficient of the color former is more preferably 5000 or more, and most preferably 10,000 or more in the wavelength range of the light irradiated in the second step.
Of the above a) or b), b) is more preferred.

Here, in the photon mode recording material or the two-photon absorption optical recording material of the present invention, recording and amplification are performed by the first step and the second step as described above to record the refractive index difference or the absorptance difference. After that, it is preferable to reproduce by irradiating the recording material with light and detecting a difference in reflectance or transmittance of light based on a difference in refractive index or absorptance between the recording portion and the non-recording portion.
This is because, in an optical recording medium, it is possible to record and reproduce digital signals by irradiating light on an absorptive or refractive index modulated material, and in an imaging (display) material, the absorptance or refractive index is modulated. This is because the image can be viewed by irradiating the material with light.

  At that time, it is preferable that the wavelength of light irradiated for detecting a difference in reflectance or transmittance during reproduction is the same as the wavelength of light irradiated in the first step or the second step. More preferably, it is the same as the wavelength of the light irradiated in the step.

  Therefore, the wavelength of the light that amplifies the latent image in the second step to form the refractive index difference or the absorptivity difference is larger than the wavelength of the light that forms the latent image by the two-photon absorption recording in the first step. It is a short wavelength and a two-photon absorption compound linear (one-photon) absorption has a molar extinction coefficient of 5000 or less, and further, the wavelength of light irradiated when recording by two-photon absorption and reflection during reproduction Two-photon absorption optical recording / reproducing method, and a two-photon absorption optical recording material capable of such recording / reproduction, characterized in that the wavelengths of light irradiated for detecting a difference in transmittance or transmittance are the same Is most preferred in the present invention.

Here, the refractive index of the dye generally takes a high value in the region having a longer wavelength from near the linear absorption maximum wavelength (λmax), 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 2 and in some cases exceeding 2.5. On the other hand, organic compounds which 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 can preferably form not only an absorptivity difference but also a large refractive index difference.
In the dye-only film of the dye formed from the recording component, the refractive index at the recording wavelength is more preferably 1.8 or more, further preferably 2 or more, and preferably 2.2 or more. Most preferred.

Therefore, in the photon mode recording material or the two-photon absorption optical recording material of the present invention, when a refractive index difference is used for recording, the recording is performed so that the refractive index difference between the recording part and the non-recording part becomes maximum near the reproduction wavelength. It is preferable to design the material, that is, it is more preferable that the absorption maximum of the color former exists between the reproduction wavelength and a wavelength near 200 nm shorter than the reproduction wavelength.
Further, in the photon mode recording material or the two-photon absorption optical recording material of the present invention, when the difference in the absorptance is used for recording, the recording is performed so that the difference in the absorptance between the recording part and the non-recording part is maximized near the reproduction wavelength. It is preferable to design the material.

  In the photon mode recording material and the two-photon absorption optical recording material of the present invention, it is preferable that the recording is not rewritable. Here, the system that cannot be rewritten is a system that is recorded by an irreversible reaction, and indicates a system that is recorded once and the data can be stored without being overwritten and recorded (without being rewritten). Therefore, it is suitable for storing important and long-term data. However, it is possible to newly record and record in an area not yet recorded. In this sense, it is generally called a write once type or a write once type. Furthermore, in the two-photon absorption optical recording material of the present invention, it is preferable not to perform wet processing, that is, dry processing.

A laser is preferably used for recording by two-photon absorption in the first step of the photon mode recording material and the two-photon absorption optical 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 400 to 800 nm visible or infrared light.
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. Preferred are semiconductor lasers, solid lasers, fiber lasers, semiconductor lasers used in DVD-R having an oscillation wavelength in the range of 620 to 680 nm, solid lasers, GaN lasers having an oscillation wavelength in the vicinity of 400 to 415 nm, etc. Can be 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.

  The light used for reproduction is also preferably laser light, and although the power or pulse shape is the same or different, it is more preferable to reproduce using the same laser used during recording.

When recording is performed on the two-photon absorption optical recording material of the present invention, it is induced by irradiation with laser light having a wavelength longer than the linear absorption band of the two-photon absorption compound and having no linear absorption. Recording is preferably performed using photon absorption.
Therefore, the linear absorption of the chromophore generated by inducing two-photon absorption by irradiating laser light having a wavelength longer than the linear absorption band of the two-photon absorption compound and having no linear absorption is the two-photon absorption. More preferably, the refractive index difference or the absorptivity difference recording is performed using the fact that the compound linear absorption appears on the long wavelength side from the long wavelength side absorption edge.

  The photon mode recording material (two-photon absorption light recording material) of the present invention preferably uses a binder in addition to the sensitizing dye (two-photon absorption compound) and the recording component, and if necessary, an electron donating compound, Additives such as an electron-accepting compound, a polymerizable monomer, a polymerizable oligomer, a polymerization initiator, a crosslinking agent, a heat stabilizer, a plasticizer, and a solvent can be used.

In the photon mode recording material and the two-photon absorption optical recording material of the present invention, the size of the reaction part or color development part produced by recording is preferably in the range of 10 nm to 100 μm, and in the range of 50 nm to 5 μm. Is more preferable, and the range of 50 nm to 2 μm is more preferable.
Further, in order to enable 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 photon mode recording material and the two-photon absorption optical recording material of the present invention, a fixing step may be performed after recording by light (one photon), heat, or both.
In particular, when an acid proliferating agent or a base proliferating agent is used in the photon mode recording material and the two-photon absorption optical 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 photon mode recording material and the two-photon absorption light recording material is irradiated with ultraviolet light or visible light (non-interference exposure). 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 present invention, the first and second steps may also serve as fixing, and the second step preferably serves as fixing.

In the photon mode recording material of the present invention, the chemical reaction, color development reaction, and the like that occur when the sensitizing dye absorbs light is not a reaction that does not involve thermal decomposition, that is, a heat mode reaction.
In the two-photon absorption optical recording material of the present invention, it is particularly preferable from the viewpoint of high sensitivity that the chemical reaction, color development reaction, and the like that occur by performing two-photon absorption occur in a reaction that does not involve thermal decomposition, that is, in a photon mode. .
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.

  When the photon mode recording material and the two-photon absorption optical recording material of the present invention are used for an optical recording medium, the two-photon absorption optical recording material is preferably stored in a light-shielding cartridge during storage. In addition, when the two-photon absorption of the present invention is used for an optical recording medium, it is preferable from the viewpoint of storage stability that the two-photon absorption compound is covered with a filter layer that absorbs light having a wavelength with linear absorption.

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

The concept of the photon mode recording material of the present invention (especially in the case of the two-photon absorption optical recording material) is shown below, but the present invention is not limited to this. In the following description, numerical values are merely examples.
For example, a two-photon absorption optical recording material is irradiated with a 780 nm laser, and a two-photon absorption compound absorbs two photons to generate an excited state (the 780 nm has no linear absorption of the two-photon absorption compound). By transferring energy or electrons from the excited state of the two-photon absorption compound to the recording component, a part of the dye precursor contained in the recording component 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 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). Since the latent image is not generated in the non-recorded portion that is not irradiated with the laser in the first step, the self-sensitized coloring reaction hardly occurs in the second step, and as a result, the recording portion and the non-recording portion are largely refracted. Rate modulation or absorption rate modulation can be formed. For example, by using a 780 nm laser again and irradiating the recorded two-photon absorption optical recording material, it becomes possible to reproduce by the difference in reflectance or transmittance of light based on a large difference in refractive index between the recording portion and the non-recording portion. , A two-photon absorption (three-dimensional) optical recording medium by 780 nm optical recording / reproduction can be provided.

  The components used in the photon mode recording material and the two-photon absorption optical recording material of the present invention will be described in detail below.

First, the sensitizing dye in the photon mode recording material of the present invention will be described.
Here, the sensitizing dye of the present invention functions as a sensitizing dye by normal linear (one-photon) absorption even if it functions as a two-photon absorption sensitizing dye by performing two-photon absorption by non-resonant two-photon absorption. Also good.

  In the present invention, the sensitizing dye preferably functions as a two-photon absorption sensitizing dye (two-photon absorption compound). That is, the photon mode recording material of the present invention is preferably a two-photon absorption optical recording material.

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 optical recording material, particularly a two-photon absorption three-dimensional optical recording material, an excited state is efficiently generated by performing two-photon absorption with high sensitivity in order to achieve a high transfer (recording) speed. A two-photon absorbing compound that can be used is needed.
The efficiency with which a 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 optical 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 is 1000 GM or more. Is more preferably 5000 GM or more, and most preferably 10,000 GM or more.

  Preferred examples of the sensitizing dye in the photon mode recording material of the present invention and the two-photon absorption compound in the two-photon absorption light recording material are given below. In the present invention, examples of preferable compounds of the sensitizing dye and the two-photon absorption compound are the same. If the compound causes linear absorption, the compound functions as a sensitizing dye, and if the compound causes nonlinear two-photon absorption, the compound becomes a two-photon absorption compound. It functions.

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

In addition, a pigment | dye here is a general term with respect to the compound which has a part of absorption in an ultraviolet region (preferably 200-400 nm) visible region (400-700 nm) or a near-infrared region (preferably 700-2000 nm). Preferred is a generic name for compounds having a part of absorption in the visible region.
Any two-photon absorption compound may be used in the present invention. 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, trinuclear merocyanine dye, tetranuclear merocyanine dye, rhodacyanine dye, complex cyanine dye, complex Russianine 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, triphenylmethane dye, Diphenylmethane dye, thioxanthene dye, phenothiazine dye, phenoxazine dye, phenazine dye, azo dye, azomethine dye, perylene dye, phthaloperylene dye, indigo dye, polyene dye, acridine dye, acridinone dye, diphenylamine dye, quinacridone dye, quinophthalone dye, Porphyrin dyes, azaporphyrin dyes, chlorophyll dyes, phthalocyanine dyes, fused aromatic dyes, styrenic dyes, metalloses Dyes, metal complex dyes, stilbazolium dyes, more preferably cyanine dyes, hemicyanine dyes, streptocyanine dyes, styryl dyes, pyrylium dyes, merocyanine dyes, trinuclear merocyanine dyes, tetranuclear merocyanine dyes, rhodacyanine dyes, complex cyanine dyes , Complex merocyanine dye, allopolar dye, arylidene dye, oxonol dye, hemioxonol dye, squalium dye, croconium dye, azurenium dye, ketocoumarin dye, styrylcoumarin dye, pyran dye, anthraquinone dye, quinone dye, triphenylmethane dye, diphenylmethane Dye, thioxanthene dye, phenothiazine dye, phenoxazine dye, phenazine dye, azo dye, azomethine dye, indigo dye Polyene dyes, acridine dyes, acridinone dyes, diphenylamine dyes, quinacridone dyes, quinophthalone dyes, azaporphyrin dyes, chlorophyll dyes, phthalocyanine dyes, fused aromatic dyes, metallocene dyes, metal complex dyes, more preferably cyanine dyes, Hemicyanine dye, streptocyanine dye, styryl dye, 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 Dyes, polyene dyes, azaporphyrin dyes, chlorophyll dyes, phthalocyanine dyes, metal complex dyes, more preferably cyanine dyes, merocyanes Emissions dyes, arylidene dyes, oxonol dyes, squarylium dyes and azo dyes, phthalocyanine dyes, more preferably a cyanine dye, merocyanine dye, oxonol dye, most preferably a cyanine dye.

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

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

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

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

In the general formula (3), Za ₁ and Za ₂ each represents an atomic group forming a 5-membered or 6-membered nitrogen-containing heterocycle. The 5-membered or 6-membered nitrogen-containing heterocycle formed is preferably an oxazole nucleus having 3 to 25 carbon atoms (hereinafter referred to as C number) (for example, 2-3-methyloxazolyl, 2-3-ethyloxazolyl). , 2-3,4-diethyloxazolyl, 2-3-methylbenzoxazolyl, 2-3-ethylbenzoxazolyl, 2-3-sulfoethylbenzoxazolyl, 2-3-sulfopropyl Benzoxazolyl, 2-3-methylthioethylbenzoxazolyl, 2-3-methoxyethylbenzoxazolyl, 2-3-sulfobutylbenzoxazolyl, 2-3-methyl-β-naphthoxazolyl 2-3-methyl-α-naphthoxazolyl, 2-3-sulfopropyl-β-naphthoxazolyl, 2-3-sulfopropyl-β-naphthoxazolyl, 2-3- ( -Naphthoxyethyl) benzoxazolyl, 2-3,5-dimethylbenzoxazolyl, 2-6-chloro-3-methylbenzoxazolyl, 2-5-bromo-3-methylbenzoxazolyl, 2- 3-ethyl-5-methoxybenzoxazolyl, 2-5-phenyl-3-sulfopropylbenzoxazolyl, 2-5- (4-bromophenyl) -3-sulfobutylbenzoxazolyl, 2-3 -Methyl-5,6-dimethylthiobenzoxazolyl, 2-3-sulfopropyloxazolyl, 2-3-sulfopropyl-γ-naphthoxazolyl, 2-3-ethyl-α-naphthoxazolyl 2-5-chloro-3-ethyl-α-naphthoxazolyl, 2-5-chloro-3-ethylbenzoxazolyl, 2-5-chloro-3-sulfopropylbenzoxa Zolyl, 2-5, 6-dichloro-3-sulfopropylbenzoxazolyl, 2-5-bromo-3-sulfopropylbenzoxazolyl, 2-3-ethyl-5-phenylbenzoxazolyl, 2- 5- (1-pyrrolyl) -3-sulfopropylbenzoxazolyl, 2-5,6-dimethyl-3-sulfopropylbenzoxazolyl, 2-3-ethyl-5-sulfobenzoxazolyl, etc. A C 3-25 thiazole nucleus (for example, 2-3-methylthiazolyl, 2-3-ethylthiazolyl, 2-3-sulfopropylthiazolyl, 2-3-sulfobutylthiazolyl, 2-3, 4-dimethylthiazolyl, 2-3,4,4-trimethylthiazolyl, 2-3-carboxyethylthiazolyl, 2-3-methylbenzothiazolyl, 2-3-ethylethyl Zothiazolyl, 2-3-butylbenzothiazolyl, 2-3-sulfopropylbenzothiazolyl, 2-3-sulfobutylbenzothiazolyl, 2-3-methyl-β-naphthothiazolyl, 2-3-sulfopropyl -Γ-naphthothiazolyl, 2-3- (1-naphthoxyethyl) benzothiazolyl, 2-3,5-dimethylbenzothiazolyl, 2-6-chloro-3-methylbenzothiazolyl, 2-6-iodo-3- Ethyl benzothiazolyl, 2-5-bromo-3-methylbenzothiazolyl, 2-3-ethyl-5-methoxybenzothiazolyl, 2-5-phenyl-3-sulfopropylbenzothiazolyl, 2 -5- (4-Bromophenyl) -3-sulfobutylbenzothiazolyl, 2-3-methyl-5,6-dimethylthiobenzothiazolyl, 2-5-chloro-3 Ethyl benzothiazolyl, 2-5-chloro-3-sulfopropylbenzothiazolyl, 2-3-ethyl-5-iodobenzothiazolyl, etc.), C 3-25 imidazole nucleus (for example, 2-1, 3-diethylimidazolyl, 2-1, 3-dimethylimidazolyl, 2-1 -methylbenzimidazolyl, 2-1, 3,4-triethylimidazolyl, 2-1, 3-diethylbenzimidazolyl, 2-1 3,5-trimethylbenzimidazolyl, 2-6-chloro-1,3-dimethylbenzimidazolyl, 2-5,6-dichloro-1,3-diethylbenzimidazolyl, 2-1,3-disulfopropyl-5-cyano-6 -Chlorobenzimidazolyl, 2-5,6-dichloro-3-ethyl-1-sulfopropylbenzimidazolyl, 2-5 Chloro-6-cyano-1,3-diethylbenzimidazolyl, 2-5-chloro-1,3-diethyl-6-trifluoromethylbenzimidazolyl, etc.), an indolenine nucleus having 10 to 30 carbon atoms (for example, 3 , 3-Dimethyl-1-pentylindolenine, 3,3, -dimethyl-1-sulfopropylindolenine, 5-carboxy-1,3,3-trimethylindolenine, 5-carbamoyl-1,3,3-trimethyl Indolenine, 1,3,3, -trimethyl-4,5-benzoindolenin, etc.), C 9-25 quinoline nucleus (for example, 2-1-methylquinolyl, 2-1-ethylquinolyl, 2- 1-methyl 6-chloroquinolyl, 2-1,3-diethylquinolyl, 2-1-methyl-6-methylthioquinolyl, 2-1-sulfop Lopyrquinolyl, 4-1-methylquinolyl, 4-1-pentylquinolyl, 4-1-sulfoethylquinolyl, 4-1-methyl-7-chloroquinolyl, 4-1,8-diethylquinolyl, 4-1-methyl -6-methylthioquinolyl, 4-1-sulfopropylquinolyl, etc.), C 3-25 selenazole nucleus (for example, 2-3 methylbenzoselenazolyl, etc.), C 5 -25 pyridine nuclei (for example, 2-pyridyl and the like) and the like, and in addition, thiazoline nuclei, oxazoline nuclei, selenazoline nuclei, tellurazoline nuclei, tellurazole nuclei, benzotelrazole nuclei, imidazoline nuclei, imidazo [4 , 5-quinoxaline] nucleus, oxadiazole nucleus, thiadiazole nucleus, tetrazole nucleus, or pyrimidine nucleus Can.

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

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

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

Ra ₁ and Ra ₂ are each independently 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 having 2 to 20 carbon atoms, for example, vinyl, allyl), aryl group ( Preferably C6-20, such as phenyl, 2-chlorophenyl, 4-methoxyphenyl, 3-methylphenyl, 1-naphthyl), or a heterocyclic group (preferably C1-20, such as pyridyl, thienyl, Furyl, thiazolyl, imidazolyl, pyrazolyl, pyrrolidino, piperidino, morpholino) and more preferred Ku is an 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).

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

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

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

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

  When the sensitizing dye and the two-photon absorption compound of the present invention are merocyanine dyes, the sensitizing dye and the two-photon absorption compound are preferably represented by the general formula (4).

In the general formula (4), Za ₃ represents an atomic group 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 ring, an imidazole ring, a thiazole ring, or an indolenine ring, and more preferably an oxazole nucleus, a thiazole ring, or an indolenine ring. is there.

Za ₄ represents an atomic group forming a 5-membered or 6-membered ring. The ring formed from Za ₄ is a part generally called an acidic nucleus and is defined by James, 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- Emissions, 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, or coumarin-2,4-dione, more preferably pyrazolidine-3,5-dione Indane-1,3-dione, 1,3-dioxane-4,6-dione, barbituric acid, or 2-thiobarbituric acid, most preferably pyrazolidine-3,5-dione, barbituric acid, Or 2-thiobarbituric acid, most preferably 2-thiobarbituric acid.

The ring formed from Za ₄ may be substituted (preferred examples of the substituent are the same as those of the substituent on Za ₃ ). More preferably, the substituent is preferably an alkyl group, an aryl group, a heterocyclic group, a halogen. An atom, a cyano group, a carboxyl group, a sulfo group, an alkoxy group, a sulfamoyl group, a carbamoyl group, or 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 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 an alkyl having 1 to 6 carbon atoms). Group) or a sulfoalkyl group (preferably 3-sulfopropyl, 4-sulfobutyl, 3-methyl-3-sulfopropyl, 2′-sulfobenzyl).

Ma _{8 to} Ma ₁₁ each independently 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 ₁ and Za ₂ ). 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. The substituent is more preferably an alkyl group.
Ma _{8 to} Ma ₁₁ are preferably unsubstituted methine groups or alkyl groups (preferably having a C number of 1 to 6) substituted methine groups, and more preferably unsubstituted, ethyl group-substituted, and methyl group-substituted methine groups.
Ma _{8 to} Ma ₁₁ may be linked to each other to form a ring, and preferred examples of the ring formed include a cyclohexene ring, a cyclopentene ring, a benzene ring, and a thiophene ring.

na ³ is 0 or 1, preferably 0.

ka ² represents an integer of 0 to 8, preferably an integer of 0 to 4, more preferably an integer of 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 sensitizing dye and the two-photon absorption compound of the present invention are oxonol dyes, they are preferably represented by the general formula (5).

In the general formula (5), Za ₅ and Za ₆ each represent a group of atoms 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, or coumarin-2,4-dione, more preferably barbituric acid, or 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 substituent on Za ₅ and Za ₆ ), and the substituent is 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. An alkyl group, a halogen atom, an alkoxy group, an aryl group, a heterocyclic group, a carbamoyl group, or a carboxy group is more preferable, and an alkyl group, an aryl group, or a heterocyclic group is more preferable.
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 an integer of 0 to 2, and more preferably 1 or 2.
When ka ³ is 2 or more, Ma ₁₂ and Ma ₁₃ may be the same or different.

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

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

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

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

X ¹ and X ² are independently an aryl group [preferably 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 the same as the substituents of Ma1 to Ma7 as examples of the substituents). And more preferably an alkyl group, an aryl group, a heterocyclic group, a halogen atom, an amino group, a hydroxyl group, an alkoxy group, an aryloxy group, an aryl group substituted with an acylamino group, and more preferably an alkyl group, an amino group Represents an aryl group substituted with a group, a hydroxyl group, an alkoxy group or an acylamino group, and most preferably a phenyl group substituted with a dialkylamino group or a diarylamino group at the 4-position. At that time, a plurality of substituents may be linked to form a ring, and a preferred ring formed includes a julolidine ring. ], A heterocyclic group (preferably having 1 to 20 carbon atoms, preferably 3 to 8 membered ring, more preferably 5 or 6 membered ring such as pyridyl, thienyl, furyl, thiazolyl, imidazolyl, pyrazolyl, pyrrolyl, indolyl, carbazolyl, Phenothiazino, pyrrolidino, piperidino, morpholino, more preferably indolyl, carbazolyl, pyrrolyl, phenothiazino, the heterocycle may be substituted, and preferred substituents are the same as in the case of the aryl group), or the general formula (2) Represents a group represented by

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

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

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

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

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

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

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

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

For reference, the meeting is explained below. As for the association, for example, James, “The Theory of the Photographic Process”, 4th edition, Macmillan Publishers, 1977, Chapter 8, 218. -222 pages and "J-Aggregates" written by Takayoshi Kobayashi, World Scientific Publishing Co. Pte. Ltd., 1996) .
A monomer means a monomer. From the viewpoint of the absorption wavelength of the aggregate, 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.

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

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

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

The intermolecular association state of a compound can be formed in various ways.
For example, in a solution system, an aqueous solution to which a matrix such as gelatin is added (for example, gelatin 0.5 wt% · compound 10 ⁻⁴ M aqueous solution), an aqueous solution to which a salt such as KCl is added (for example, KCl 5% · compound 2 × 10 ^−3). M aqueous solution), a method of dissolving a compound in a good solvent, a method of adding a poor solvent afterwards (for example, DMF-water system, chloroform-toluene system, etc.) and the like.
Examples of the film system include 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.

  Hereinafter, preferred specific examples of the sensitizing dye and the two-photon absorption compound used in the present invention are listed, but the present invention is not limited to these.

  Next, the recording components in the photon mode recording material or the two-photon absorption recording material of the present invention will be described in detail.

  The recording component of the present invention includes a dye precursor that can be a color former that has a longer absorption wavelength than the original state and has absorption in a wavelength range different from that of the sensitizing dye (or two-photon absorption compound linear absorption), and Including a sensitizing dye (two-photon absorption compound) or a compound group that can be recorded as a difference in refractive index or a difference in absorption rate by electron transfer or energy transfer from an excited state of a color former.

At that time, it is important that the refractive index or the absorption rate is different between a place where the color development reaction occurs (recording portion or laser focus portion) and a place where the color development reaction does not occur (non-recording portion or laser non-focus portion).
As described above, the refractive index of the dye generally takes a high value in the region having a wavelength longer than that near the absorption maximum wavelength (λmax), and particularly takes a very high value in a region having a wavelength longer by about 200 nm than λmax to λmax, Some dyes have high values exceeding 2 and further exceeding 2.5.
On the other hand, an organic compound that is not a pigment such as a binder polymer usually has a refractive index of about 1.4 to 1.6.
Therefore, the recording component of the present invention is obtained by directly transferring electrons or energy from the sensitizing dye excited state or the two-photon excited state of the two-photon absorbing compound, or by the two-photon excitation of the sensitizing dye excited state or the two-photon absorbing compound. It is preferable to include a dye precursor that can become a color former whose absorption is changed from the original state by an acid or base generated by electron transfer or energy transfer from the state to the acid generator or base generator.

  As the recording component in the photon mode recording material or the two-photon absorption optical recording material of the present invention, the following combinations are preferable.

A) A combination comprising at least an acid-coloring dye precursor as a dye precursor and an acid generator. A combination further containing an acid proliferating agent if necessary.
B) A combination containing at least a base color-forming dye precursor as a dye precursor, a base generator, and a base proliferating agent as necessary.
C) An organic compound moiety having a function of cleaving a covalent bond by electron transfer or energy transfer with a sensitizing dye excited state or a two-photon excited state of a two-photon absorption compound, and when the covalent bond is released In the case of containing a compound in which an organic compound moiety having a characteristic to be a color former is covalently bonded. A combination further containing a base if necessary.
D) When the compound contains a compound capable of reacting by electron transfer with the sensitizing dye excited state or the two-photon excited state of the two-photon absorbing compound to change the absorption form.

In any case, in the case of the energy transfer mechanism from the sensitizing dye excited state or the two-photon excited state of the two-photon absorption compound, the Forster mechanism in which energy transfer occurs from the singlet excited state is also from the triplet excited state. Either a Dexter type mechanism in which energy transfer occurs may be used.
In that case, in order for energy transfer to occur efficiently, it is preferable that the excitation energy in the sensitized dye excited state or the two-photon excited state of the two-photon absorption compound is larger than the excitation energy of the dye precursor.

On the other hand, in the case of the electron transfer mechanism from the sensitizing dye excited state or the two-photon excited state of the two-photon absorbing compound, the mechanism in which the electron transfer from the triplet excited state occurs even in the mechanism in which the electron transfer from the singlet excited state occurs. But either is fine.
The sensitizing dye excited state or the two-photon excited state of the two-photon absorption compound may give electrons to the dye precursor, the acid generator or the base generator, or may receive electrons. When electrons are supplied from the sensitizing dye excited state or the two-photon absorption state of the two-photon absorption compound, in order for the electron transfer to occur efficiently, the excited electrons in the sensitizing dye excitation state or the two-photon absorption state of the two-photon absorption compound Preferably, the orbital (LUMO) energy present is higher than the LUMO orbital energy of the dye precursor, acid generator or base generator.
When electrons are received in the sensitizing dye excited state or in the two-photon absorption state of the two-photon absorption compound, the presence of holes in the sensitizing dye excitation state or in the two-photon absorption state of the two-photon absorption compound is effective. The orbital (HOMO) energy is preferably lower than the energy of the HOMO orbital of the dye precursor, acid generator or base generator.

  Hereinafter, preferred combinations of recording components in the photon mode recording material and the two-photon absorption optical recording material of the present invention will be described in detail.

  First, the case where the recording component in the photon mode recording material and the two-photon absorption optical recording material of the present invention contains at least an acid-coloring type dye precursor as a dye precursor and an acid generator will be described.

  In this case, the acid generator is a compound capable of generating an acid by energy transfer or electron transfer from the sensitizing dye excited state or the two-photon excited state of the two-photon absorbing 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 a sensitizing dye excited state or a two-photon excited state of a two-photon absorption compound.

The following six systems are preferably used as the acid generator of the present invention.
In addition, you may use these acid generators as 2 or more types of mixtures by arbitrary ratios as needed.

1) trihalomethyl-substituted triazine acid generator 2) diazonium salt acid generator 3) diaryliodonium salt acid generator 4) sulfonium salt acid generator 5) metal arene complex acid generator 6) sulfonate ester Acid generator

  The preferred system described above will be specifically described below.

1) Trihalomethyl-substituted triazine acid generator

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

In the general formula (11), R ₂₁ , R ₂₂ and R ₂₃ each independently represent a halogen atom, preferably a chlorine atom. R ₂₄ and R ₂₅ each independently represent a hydrogen atom, —CR ₂₁ R ₂₂ R ₂₃ , or other substituents.
Preferred examples of the substituent include, for example, an alkyl group (preferably having a C number of 1 to 20, for example, methyl, ethyl, n-propyl, isopropyl, n-butyl, n-pentyl, benzyl, 3-sulfopropyl, 4-sulfobutyl, Carboxymethyl, 5-carboxypentyl), alkenyl group (preferably C 2-20, for example, vinyl, allyl, 2-butenyl, 1,3-butadienyl), cycloalkyl group (preferably C 3-20, for example, Cyclopentyl, cyclohexyl), an aryl group (preferably having 6 to 20 carbon atoms, for example, phenyl, 2-chlorophenyl, 4-methoxyphenyl, 3-methylphenyl, 1-naphthyl), a heterocyclic group (preferably having 1 to 20 carbon atoms). For example, pyridyl, thienyl, furyl, thiazolyl, imidazolyl, pyrazolyl, pyro Dino, piperidino, morpholino), alkynyl groups (preferably C 2-20, eg ethynyl, 2-propynyl, 1,3-butadiynyl, 2-phenylethynyl), halogen atoms (eg F, Cl, Br, I ), Amino group (preferably C 0-20, such as amino, dimethylamino, diethylamino, dibutylamino, anilino), cyano group, nitro group, hydroxyl group, mercapto group, carboxyl group, sulfo group, phosphonic acid group, An acyl group (preferably having 1 to 20 carbon atoms, such as acetyl, benzoyl, salicyloyl, pivaloyl), an alkoxy group (preferably having 1 to 20 carbon atoms, such as methoxy, butoxy, cyclohexyloxy), an aryloxy group (preferably having C number) Formula 6-26, for example, phenoxy, 1-naphthoxy), alkyl O group (preferably C number 1-20, for example, methylthio, ethylthio), arylthio group (preferably C number 6-20, for example, phenylthio, 4-chlorophenylthio), alkylsulfonyl group (preferably C number 1-20) , For example, methanesulfonyl, butanesulfonyl), arylsulfonyl group (preferably C number 6-20, such as benzenesulfonyl, paratoluenesulfonyl), sulfamoyl group (preferably C number 0-20, such as sulfamoyl, N-methyl) Sulfamoyl, N-phenylsulfamoyl), carbamoyl group (preferably having 1 to 20 carbon atoms, for example, carbamoyl, N-methylcarbamoyl, N, N-dimethylcarbamoyl, N-phenylcarbamoyl), acylamino group (preferably C number 1-20, for example, acetyla Mino, benzoylamino), imino group (preferably C 2-20, eg phthalimino), acyloxy group (preferably C 1-20, eg acetyloxy, benzoyloxy), alkoxycarbonyl group (preferably C 2 20, for example, methoxycarbonyl, phenoxycarbonyl), or a carbamoylamino group (preferably having 1 to 20 carbon atoms, such as carbamoylamino, N-methylcarbamoylamino, N-phenylcarbamoylamino), more preferably an alkyl group An aryl group, a heterocyclic group, a halogen atom, a cyano group, a carboxyl group, a sulfo group, an alkoxy group, a sulfamoyl group, a carbamoyl group, or an alkoxycarbonyl group.
R ₂₄ is preferably a -CR ₂₁ R ₂₂ R _23, more preferably represents a ₃ group -CCl, R ₂₅ is preferably, -CR ₂₁ R ₂₂ R _23, an alkyl group, an alkenyl group or an aryl group.

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

2) Diazonium salt acid generator

  The diazonium salt acid generator is preferably represented by the following general formula (12).

R ₂₆ represents an aryl group or a heterocyclic group, preferably an aryl group, and more preferably a phenyl group.
R ₂₇ is (the same as examples of preferably substituents exemplified for R ₂₄ as above substituents) represent a substituent, a21 represents an integer of 0 to 5, preferably an integer of 0 to 2. a21 is when 2 or more, the plurality of R ₂₇ may be the same or different and may form a ring.
X ₂₁ ⁻ is an anion in which HX ₂₁ becomes an acid having a pKa of 4 or less (in water, 25 ° C.), preferably 3 or less, more preferably 2 or less, preferably, for example, chloride, bromide, iodide, tetrafluoroborate, hexa Fluorophosphate, hexafluoroarsenate, hexafluoroantimonate, perchlorate, trifluoromethanesulfonate, 9,10-dimethoxyanthracene-2-sulfonate, methanesulfonate, benzenesulfonate, 4-trifluoromethylbenzenesulfonate, tosylate, tetra (penta Fluorophenyl) borate and the like.

Specific examples of the diazonium-based acid generators such as benzene diazonium, 4-methoxy diazonium, 4-methyl aforementioned X ₂₁ of diazonium ^- such salts.

3) Diaryliodonium salt acid generator

  The diaryliodonium salt acid generator is preferably represented by the following general formula (13).

In general formula (13), X ₂₁ ^- has the same meaning as in general formula (12). R ₂₈ and R ₂₉ each independently represents a substituent (preferably the same as the substituents described above as R ₂₄ as substituents), preferably an alkyl group, an alkoxy group, a halogen atom, a cyano group, or Represents a nitro group.
a22 and a23 each independently represents an integer of 0 to 5, preferably an integer of 0 to 1. When a21 is 2 or more, a plurality of R ₂₈ and R ₂₉ may be the same or different, and may be connected to each other to form a ring.

Specific examples of the diaryliodonium salt acid generator include diphenyliodonium, 4,4′-dichlorodiphenyliodonium, 4,4′-dimethoxydiphenyliodonium, 4,4′-dimethyldiphenyliodonium, 4,4′-di- t-butyldiphenyliodonium, 4,4′-di-t-amyldiphenyliodonium, 3,3′-dinitrodiphenyliodonium, phenyl (p-methoxyphenyl) iodonium, phenyl (p-octyloxyphenyl) iodonium, bis (p Chloride such as cyanophenyl) iodonium, bromide, iodide, tetrafluoroborate, hexafluorophosphate, hexafluoroarsenate, hexafluoroantimonate, perchlorate, trifluoromethanesulfonate, 9,10-dimeth Examples include xianthracene-2-sulfonate, methanesulfonate, benzenesulfonate, 4-trifluoromethylbenzenesulfonate, tosylate, tetra (pentafluorophenyl) borate, perfluorobutanesulfonate, and pentafluorobenzenesulfonate.
Further, compounds described in “Macromolecules”, Vol. 10, p1307 (1977), Japanese Patent Application Laid-Open No. 58-29803, Japanese Patent Application Laid-Open No. 1-287105, Japanese Patent Application No. 3-5569. And diaryliodonium salts as described in 1).

4) Sulfonium salt acid generator

  The sulfonium salt acid generator is preferably represented by the following general formula (14).

In general formula (14), X ₂₁ ^- has the same meaning as in general formula (12). R ₃₀ , R ₃₁ , and R ₃₂ each independently represents an alkyl group, an aryl group, or a heterocyclic group (preferred examples are the same as those for R ₂₄ ), preferably an alkyl group, a phenacyl group, or an aryl group.

  Specific examples of the sulfonium salt acid generator include triphenylsulfonium, diphenylphenacylsulfonium, dimethylphenacylsulfonium, benzyl-4-hydroxyphenylmethylsulfonium, 4-tertiarybutyltriphenylsulfonium, tris (4-methylphenyl). ) Chloride, bromide, tetrafluoroborate, hexafluorophosphate of sulfonium salts such as sulfonium, tris (4-methoxyphenyl) sulfonium, 4-phenylthiotriphenylsulfonium, bis-1- (4- (diphenylsulfonium) phenyl) sulfide , Hexafluoroarsenate, hexafluoroantimonate, perchlorate, trifluoromethanesulfonate, 9,10-dimethoxyanthracene-2-sulfonate , Methanesulfonate, benzenesulfonate, 4-trifluoromethylbenzenesulfonate, tosylate, tetra (pentafluorophenyl) borate, perfluorobutanesulfonate, pentafluorobenzenesulfonate and the like.

5) Metal arene complex acid generator

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

6) Sulfonate acid generator

  Preferred examples of the sulfonic acid ester-based acid generator include sulfonic acid esters, sulfonic acid nitrobenzyl esters, and imide sulfonates.

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

  In addition, as an acid generator, for example, “UV curing; science and technology (UV CURING; SCIENCE AND TECHNOLOGY)” [p. 23-76, S.M. Edited by S. PETER PAPPAS, A TECHNOLOGY MARKING PUBLICATION] and “Comments Inorg. Chem.” [B. Klingelt, M.M. Reedy Car and A. Rolov (B. KLINGERT, M. RIEDICER and A. ROLOFF), Volume 7, No. 3, p109-138 (1988)] and the like can also be used.

  As acid generators other than the above, S.I. Hayase et al. PolymerSci. 25, 753 (1987), E.I. Reichmanisetal, J.A. PolymerSci. , Polymer Chem. Ed. 23, 1 (1985), D.M. H. R. Bartonetal, J.M. Chem. Soc. 3571 (1965), p. M.M. Collinsetal, J.A. Chem. Soc. Perkin I, 1695 (1975), M .; Rudinstein et al., Tetrahedron Lett. , (17), 1445 (1975), J. MoI. W. Walkeretal, J. et al. Am. Chem. Soc. 110, 7170 (1988), S.A. C. Busmanetal, J.M. ImagingTechnol. 11 (4), 191 (1985), H. et al. M.M. Houlihanetal, Macromolecules, 21, 2001 (1988), P.M. M.M. Collinsetal, J.A. Chem. Soc. , Chem. Commun. 532 (1972), S.A. Hayase et al., Macromolecules, 18, 1799 (1985), E.I. Reichmanisetal, J.A. Electrochem. Soc. , SolidStateSci. Technol. , 130 (6), F.M. M.M. Houlihanetal, Macro-molecules, 21, 2001 (1988), European Patent Nos. 0290,750, 046,083, 156,535, 271,851, 0,388,343, US Patent 3,901,710, 4,181,531, JP-A-60-198538, JP-A-53-133022 and the like, a photoacid generator having an o-nitrobenzyl type protecting group, Halogenated sulfolane derivatives (specifically, 3,4-dibromosulfolane, 3,4-dichlorosulfolane, etc.) disclosed in JP-A-4-338757, methylene glycol bis (2,3-dibromopropyl) ether, etc. Halogen-containing alkylene glycol ether compounds, 1,1,3,3-tetrabromoacetate , Halogen-containing ketones such as hexachloroacetone, and halogen-containing alcohols such as 2,3-dibromo-propanol can be exemplified.

Furthermore, a polymer in which a group capable of generating an acid is introduced into the main chain or side chain can also be used as the acid generator of the present invention. When the acid generator of the present invention is a polymer in which a group capable of generating an acid is introduced into the main chain or side chain, the polymer may also serve as a binder.
Specific examples of the acid-generating group of the present invention or a compound in which a compound is introduced into the main chain or side chain of the polymer are as follows. E. Woodhouse et al. Am. Chem. Soc. 104, 5586 (1982), S .; P. Pappasetal, J.A. ImagingSci. , 30 (5), 218 (1986), S .; Kondo et al. Makromol. Chem. , RapidCommun. , 9, 625 (1988), J. Am. V. Crivello et al. J. et al. PolymerSci. , Polymer Chem. Ed. , 17, 3845 (1979), U.S. Pat. No. 3,849,137, German Patent 3,914,407, JP-A 63-26653, JP-A 55-164824, JP-A 62-69263. , JP-A-63-146037, JP-A-63-163452, JP-A-62-153853, JP-A-63-146029, JP-A-2000-143796 can be used. .

As the acid generator of the present invention, more preferably,
3) Diaryl iodonium salt acid generator 4) Sulfonium salt acid generator 6) Sulfonic acid ester acid generator.

In addition, all the above-mentioned acid generators can serve as a cationic polymerization initiator.
Also,
1) trihalomethyl-substituted triazine acid generator 2) diazonium salt acid generator 3) diaryliodonium salt acid generator 4) sulfonium salt acid generator 5) metal arene complex acid generator is a cationic polymerization initiator And a radical polymerization initiator.
Accordingly, the photon mode recording material and the two-photon absorption recording material of the present invention, and the composition thereof are used in combination with a polymerizable monomer, a polymerizable binder, a reactive binder, and a crosslinking agent to perform polymerization, crosslinking, etc. The film can be cured by the above.

  Next, the acid-color-forming dye precursor in the case where the recording component in the photon mode recording material and the two-photon absorption light-recording material of the present invention contains at least an acid-color-forming dye precursor and an acid generator, and explain.

  The acid coloring precursor in the present invention is a dye precursor that can be a coloring body whose absorption is changed from the original state by an acid generated by an acid generator. As the acid coloring precursor of the present invention, a compound whose absorption is increased in wavelength by an acid is preferable, and a compound which develops a color from colorless by an acid is more preferable.

  The acid coloring dye precursor is preferably triphenylmethane, phthalide (including indolylphthalide, azaphthalide, and triphenylmethanephthalide), phenothiazine, phenoxazine, fluoran, thiofluorane, Examples include xanthene, diphenylmethane, chromenopyrazole, leucooramine, methine, azomethine, rhodamine lactam, quinazoline, diazaxanthene, fluorene, and spiropyran compounds. Specific examples of these compounds are disclosed in, for example, JP-A No. 2002-156454 and its cited patent, JP-A No. 2000-281920, JP-A No. 11-279328, JP-A No. 8-240908, and the like.

  More preferably, the acid coloring dye precursor is a leuco dye having a partial structure such as lactone, lactam, oxazine, and spiropyran, and examples thereof include fluorane-based, thiofluorane-based, phthalide-based, rhodamine lactam-based, and spiropyran-based compounds.

In the recording component of the present invention, the dye produced from the acid coloring dye precursor is preferably a xanthene (preferably fluorane) dye or a triphenylmethane dye.
These acid coloring dye precursors may be used as a mixture of two or more at an arbitrary ratio as required.

  Specific examples of the acid color-forming dye precursor that is preferable as the recording component of the present invention will be given below, but the present invention is not limited to the following specific examples.

  The phthalide dye precursor is preferably represented by the following general formula (21).

In the general formula (21), X ₄₁ represents CH or N, R ₃₃ and R ₃₄ each independently represents an alkyl group having 1 to 20 carbon atoms (hereinafter referred to as C number), an aryl group having 6 to 24 carbon atoms, C Represents a heterocyclic group of formula 1 to 24 or a group represented by the following general formula (22), and R ₃₅ represents a substituent (preferably the same as the example of the substituent mentioned in R ₂₄ as the substituent). . R ₃₅ is more preferably a halogen atom such as a chlorine atom or a bromine atom, an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, an amino group, or an alkylamino group having 1 to 20 alkyl groups. A dialkylamino group having an alkyl group having 1 to 20 carbon atoms, an arylamino group having an aryl group having 6 to 24 carbon atoms, a diarylamino group having an aryl group having 6 to 24 carbon atoms, Represents a hydroxyl group, an alkoxy group having 1 to 20 carbon atoms, or a heterocyclic group, k ₄₁ represents an integer of 0 to 4, and when k ₄₁ is an integer of 2 or more, a plurality of R ₃₅ are each independently Represents the above group. These groups may further have a substituent, and examples of the preferred substituent include the groups listed for R ₂₄ .

In the general formula (22), R ₃₆ represents an alkylene group having 1 to 3 carbon atoms, k ₄₂ represents an integer of 0 to 1, and R ₃₇ represents a substituent (preferably exemplified by R ₂₄ as a substituent). The same as the examples of substituents). R ₃₇ is more preferably a halogen atom such as a chlorine atom or a bromine atom, an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, an amino group, or an alkylamino having an alkyl group having 1 to 20 carbon atoms. Group, each independently a dialkylamino group having an alkyl group having 1 to 20 carbon atoms, an arylamino group having an aryl group having 6 to 24 carbon atoms, and each independently a diarylamino group having an aryl group having 6 to 24 carbon atoms , A hydroxyl group, an alkoxy group having 1 to 20 carbon atoms, or a heterocyclic group, k ₄₃ represents an integer of 0 to 5, and when k ₄₃ is an integer of 2 or more, a plurality of R ₃₇ are independent of each other. Represents the above group. These groups may further have a substituent, and examples of the preferred substituent include the groups listed for R ₂₄ .

In general formula (21), the heterocyclic group represented by R ₃₃ and R ₃₄ is more preferably an indolyl group represented by the following general formula (23).

In the general formula (23), R ₃₈ represents a substituent (as a substituent, preferably the same as the examples of the substituent listed for R ₂₄ ), and more preferably R ₃₈ is a halogen atom such as a chlorine atom or a bromine atom. , An alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, an amino group, an alkylamino group having an alkyl group having 1 to 20 carbon atoms, and each independently having an alkyl group having 1 to 20 carbon atoms. A dialkylamino group, an arylamino group having an aryl group having 6 to 24 carbon atoms, a diarylamino group having an aryl group having 6 to 24 carbon atoms, a hydroxyl group, an alkoxy group having 1 to 20 carbon atoms, or a heterocyclic ring represents a group, k ₄₄ represents an integer of 0 to 4, when k ₄₄ is an integer of 2 or more, multiple R ₃₈ are each independently represent the group above. R ₃₉ represents a hydrogen atom or an alkyl group having 1 to 20 carbon atoms, and R ₄₀ represents an alkyl group having 1 to 20 carbon atoms or an alkoxy group having 1 to 20 carbon atoms. These groups may further have a substituent, and preferred examples of the substituent include the groups exemplified for R ₂₄ .

  Specific examples of phthalide dye precursors (including indolylphthalide dye precursors and azaphthalide dye precursors) include 3,3-bis (4-diethylaminophenyl) -6-diethylaminophthalide, 3- ( 4-diethylaminophenyl) -3- (1-ethyl-2-methylindol-3-yl) phthalide, 3- (4-dimethylaminophenyl) -3- (1,3-dimethylindol-3-yl) phthalide, 3,3-bis (1-n-butyl-2-methylindol-3-yl) phthalide, 3,3-bis (1-ethyl-2-methylindol-3-yl) phthalide, 3- (4-diethylamino) -2-ethoxyphenyl) -3- (1-ethyl-2-methylindol-3-yl) -4-azaphthalide, 3,3-bis (4-hydroxyphenyl) -6 Dorokishifutarido, 3,3-bis (4-hexyloxyphenyl) phthalide, 3,3-bis (4-hexyloxy-phenyl) -6-methoxy phthalide, and the like.

  More preferred as the phthalide dye precursor represented by the general formula (21) is a triphenylmethane phthalide dye precursor represented by the following general formula (24).

In the general formula _{(24), R 41, R} 42, R 43 independently represents a substituent (preferred substituents are the same as the substituents exemplified in _{R 24), R 41, R} 42, R Preferred as the substituent of ₄₃ is a halogen atom such as a chlorine atom or a bromine atom, an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, an amino group, or an alkyl group having 1 to 20 alkyl groups. Amino group, each independently a dialkylamino group having a C1-20 alkyl group, each arylamino group having a C6-24 aryl group, each independently a diarylamino having a C6-24 aryl group Group, a hydroxyl group, an alkoxy group having 1 to 20 carbon atoms and a heterocyclic group, k ₄₅ , k ₄₆ and k ₄₇ each independently represents an integer of 0 to 4, and each of k ₄₅ , k ₄₆ and k ₄₇ When is an integer greater than 1, Number of R _41, R _42, R ₄₃ each independently represent the group above. These groups may further have a substituent, and preferred examples of the substituent include the groups exemplified for R ₂₄ .

  Specific examples of the triphenylmethane phthalide dye precursor include 3,3-bis (p-dimethylaminophenyl) -6-dimethylaminophthalide (that is, crystal violet lactone), 3,3-bis (p-dimethyl). Aminophenyl) phthalide, 3,3-bis (p-dihexylaminophenyl) -6-dimethylaminophthalide, 3,3-bis (p-dioctylaminophenyl) phthalide, 3,3-bis (p-dimethylaminophenyl) ) -6-diethylaminophthalide, 4-hydroxy-4'-dimethylaminotriphenylmethanelactone, 4,4'-bisdihydroxy-3,3'-bisdiaminotriphenylmethanelactone, 3,3-bis (4- Hydroxyphenyl) -4-hydroxyphthalide, 3,3-bis (4-hexyloxypheny) ) Phthalide, 3,3-bis (4-hexyloxy-phenyl) -6-methoxy phthalide, and the like.

  The fluorane dye precursor is preferably represented by the following general formula (25).

In the general formula (25), R ₄₄ , R ₄₅ and R ₄₆ each independently represent a substituent (preferably the same as the examples of substituents mentioned for R ₂₄ as the substituent), R ₄₄ , R ₄₅ , R _As the substituent of ₄₆ , an alkyl having a halogen atom such as a chlorine atom or a bromine atom, an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, an amino group, or an alkyl group having 1 to 20 carbon atoms Amino group, each independently a dialkylamino group having a C1-20 alkyl group, each arylamino group having a C6-24 aryl group, each independently a diarylamino having a C6-14 aryl group A group, a hydroxyl group, or a heterocyclic group, k ₄₈ , k ₄₉ , k ₅₀ each independently represents an integer of 0-4, and each of k ₄₈ , k ₄₉ , k ₅₀ is an integer of 2 or more, A plurality of R ₄₄ , R ₄₅ , R ₄₆ Each independently represents the above group. These groups may further have a substituent, and examples of the preferred substituent include the groups listed for R ₂₄ .

  Specific examples of the fluorane dye precursor include 3-diethylamino-6- (2-chloroanilino) fluorane, 3-dibutylamino-6- (2-chloroanilino) fluorane, 3-diethylamino-7-methyl-6-anilino. Fluorane, 3-dibutylamino) -7-methyl-6-anilinofluorane, 3-dipentylamino-7-methyl-6-anilinofluorane, 3- (N-ethyl-N-isopentylamino)- 7-methyl-6-anilinofluorane, 3-diethylamino-7-methyl-6-xylidinofluorane, 3-diethylamino-6,7-benzofluorane, 3-diethylamino-7-methoxy-6, 7- Benzofluorane, 1,3-dimethyl-6-diethylaminofluorane, 2-bromo-3-methyl-6-dibutylaminofluor 2-N, N-dibenzylamino-6-diethylaminofluorane, 3-dimethylamino-6-methoxyfluorane, 3-diethylamino-7-methyl-6-chlorofluorane, 3-diethylamino-6- Examples include methoxyfluorane, 3,6-bisdiethylaminofluorane, 3,6-dihexyloxyfluorane, 3,6-dichlorofluorane, 3,6-diacetyloxyfluorane, and the like.

  Specific examples of the rhodamine lactam dye precursor include rhodamine-B-anilinolactam, rhodamine (p-nitroanilino) lactam, rhodamine-B- (p-chloroanilino) lactam, rhodamine-B- (o-chloroanilino) lactam, and the like. Is mentioned.

Specific examples of the spiropyran dye precursor include 3-methyl-spirodinaphthopyran, 3-ethyl-spirodinaphthopyran, 3,3′-dichloro-spirodinaphthopyran, 3-benzyl-spirodinaphthopyran, Examples include 3-propyl-spirodibenzopyran, 3-phenyl-8′-methoxybenzoindolinospiropyran, 8′-methoxybenzoindolinospiropyran, 4,7,8′-trimethoxybenzoindolinospiropyran, and the like.
Furthermore, a spiropyran dye precursor disclosed in Japanese Patent Application Laid-Open No. 2000-281920 can be given as a specific example.

  Examples of the acid coloring dye precursor of the present invention include a BLD compound represented by the general formula (6) disclosed in JP 2000-284475 A, a leuco dye disclosed in JP 2000-144004, and A leuco dye having the structure shown below can also be suitably used.

  Furthermore, the dye precursor of the present invention is also preferably a compound represented by the general formula (26) that develops color by addition of an acid (proton).

In the above formula, Za ₁ , Za ₂ , Ra ₂ , Ma _{1 to} Ma ₇ , na ¹ , na ² , and ka ¹ are respectively synonymous with those in the general formula (3), and preferred examples are also in the general formula (3). It is the same.

  Although the preferable example of a compound represented by General formula (26) of this invention is given below, this invention is not limited to these.

When the recording component of the present invention contains at least an acid color-forming dye precursor as a dye precursor and an acid generator, it may further contain an acid proliferating agent.
The acid proliferating agent of the present invention is stable in the absence of an acid, but in the presence of an acid, it decomposes to release an acid, and that acid decomposes another acid proliferating agent to release an acid. In other words, it is a compound that proliferates with a small amount of acid generated by an acid generator as a trigger.
At that time, the acid proliferating agent is preferably represented by the following general formulas (34-1) to (34-6).

In the general formulas (34-1) to (34-6), R ₁₀₁ represents a group in which R ₁₀₁ OH becomes an acid having a pKa of 5 or less, preferably a group in which an acid with a pKa of 3 or less is formed.
R ₁₀₁ is preferably a group in which R ₁₀₁ OH is any one of sulfonic acid, carboxylic acid, phosphoric acid, phosphonic acid, and phosphinic acid, and is either sulfonic acid or electron-withdrawing group-substituted carboxylic acid In this case, the electron withdrawing group is preferably a halogen atom, a cyano group, a nitro group, an alkoxycarbonyl group, a carbamoyl group, an alkylsulfonyl group, an arylsulfonyl group, or a heterocyclic group. R ₁₀₁ is most preferably a group in which R ₁₀₁ OH is a sulfonic acid.

Preferable specific examples of R ₁₀₁ are listed below, but the present invention is not limited thereto.

In formula (34-1), one of R ₁₀₂ is 2-alkyl-2-propyl, 2-aryl-2-propyl group, a cyclohexyl group, a tetrahydropyranyl group, bis (p- alkoxyphenyl) methyl group Preferably represents a 2-alkyl-2-propyl group or a 2-aryl-2-propyl group, more preferably a 2-alkyl-2-propyl group, most preferably a t-butyl group. Represent.

In general formula (34-1), R ₁₀₃ and R ₁₀₄ each independently represents a substituent (more preferably, the same as the examples of the substituents mentioned for R ₂₄ as substituents above), and more preferably each independently alkyl. A group, an alkenyl group, a cycloalkyl group, an aryl group, and a heterocyclic group, more preferably an alkyl group or an aryl group, and most preferably an alkyl group.

In the general formulas (34-1) to (34-6), R ₁₀₅ , R ₁₀₆ , R ₁₀₇ , R ₁₁₀ , R ₁₁₃ , and R ₁₁₆ are each independently a hydrogen atom or a substituent (preferably R ₂₄ is preferably a substituent). The same as the examples of the substituents mentioned above, more preferably a hydrogen atom, an alkyl group, an alkenyl group, a cycloalkyl group, an aryl group, or a heterocyclic group, and even more preferably a hydrogen atom, an alkyl group, or an aryl group. Represent.
R ₁₀₅ , R ₁₀₆ and R ₁₁₆ are all preferably hydrogen atoms. R ₁₀₇ , R ₁₁₀ and R ₁₁₃ are more preferably all alkyl groups.

In general formula (34-2), R ₁₀₈ and R ₁₀₉ each independently represents an alkyl group, preferably a methyl group or an ethyl group, and may be linked to each other to form a ring. Is preferably a dioxal ring or a dioxane ring.

In general formula (34-3), R ₁₁₁ and R ₁₁₂ represent an alkyl group that is linked to each other to form a ring. The ring to be formed is preferably a saturated cycloalkane ring.

In formula (34-4), R ₁₁₄ represents a hydrogen atom or a nitro group, or a nitro group. R ₁₁₅ represents a substituent, n101 represents an integer of 0 to 3, is preferably n101 0 or 1, more preferably 0.

In formula (34-6), R ₁₁₇ (preferably a more substituents the same as the substituents exemplified in R ₂₄₎ represents a substituent, and more preferably each independently an alkyl group, an alkenyl group, a cycloalkyl Represents an alkyl group, an aryl group, or a heterocyclic group, more preferably an alkyl group or an aryl group, and most preferably an alkyl group.

  The acid proliferating agent of the present invention is more preferably represented by any one of the general formulas (34-1), (34-3), and (34-4), and is represented by the general formula (34-1). Is most preferred.

  Specific examples of the acid proliferating agent of the present invention are shown below, but the present invention is not limited thereto.

  Since it is preferable to heat at the time of acid multiplication, it is preferable to heat-process after exposure.

  Next, the case where the recording component in the photon mode recording material and the two-photon absorption optical recording material of the present invention contains at least a base coloring type dye precursor as a dye precursor and a base generator will be described.

In this case, the base generator is a compound capable of generating a base by energy transfer or electron transfer from the sensitizing dye excited state or the two-photon excited state of the two-photon absorbing 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 a sensitizing dye excited state or a two-photon excited state of a 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 (31-1) to (31-4). In addition, you may use these base generators as 2 or more types of mixtures by arbitrary ratios as needed.

In the general formula (31-1) or (31-2), R ₂₀₁ and R ₂₀₂ each independently represent 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 C 3-20, such as cyclopentyl, cyclohexyl), an aryl group (preferably C 6-20, such as phenyl 2-chlorophenyl, 4-methoxyphenyl, 3-methylphenyl, 1-naphthyl, 2-naphthyl), heterocyclic group Preferably it represents any one of C 1-20, for example, pyridyl, thienyl, furyl, thiazolyl, imidazolyl, pyrazolyl, pyrrolidino, piperidino, morpholino), more preferably a hydrogen atom, an alkyl group, a cycloalkyl group, Preferably, it represents a hydrogen atom, a methyl group, an ethyl group, a cyclohexyl group, or a cyclopentyl group.
R ₂₀₁ and R ₂₀₂ 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 morpholine ring, a pyridine ring, a quinoline ring, or an imidazole ring, and more A piperidine ring, a pyrrolidine ring and an imidazole ring are preferable, and a piperidine ring is most preferable.
As a more preferable combination of R ₂₀₁ and R ₂₀₂ , R ₂₀₁ may be a substituted cyclohexyl group, R ₂₀₂ is a hydrogen atom, R ₂₀₁ may be a substituted alkyl group, R ₂₀₂ is a hydrogen atom, R ₂₀₁ , R _{202 202} may be linked to form a piperidine ring or an imidazole ring.

  In the general formula (31-1) or (31-2), n201 is 0 or 1, preferably 1.

In General Formula (31-1), R ₂₀₃ represents a substituent, and examples of preferable substituents include alkyl groups (preferably having 1 to 20 carbon atoms, such as methyl, ethyl, n-propyl, isopropyl, n -Butyl, n-pentyl, benzyl, 3-sulfopropyl, 4-sulfobutyl, carboxymethyl, 5-carboxypentyl), an alkenyl group (preferably having 2 to 20 carbon atoms, such as vinyl, allyl, 2-butenyl, 1, 3-butadienyl), cycloalkyl group (preferably C 3-20, such as cyclopentyl, cyclohexyl), aryl group (preferably C 6-20, such as phenyl, 2-chlorophenyl, 4-methoxyphenyl, 3-methyl Phenyl, 1-naphthyl), heterocyclic group (preferably having 1 to 20 carbon atoms, such as pyridyl, thienyl, 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), an amino group (preferably C 0-20, such as amino, dimethylamino, diethylamino, dibutylamino, anilino), cyano group, nitro group, hydroxyl group, mercapto group, 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 to 20, for example, methoxy, butoxy, cyclohexyloxy), Aryloxy groups (preferably having 6 to 26 carbon atoms, eg Phenoxy, 1-naphthoxy), alkylthio group (preferably C1-20, such as methylthio, ethylthio), arylthio group (preferably C6-20, such as phenylthio, 4-chlorophenylthio), alkylsulfonyl Group (preferably C number 1-20, for example, methanesulfonyl, butanesulfonyl), arylsulfonyl group (preferably C number 6-20, for example, benzenesulfonyl, paratoluenesulfonyl), sulfamoyl group (preferably C number 0) -20, such as sulfamoyl, N-methylsulfamoyl, N-phenylsulfamoyl), carbamoyl group (preferably having 1 to 20 carbon atoms, such as carbamoyl, N-methylcarbamoyl, N, N-dimethylcarbamoyl, N- Phenylcarbamoyl), acylami A group (preferably having 1 to 20 carbon atoms, such as acetylamino, benzoylamino), an imino group (preferably having 2 to 20 carbon atoms, such as phthalimino), an acyloxy group (preferably having 1 to 20 carbon atoms, such as acetyloxy, benzoyloxy) ), An alkoxycarbonyl group (preferably C 2-20, such as methoxycarbonyl, phenoxycarbonyl), or a carbamoylamino group (preferably C 1-20, such as carbamoylamino, N-methylcarbamoylamino, N-phenylcarbamoyl) Amino), and more preferably an alkyl group, aryl group, heterocyclic group, halogen atom, amino group, cyano group, nitro group, carboxyl group, sulfo group, alkoxy group, alkylthio group, arylsulfonyl group, sulfamoyl group , Carbamoyl group, Or an alkoxycarbonyl group.

In the general formula (31-1), R ₂₀₃ 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 (31-1), n202 is an integer of 0 to 5, preferably an integer of 0 to 3, and more preferably 1 or 2. When n202 is 2 or more, a plurality of R ₂₀₃ 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 the general formula (31-1), when R ₂₀₃ is a nitro group, it is preferably substituted at the 2-position or 2,6-position, and when R ₂₀₃ is an alkoxy group, it is substituted at the 3, 5-position Is preferred.

In the formula (31-1), preferred examples (Examples in the same substituents as the preferred substituents exemplified in R ₃₎ R _204, R ₂₀₅ each independently represent a hydrogen atom or a substituent R ₂₀₃ 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.
A more preferable combination of _{R 204, R 205, R 204} , R 205 Kyomizu, R ₂₀₅ R ₂₀₄ is a methyl group is a hydrogen atom, R _204, R ₂₀₅ both methyl, R ₂₀₄ is 2-nitrophenyl group R ₂₀₅ is a hydrogen atom, and the like, more preferably R ₂₀₄ and R _{205 are} co-hydrogen atoms.

In the general formula (31-2), R ₂₀₆ and R ₂₀₇ each independently represent a substituent (preferably the same as the examples of the substituent described in R ₂₀₃ as the substituent), preferably an alkoxy group, alkylthio Represents a group, a nitro group, or an alkyl group, more preferably a methoxy group.
In General Formula (31-2), n203 and n204 each independently represents an integer of 0 to 5, and preferably represents an integer of 0 to 2. n203, when n204 is 2 or more, plural R _206, R ₂₀₇ may be the same or different and may be bonded to form a ring, and preferably a benzene ring, a naphthalene ring, and examples of the ring formed .
In general formula (31-2), R ₂₀₆ 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 (31-2), R ₂₀₈ represents a hydrogen atom or a substituent (preferably the same as the substituents exemplified in R ₂₀₃ as the substituent), preferably a hydrogen atom or an aryl group, More preferably, it is a hydrogen atom.

In the general formula (31-3), R ₂₀₉ represents a substituent (preferably the same as the examples of the substituent mentioned in R ₂₀₃ as the substituent), preferably an alkyl group, an aryl group, a benzyl group, or amino More preferably an alkyl group that may be substituted, a t-butyl group, a phenyl group, a benzyl group, an anilino group that may be substituted, or a cyclohexylamino group.
The compound represented by the general formula (31-3) may be a compound in which R ₂₀₉ is linked to a polymer chain.

In the general formula (31-3), R ₂₁₀ and R ₂₁₁ each independently represents a hydrogen atom or a substituent (preferably the same as the substituents exemplified in R ₂₀₃ as the substituent), preferably an alkyl group Or an aryl group, more preferably a methyl group, a phenyl group, or a 2-naphthyl group.
R ₂₁₀ and R ₂₁₁ may _combine with each other to form a ring, and the ring formed is preferably, for example, a fluorene ring.

In General Formula (31-4), R ₂₁₂ represents an aryl group or a heterocyclic group, and more preferably the following aryl group or heterocyclic group.

In formula (31-4), R ₂₁₃ , R ₂₁₄ and R ₂₁₅ are each independently a hydrogen atom, an alkyl group, an alkenyl group, a cycloalkyl group, an aryl group or a heterocyclic group (preferred examples are R ₂₀₁ , R _The same as ₂₀₂ ), preferably an alkyl group, more preferably a butyl group. R ₂₁₃ , R ₂₁₄ , and R ₂₁₅ may be linked to each other to form a ring, and the heterocyclic ring to be formed is preferably a piperidine ring, pyrrolidine ring, piperazine ring, morphophore ring, pyridine ring, quinoline ring, or An imidazole ring, more preferably a piperidine ring, a pyrrolidine ring, or an imidazole ring.

In General Formula (31-4), R ₂₁₆ , R ₂₁₇ , R ₂₁₈ , and R ₂₁₉ each independently represents an alkyl group or an aryl group, and R ₂₁₆ , R ₂₁₇ , and R ₂₁₈ are all phenyl groups, and R ₂₁₉ 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 (31-1) or (31-3), and more preferably represented by the general formula (31-1).

  Although the preferable specific example of the base generator of this invention is shown below, this invention is not limited to this.

  Next, a base color-forming dye precursor when the recording component in the photon mode recording material and the two-photon absorption optical recording material of the present invention contains at least a base color-forming dye precursor as a dye precursor, and a base generator. explain.

  The base color-forming dye precursor in the present invention is a dye precursor that can be a color former whose absorption is changed from the original state by the base generated by the base generator. As the base color-forming dye precursor of the present invention, a compound whose absorption is increased in wavelength by a base is preferable, and a compound whose molar extinction coefficient is greatly increased by a base is more preferable.

The base color-forming dye precursor in the present invention is preferably a non-dissociated form of a dissociative dye. The dissociation type dye has a dissociation group that easily dissociates and releases protons of pKa12 or less, more preferably pKa10 or less, on the dye chromophore. It is a compound that becomes longer wavelength or becomes colorless to colored. Preferably, the dissociation group includes OH group, SH group, COOH group, PO ₃ H ₂ group, SO ₃ H group, NR ₉₁ R ₉₂ H ⁺ group, NHSO ₂ R ₉₃ group, CHR ₉₄ R ₉₅ group, and NHR ₉₆ group. Can be mentioned.
Here, R ₉₁ , R ₉₂ , and R ₉₆ each independently represent a hydrogen atom, an alkyl group, an alkenyl group, a cycloalkyl group, an aryl group, or a heterocyclic group (preferred examples are the same as those of R ₂₀₃ ), Preferably it represents a hydrogen atom or an alkyl group. R ₉₃ represents an alkyl group, an alkenyl group, a cycloalkyl group, an aryl group, or a heterocyclic group (preferred examples are the same as those of R ₂₀₃ ), preferably an optionally substituted alkyl group or a substituted group. It is more preferably an alkyl group that represents an aryl group and may be substituted. In this case, the substituent is preferably electron withdrawing, and is preferably fluorine.
R ₉₄ and R ₉₅ each independently represent a substituent (preferably the same as the examples of the substituents listed for R ₂₀₃ as a substituent), but an electron-withdrawing substituent is preferable, and a cyano group, alkoxycarbonyl It is preferably a group, a carbamoyl group, an acyl group, an alkylsulfonyl group, or an arylsulfonyl group.
The dissociation group of the dissociation type dye of the present invention is more preferably an OH group, COOH group, NHSO ₂ R ₉₃ group, NHR ₉₆ group, or CHR ₉₄ R ₉₅ group, and more preferably an OH group or CHR ₉₄ R ₉₅ group. The OH group is most preferred.

  Examples of preferred dissociable dye non-dissociated as a base coloring dye precursor in the present invention include dissociable azo dyes, dissociable azomethine dyes, dissociable oxonol dyes, dissociable xanthene (fluorane) dyes, dissociable triphenylamine dyes. More preferably, it is a non-dissociated form of a dissociable azo dye, dissociated azomethine dye, or dissociated oxonol dye.

  Hereinafter, examples of the dissociable dye non-dissociated substance will be given as examples of the base color-forming dye precursor of the present invention, but the present invention is not limited thereto.

When the recording component of the present invention contains at least a base color-forming dye precursor as a dye precursor and a base generator, it may further contain a base proliferating agent.
The base proliferating agent of the present invention is stable in the absence of a base, but decomposes to release a base in the presence of a base, and then releases another base proliferating agent by that base to release another base. It is a compound that proliferates a base with a small amount of base generated by the base generator as a trigger.
At that time, the base proliferating agent is preferably represented by the general formula (35).

In the general formula (35), R ₁₂₁ and R ₁₂₂ each independently represent a hydrogen atom, an alkyl group, an alkenyl group, a cycloalkyl group, an aryl group, or a heterocyclic group (the substituents are preferably listed as R ₂₀₁ above). The same as the examples of substituents), more preferably a hydrogen atom, an alkyl group, and a cycloalkyl group, and still more preferably a hydrogen atom, a methyl group, an ethyl group, a cyclohexyl group, and a cyclopentyl group.
R ₁₂₁ and R ₁₂₂ may be connected to each other to form a ring, and the heterocycle formed is preferably a piperidine ring, a pyrrolidine ring, a piperazine ring, a morpholine ring, a pyridine ring, a quinoline ring, or an imidazole ring, and more A piperidine ring, a pyrrolidine ring and an imidazole ring are preferable, and a piperidine ring is most preferable.
As a more preferable combination of R ₁₂₁ and R ₁₂₂ , R ₁₂₁ is a cyclohexyl group which may be substituted, R ₁₂₂ is a hydrogen atom, R ₁₂₁ is an alkyl group which may be substituted, R ₁₂₂ is a hydrogen atom, R ₁₂₁ , R ₁₂₂ may be linked to form a piperidine ring or an imidazole ring.

R ₁₂₃ and R ₁₂₄ each independently represent a hydrogen atom or a substituent (preferably the same as the substituents exemplified in R ₂₀₃ as the substituent), preferably a hydrogen atom, an aryl group or an arylsulfonyl group, More preferably, it represents an aryl group.
R ₁₂₃ and R ₁₂₄ may be bonded to each other to form a ring, and a preferable example of the ring formed is a fluorene ring.

R ₁₂₅ and R ₁₂₆ each independently represents a hydrogen atom or a substituent (preferably the same as the substituents exemplified in R ₂₀₃ as the substituent), preferably a hydrogen atom or an alkyl group, more preferably a hydrogen atom. Represents an atom or a methyl group.

  n102 represents an integer of 0 or 1, preferably 1.

The base proliferating agent of the present invention is more preferably a compound represented by the general formula (36-1) or (36-2).
In general formulas (36-1) and (36-2), R ₁₂₁ and R ₁₂₂ have the same meanings as in general formula (35).

  The base proliferating agent of the present invention is more preferably a compound represented by the general formula (36-1).

  Specific examples of the base proliferating agent of the present invention are shown below, but the present invention is not limited thereto.

  Since it is preferable to heat at the time of base multiplication, when a base proliferating agent is used in the photon mode recording material and the two-photon absorption optical recording material of the present invention, it is preferable to perform heat treatment after exposure.

  Next, the recording component of the present invention is covalently bonded to an organic compound moiety having a function of breaking a covalent bond by electron transfer or energy transfer between the sensitizing dye excited state or the two-photon excited state of the two-photon absorbing compound. The case where the organic compound site | part which has the characteristics used as a color body at the time of being released | released and contains the compound which has covalently bonded is demonstrated.

  In that case, it is preferable that the recording component of the present invention contains at least a dye precursor represented by the general formula (32).

In general formula (32), A1 and PD are covalently bonded, and A1 breaks the covalent bond with PD by electron transfer or energy transfer between the sensitizing dye excited state or the two-photon excited state of the two-photon absorption compound. PD is a functional organic compound moiety, and PD represents an organic compound moiety having a feature that becomes a color former when covalently bonded to A1 and when the covalent bond with A1 is cleaved and released.
A1 is more preferably an organic compound site having a function of breaking a covalent bond with PD by electron transfer with a sensitizing dye excited state or a two-photon excited state of a two-photon absorption compound.

PD is preferably a dissociable azo dye, dissociable azomethine dye, dissociable oxonol dye, dissociable dye such as dissociated arylidene dye, or so-called “leuco dye” such as triphenylmethane dye or xanthene (fluorane) dye. And these are covalently linked to A1 on the chromophore.
PD is more preferably any one of a dissociation azo dye, a dissociation azomethine dye, a dissociation oxonol dye, and a dissociation arylidene dye.

  PD is preferably colorless or light colored when covalently bonded to A1, or has a short wavelength of absorption, and is strongly colored or has a long wavelength when released when the covalent bond with A1 is cut. .

  Although the preferable specific example of PD is given to the following, this invention is not limited to this.

  When PD forms a covalent bond with A1, it may be covalently bonded at any part on A1 as long as it is on the dye chromophore, but it is preferably covalently bonded to A1 at an atom indicated by an arrow in the above figure.

  It is more preferable that the dye precursor of the general formula (32) is represented by any one of the general formulas (33-1) to (33-6).

  In general formulas (33-1) to (33-6), PD has the same meaning as in general formula (32).

In the general formula (33-1), R ₇₁ represents a hydrogen atom or a substituent (preferably the same as the substituents exemplified in R ₂₀₃ as the substituent), preferably an alkyl group or an aryl group, More preferably, it is a t-butyl group.
R ₇₂ represents a substituent (preferably the same as the substituents exemplified in R ₂₀₃ as a substituent), preferably an electron-withdrawing group, more preferably a nitro group, sulfamoyl group, carbamoyl group, alkoxycarbonyl. Represents a group, a cyano group, or a halogen atom. a71 each independently represents an integer of 0 to 5, when a71 is 2 or more, the plurality of R ₇₂ may be the same or different and may form a ring. a71 is preferably 1 or 2, and R ₇₂ is preferably substituted at the 2- or 4-position.

In the general formula (33-2), R ₇₃ represents a substituent (preferably the same as the example of the substituent listed for R ₂₀₃ as a substituent), preferably represents an electron-withdrawing group, more preferably nitro. Represents a group, a sulfamoyl group, a carbamoyl group, an alkoxycarbonyl group, a cyano group, or a halogen atom, more preferably a nitro group. a72 each independently represents an integer of 0 to 5, when a72 is 2 or more, plural R ₇₃ may be the same or different, they may form a ring. a72 is preferably 1 or 2, and when a72 is 1, it is preferably substituted at the 2-position, and when a72 is 2, it is preferably substituted at the 2-position, 4-position, 2-position or 6-position. It is more preferable to substitute at the 6th position.
a73 represents 0 or 1.

In the general formula (33-3), R _{74 to} R ₇₇ each independently represents an alkyl group, preferably each represents a methyl group.

In the general formula (33-4), R ₇₈ and R ₇₉ each independently represent a substituent (preferably the same as the examples of substituents described above for R ₂₀₃ as a substituent), and R ₇₉ is preferably alkoxy. Represents a group, more preferably a methoxy group. a74 and a75 each independently represents an integer of 0 to 5, and when a74 and a75 are 2 or more, a plurality of R ₇₈ and R ₇₉ may be the same or different and may be linked together to form a ring. . a74 and a75 are preferably 0 to 2, a74 is more preferably 0 or 1, and a75 is more preferably 2. When a75 is 2, R ₇₉ is preferably substituted at the 3rd and 5th positions.
a76 represents 0 or 1;

In the formula (33-5), (preferred more substituents the same as the substituents exemplified in R ₂₀₃₎ R _80, R ₈₁ each independently represent a hydrogen atom or a substituent represents a R ₈₀ R ₈₁ may be linked to each other to form a ring, and the ring formed is preferably a benzene ring or a norbornene ring. When no ring is formed, R ₈₀ and R ₈₁ are preferably hydrogen atoms.

In the general formula (33-6), R ₈₂ and R ₈₃ each independently represents a substituent (preferably the same as the examples of the substituent mentioned in R ₂₀₃ as a substituent), preferably an alkyl group or alkenyl. Represents an aryl group. R ₈₂ and R ₈₃ are preferably connected to each other to form a ring, and the ring formed is preferably a fluorene ring, a dibenzopyran ring or a tetrahydronaphthalene ring.

  The dye precursor represented by the general formula (32) is preferably a compound represented by the general formula (33-1), (33-2), or (33-4).

  Although the preferable example of the dye precursor of this invention represented by general formula (33-1)-(33-6) below is shown, this invention is not limited to this.

  When the recording component of the present invention contains at least a dye precursor represented by the following general formula (32) or (33-1) to (33-6), the photon mode recording material or two-photon of the present invention. The absorbing optical recording material preferably further contains a base as necessary for the purpose of dissociating the dissociation type dye to be produced. The base may be an organic base or an inorganic base, and preferred examples include alkylamines, anilines, imidazoles, pyridines, carbonates, hydroxide salts, carboxylates, and metal alkoxides. Or the polymer containing those bases is also mentioned preferably.

Next, the case where the recording component of the present invention contains a compound capable of reacting with an electron transfer with a sensitizing dye excited state or a two-photon excited state of a two-photon absorbing compound to change the absorption form will be described.
The compounds capable of causing the above are collectively referred to as so-called “electrochromic compounds”.
The electrochromic compound used as the dye precursor in the present invention is preferably polypyrroles (preferably, for example, polypyrrole, poly (N-methylpyrrole), poly (N-methylindole), polypyrrolopyrrole), polythiophenes (preferably, for example, Polythiophene, poly (3-hexylthiophene), polyisothianaphthene, polydithienothiophene, poly (3,4-ethylenedioxy) thiophene), polyaniline (preferably for example polyaniline, poly (N-naphthylaniline), poly (o -Phenylenediamine), poly (aniline-m-sulfonic acid), poly (2-methoxyaniline), poly (o-aminophenol), poly (diallylamine)), poly (N-vinylcarbazole), Copyridinoporphyrazine Complex, Ni They are a phenanthroline complex and an Fe bathophenanthroline complex.

  Furthermore, electrochromic materials such as viologens, polyviologens, lanthanoid diphthalocyanines, styryl dyes, TNFs, TCNQ / TTF complexes, and Ru trisbipyridyl complexes are also preferable.

  The recording component of the present invention is a commercial product or can be synthesized by a known method.

  The two-photon absorption optical recording material of the present invention includes a sensitizing dye, an electron-donating compound having the ability to reduce radical cations of the two-photon absorption compound or the color former, or a sensitizing dye, a two-photon absorption compound or a color former. An electron accepting compound having the ability to oxidize radical anions can be preferably used. In particular, the use of an electron donating compound is preferable from the viewpoint of improving color developability.

  Preferred examples of the electron donating compound include alkylamines (preferably, for example, triethylamine, tributylamine, trioctylamine, N, N-dimethyldodecylamine, triethanolamine, triethoxyethylamine), anilines (preferably, for example, N, N-dioctylaniline, N, N-dimethylaniline, 4-methoxy-N, N-dibutylaniline, 2-methoxy-N, N-dibutylaniline), phenylenediamines (preferably, for example, N, N, N ', N'-tetramethyl-1,4-phenylenediamine, N, N, N', N'-tetramethyl-1,2-phenylenediamine, N, N, N ', N'-tetraethyl-1,3 -Phenylenediamine, N, N'-dibutylphenylenediamine), triphenylamines Preferably, for example, triphenylamine, tri (4-methoxyphenyl) amine, tri (4-dimethylaminophenyl) amine, TPD), carbazoles (preferably, for example, N-vinylcarbazole, N-ethylcarbazole), phenothiazines ( Preferably, for example, N-methylphenothiazine, N-phenylphenothiazine), phenoxazines (preferably, for example, N-methylphenoxazine, N-phenylphenoxazine), phenazines (preferably, for example, N, N′-dimethylphenazine) N, N'-diphenylphenazine), hydroquinones (preferably, for example, hydroquinone, 2,5-dimethylhydroquinone, 2,5-dichlorohydroquinone, 2,3,4,5-tetrachlorohydroquinone, 2,6-dichloro 3,5-dicyanohydroquinone, 2,3-dichloro-5,6-dicyanohydroquinone, 1,4-dihydroxynaphthalene, 9,10-dihydroxyanthracene), catechols (preferably, for example, catechol, 1,2,4- Trihydroxybenzene), alkoxybenzenes (preferably, for example, 1,2-dimethoxybenzene, 1,2-dibutoxybenzene, 1,2,4-tributoxybenzene, 1,4-dihexyloxybenzene), aminophenols (Preferably, for example, 4- (N, N-diethylamino) phenol, N-octylaminophenol), imidazoles (preferably, for example, imidazole, N-methylimidazole, N-octylimidazole, N-butyl-2-methylimidazole) ), Pyridines (preferred For example, pyridine, picoline, lutidine, 4-t-butylpyridine, 4-octyloxypyridine, 4- (N, N-dimethylamino) pyridine, 4- (N, N-dibutylamino) pyridine, 2- (N -Octylamino) pyridine), metallocenes (preferably eg ferrocene, titanocene, ruthenocene), metal complexes (preferably eg Ru bisbipyridine complexes, Cu phenanthroline complexes, Co trisbipyridine complexes, FeEDTA complexes, In addition, Ru, Fe, Re, Pt, Cu, Co, Ni, Pd, W, Mo, Cr, Mn, Ir, Ag complex, etc.), semiconductor fine particles (preferably, for example, Si, CdSe, GaP, PbS, ZnS) ) And the like. As the electron donating compound, phenothiazines are more preferable, and N-methylphenothiazine is most preferable.

On the other hand, the electron accepting compound is preferably an aromatic compound into which an electron withdrawing group is introduced (preferably, for example, 1,4-dinitrobenzene, 1,4-dicyanobenzene, 4,5-dichloro-1, 2-dicyanobenzene, 4-nitro-1,2-dicyanobenzene, 4-octanesulfonyl-1,2-dicyanobenzene, 1,10-dicyanoanthracene), a heterocyclic compound, or a hetero in which an electron withdrawing group is introduced A ring compound (preferably, for example, pyrimidine, pyrazine, triazine, dichloropyrazine, 3-cyanopyrazole, 4,5-dicyano-1-methyl-2-octanoylaminoimidazole, 4,5-dicyano-imidazole, 2,4- Dimethyl-1,3,4-thiadiazole, 5-chloro-3-phenyl-1,2,4-thiadiazole 1,3,4-oxadiazole, 2-chlorobenzothiazole, N-butyl-1,2,4-triazole), N-alkylpyridinium salts (preferably, for example, N-butylpyridinium iodide, N-butyl) Pyridinium bis (trifluoromethanesulfonyl) imide, N-butyl-3-ethoxycarbonyl-pyridinium butanesulfonate, N-octyl-3-carbamoylpyridinium bis (trifluoromethanesulfonyl) imide, N, N-dimethylviologen di (hexafluorophosphate) N, N-diphenylviologen bis (bis (trifluoromethanesulfonyl) imide), benzoquinones (preferably, for example, benzoquinone, 2,5-dimethylbenzoquinone, 2,5-dichlorobenzoquinone, 2,3,4, -Tetrachlorobenzoquinone, 2,6-dichloro-3,5-dicyanobenzoquinone, 2,3-dichloro-5,6-dicyanobenzoquinone, naphthoquinone, anthraquinone), imides (preferably, for example, N, N'-dioctylpyro Meritimide, 4-nitro-N-octylphthalimide), metal complexes (preferably, for example, Ru trisbipyridine complexes, Ru bisbipyridine complexes, Co trisbipyridine complexes, Cr trisbipyridine complexes, PtCl ₆ complexes, In addition, Ru, Fe, Re, Pt, Cu, Co, Ni, Pd, W, Mo, Cr, Mn, Ir, Ag complex, etc., semiconductor fine particles (preferably, for example, TiO ₂ , Nb ₂ O ₅ , ZnO) SnO ₂ , Fe ₂ O ₃ , WO ₃ ) and the like.

  The oxidation potential of the electron donating compound is preferably lower (minus side) than the oxidation potential of the sensitizing dye, the two-photon absorption compound, the two-photon excitation state, or the oxidation potential of the color former or the reduction potential of the excited state. The reduction potential of the compound is preferably nobler (plus side) than the oxidation potential of the sensitizing dye excited state, the two-photon absorption compound two-photon excited state, or the reduction potential of the color former or the excited state.

In the photon mode recording material and the two-photon absorption optical recording material of the present invention, a binder is preferably used. The binder is usually used for the purpose of improving the film formability of the composition, the uniformity of the film thickness, and the stability during storage. As the binder, those having good compatibility with the sensitizing dye, the two-photon absorption compound and the recording component are preferable.
As the binder, a solvent-soluble thermoplastic polymer is preferable and can be used alone or in combination with each other.

  The binder has a reactive site and may be cross-linked or hardened by reacting with a cross-linking agent, a polymerizable monomer or an oligomer. In this case, the reactive site includes an ethylenically unsaturated group represented by an acrylic group and a methacryl group as a radical reactive site, an oxirane compound, an oxetane compound, a vinyl ether group as a cationic reactive site, and a carboxyl group as a condensation polymerization reaction site. Preferred are acids, alcohols, amines and the like.

Preferred binders for use in the present invention include, for example, 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). Polymers), 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, butadiene And isoprene polymers and copolymers and polyglycols having a weight average molecular weight of approximately 4,000 to 1,000,000, high molecular weight poly (ethylene oxide), epoxides (eg epoxies having acrylate or methacrylate groups) Compound), 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 (polyvinyl butyral and polyvinyl formal), polyvinyl alcohol, polyvinyl pyrrolidone, acid-containing polymers and copolymers that function as suitable binders in US Pat. No. 3,458,311 and US Pat. No. 4,273. , 857, and the like.
In addition, polystyrene polymers and copolymers such as acrylonitrile, maleic anhydride, acrylic acid, methacrylic acid and esters thereof, vinylidene chloride copolymers (eg vinylidene chloride / acrylonitrile copolymers, vinylidene chloride / methacrylate copolymers) Polymers, vinylidene chloride / vinyl acetate copolymer), polyvinyl chloride and copolymers (eg, polyvinyl chloride / acetate, vinyl chloride / acrylonitrile copolymer), polyvinyl benzal synthetic rubber (eg, butadiene / acrylonitrile copolymer) , Acrylonitrile / butadiene / styrene copolymer, methacrylate / acrylonitrile / butadiene / styrene copolymer, 2-chlorobutadiene-1,3 polymer, chlorinated rubber, styrene / butadiene / styrene, styrene / Isoprene / styrene block copolymer), copolyesters (eg, polymethylene glycols of the formula HO (CH ₂ ) nOH, where n is an integer from 2 to 10), and (1) hexahydroterephthalic acid, sebacine Acid and terephthalic acid, (2) terephthalic acid, isophthalic acid and sebacic acid, (3) terephthalic acid and sebacic acid, (4) produced from the reaction product of terephthalic acid and isophthalic acid, and (5) the glycol And (i) a mixture of terephthalic acid, isophthalic acid and sebacic acid and (ii) a copolyester prepared from terephthalic acid, isophthalic acid, sebacic acid and adipic acid), poly N-vinylcarbazole and copolymers thereof, and H . Examples include carbazole-containing polymers as disclosed in Kamogawa et al. In Journal of Polymer Science: Polymer Chemistry Edition, Vol. 18, pp. 9-18 (1979).

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

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

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

  The binder used in the photon mode recording material and the two-photon absorption optical recording material of the present invention is preferably a binder having a refractive index of 1.5 or less.

  In the photon mode recording material and the two-photon absorption optical recording material of the present invention, additives such as a polymerizable monomer, a polymerizable oligomer, a crosslinking agent, a heat stabilizer, a plasticizer, and a solvent can be appropriately used as necessary.

  Preferable examples when the polymerizable monomer, polymerizable oligomer, and crosslinking agent are used for the photon mode recording material and the two-photon absorption optical recording material of the present invention include those described in Japanese Patent Application No. 2003-82732.

A heat stabilizer can be added to the photon mode recording material and the two-photon absorption optical 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. Also useful are dinitroso dimers described in US Pat. No. 4,168,982 to Pazos.

  Plasticizers are used to change the adhesion, flexibility, hardness, and other mechanical properties of photon mode recording materials and two-photon absorption optical recording materials. Examples of the plasticizer include triethylene glycol dicaprylate, triethylene glycol bis (2-ethylhexanoate), tetraethylene glycol diheptanoate, diethyl sebacate, dibutyl suberate, tris (2-ethylhexyl) phosphate, Examples include tricresyl phosphate and dibutyl phthalate.

In general, the proportion of each component in the photon mode recording material and the two-photon absorption optical recording material of the present invention is preferably in the following range based on the total mass of the composition.
(Reactive) Binder, polymerizable monomer, polymerizable oligomer, crosslinking agent:
Preferably 0 to 95% by mass, more preferably 30 to 95% by mass,
Recording component: preferably 3 to 80% by mass, more preferably 5 to 60% by mass,
Sensitizing dye or two-photon absorbing compound:
Preferably it is 0.01-10 mass%, More preferably, it is 0.1-3 mass%
Electron donating compound or electron accepting compound:
Preferably it is 0.1-30 mass%, More preferably, it is 1-20 mass%

The photon mode recording material and the composition for a two-photon absorption optical recording material of the present invention may be prepared by a usual method. For example, the above-mentioned essential components and optional components can be prepared as they are or by adding a solvent as necessary.
Examples of the solvent include ketone solvents such as methyl ethyl ketone, methyl isobutyl ketone, acetone and cyclohexanone, ester solvents such as ethyl acetate, butyl acetate, ethylene glycol diacetate, ethyl lactate and cellosolve acetate, carbonization such as cyclohexane, toluene and xylene. Hydrogen solvent, ether solvents such as tetrahydrofuran, dioxane, diethyl ether, cellosolv solvents such as methyl cellosolve, ethyl cellosolve, butyl cellosolve, dimethyl cellosolve, methanol, ethanol, n-propanol, 2-propanol, n-butanol, diacetone Alcohol solvents such as alcohol, fluorine solvents such as 2,2,3,3-tetrafluoropropanol, dichloromethane, chloroform, 1,2-dichloro Halogenated hydrocarbon solvents such as Roetan, N, N-amide solvents such as dimethylformamide, acetonitrile, and a nitrile solvent such as such as propionitrile.

The photon mode recording material and the two-photon absorption optical 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 cast as a film and then applied to the substrate by a usual method. Lamination can also be performed, whereby a photon mode recording material and a two-photon absorption optical 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.

  Further, a protective layer for blocking oxygen may be formed on the photon mode recording material and the two-photon absorption optical 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.

[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.

  [Synthesis of sensitizing dye and two-photon absorption compound used in the present invention]

(1) Synthesis of D-73

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

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

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

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

(2) Synthesis of D-84

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

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

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

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

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

  However, the method for synthesizing the sensitizing dye and the two-photon absorption compound of the present invention is not limited to this.

  Many of the decolorizer precursors of the present invention are commercially available or can be synthesized by known methods.

[Two-photon absorption latent image color development-evaluation of refractive index modulation and absorptance modulation increase by amplification reaction]

Next, the refractive index modulation and the absorption modulation increasing method by the two-photon absorption optical recording material and the recording method of the present invention capable of causing the self-sensitized amplification reaction of the latent image color produced by two-photon absorption will be described.
Samples 101 to 103 and comparative samples 1 to 3 of the two-photon absorption tertiary optical recording material of the present invention were prepared with the following compositions.

<Sample 101: Two-photon absorption optical recording material of the present invention>
Two-photon absorption compound: D-128 1 part by mass Recording component: 23 parts by mass of acid generator I-103
Acid coloring dye precursor R-9 10 parts by mass
Electron-donating compound ED-1 20 parts by mass Binder: Aldrich poly (methyl methacrylate-ethyl acrylate copolymer) (average molecular weight 101000) 46 parts by mass Solvent: chloroform (if necessary, acetonitrile) 3 times mass of the above components < Comparative sample 1>
Recording component: 23 parts by mass of acid generator I-103
Acid coloring dye precursor R-9 10 parts by mass
Electron-donating compound ED-1 20 parts by mass Binder: Aldrich poly (methyl methacrylate-ethyl acrylate copolymer) (average molecular weight 101000) 47 parts by mass Solvent: Chloroform (using acetonitrile if necessary) 3 times mass of the above components

<Sample 102: Two-photon absorption optical recording material of the present invention>
Two-photon absorption compound: D-128 1 part by mass Recording component: Base generator PB-3 20 parts by mass
10 parts by mass of base coloring dye precursor DD-17
Electron-donating compound ED-1 20 parts by mass Binder: Polymethyl methacrylate (average molecular weight 120,000) manufactured by Aldrich 49 parts by mass Solvent: Chloroform 3 times the mass of the above components <Comparative Sample 2>
Recording component: 20 parts by mass of base generator PB-3
Base coloring dye precursor DD-17 10 parts by mass Binder: Aldrich polymethyl methacrylate (average molecular weight 120,000) 70 parts by mass Solvent: Chloroform 3 times mass of the above components

<Sample 103: Two-photon absorption optical recording material of the present invention>
Two-photon absorption compound: D-128 1 part by mass Recording component: Dye precursor E-14 24 parts by mass Electron donating compound ED-1 20 parts by mass Base: Trioctylamine 5 parts by mass Binder: Polymethyl methacrylate (manufactured by Aldrich) (Average molecular weight 120,000) 50 parts by mass Solvent: chloroform 3 times mass of the above components <Comparative Sample 1>
Recording component: Dye precursor E-14 24 parts by mass Base: Trioctylamine 5 parts by mass Binder: Aldrich polymethyl methacrylate (average molecular weight 120,000) 71 parts by mass Solvent: Chloroform 3 times mass of the above components

  Samples 101 to 103 and comparative samples 1 to 3 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. When the refractive indexes of the samples 101 to 103 were measured with an ellipsometer, they were 1.49, 1.48 and 1.49 at 720 nm.

For the performance evaluation of the two-photon absorption recording material 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 is used. The two-photon absorption recording material of the present invention was condensed and irradiated with the laser beam with a lens having NA of 0.6.
The irradiation wavelength used was around the wavelength at which the two-photon absorption cross section δ was maximum in a 10 ⁻⁴ M solution of the two-photon absorption compound.
Samples 101 to 103 and comparative samples 1 to 3 were irradiated with a laser beam of 740 nm to cause two-photon absorption (first step). In samples 101 to 103, the laser focal point ( A slight color development was confirmed in the recording section). When the refractive index of the color-developing part was measured with an ellipsometer, it was 1.50, 1.48, 1.49 at 740 nm, slightly increased compared to the laser non-focused part (non-recording part), or almost the same There wasn't.
Furthermore, as a result of exposing the entire surface of light in the wavelength range of 680 to 720 nm (second step), color development was clearly confirmed in the recording portion of the first step. The change in the absorptance between the recorded portion and the non-recorded portion could be confirmed visually. When the refractive index of the color developing part was measured with an ellipsometer, it increased to 1.57, 1.56, 1.57 at 740 nm, as compared with the laser non-focused part (non-recording part). When the laser of 740 nm was irradiated, the difference in reflectance due to the difference in refractive index could be confirmed between the colored recording portion and the non-recording portion.
Further, when the recorded samples 101 to 103 were irradiated with a laser beam of 660 nm, a difference in reflectance due to a difference in absorptance could be confirmed between the recording part and the non-recording part.
For samples 101 to 103, if it is attempted to perform the same absorption rate and refractive index modulation as in the case where the second step is performed only by 740 nm laser irradiation in the first step, the irradiation time is about 10 times longer. I needed it. That is, the latent image color-self-sensitized amplification recording system of the present invention shows that about 10 times amplification is possible in the second step. It was also confirmed that further amplification is possible by increasing the irradiation time in the second step.

In contrast, Comparative Samples 1 to 3 that do not contain the two-photon absorption compound D-128 of the present invention do not change anything even when irradiated with a 740 nm laser, and the color development (refractive index modulation) is 2 for the two-photon absorption compound. It is clear that this occurs by generating an excited state by photon absorption.
In addition, by scanning the laser focus position in the horizontal and depth directions, it is possible to develop a color at an arbitrary place in the three-dimensional direction, and it is possible to modulate the reflectance of light by three-dimensional refractive index modulation and absorptivity modulation. I confirmed that there was.

The two-photon absorption compound is D-1, D-5, D-22, D-41, D-56, D-58, D-73, D-75, D-77, D-84, D-117. Even if the binder is changed to D-118, D-123, D-132, D-142, D-143, or the binder is changed to polyvinyl acetal, cellulose acetate butyrate, polymethylphenylsiloxane, etc., the same effect is obtained. Obtained.
Furthermore, in sample 101, the acid generator of the recording component was 2- (4′-methoxyphenyl) -4,6-bis (trichloromethyl) -1,3,5-triazine, 4-diethylaminophenyldiazonium tetrafluoroborate, Di (t-butylphenyl) iodonium tetra (pentafluorophenyl) borate, tris (4-methylphenyl) sulfonium tetra (pentafluorophenyl) borate, triphenylsulfonium methanesulfonate, triphenylsulfonium perfluoropentanoate, bis (1 Even if it is changed to-(4-diphenylsulfonium) phenyl sulfide ditriflate, benzoin tosylate, 2,6-dinitrobenzyl tosylate or N-tosyl phthalimide, the sample 101 has an acid coloring dye precursor as a recording component. Kuru The same effect was obtained even when changed to Star Violet Lactone, R-7, or R-8.
Further, the base generator of the recording component in the sample 102 is PB-4, PB-8, PB-10, PB-12, PB-13, PB-19, PB-22, PB-32, PB-33, Even if it changes to PB-52, the base coloring type | mold dye precursor (dissociation type | mold non-dissociation body) is changed to DD-3, DD-9, DD-12, DD-23, DD-24, DD- in the sample 102. Similar effects were obtained even when changed to 30, DD-32, DD-33, DD-34, DD-37, DD-38, DD-43, DD-45, DD-46.
In the sample 103, the recording components were E-4, E-5, E-11, E-12, E-13, E-16, E-17, E-18, E-19, E-25, E The same effect was obtained even when changed to -26, E-27, E-29, E-32, E-34, E-37, E-38, E-39, E-42.
In the above case, the laser wavelength for causing the two-photon absorption, the wavelength of the light for performing the entire exposure, the wavelength of the light for viewing the reflectance change due to the refractive index modulation, and the wavelength of the light for viewing the reflectance variation due to the change in the absorbance are as follows: The optimum wavelength was used in each system, and when an electron donating compound was necessary, it was changed to the optimum one.

  Even if the experiment similar to the above was performed by linear absorption instead of two-photon absorption, the same effect was obtained if recording was performed only in the plane direction. Therefore, the recording system of the present invention can also be applied to photon mode recording systems and materials based on linear absorption.

Claims (14)

And at least 1) a sensitizing dye, and 2) a dye precursor that has a wavelength longer than that of the original state and can become a color former having absorption in a wavelength region different from that of the sensitizing dye, and the sensitizing dye Or a recording method of a photon mode recording material having a recording component that can be recorded as a difference in refractive index or an absorption difference through an electron transfer or energy transfer process from an excited state of the color former, at least by light irradiation A first step of generating the color former as a latent image, and a second step of recording the color former latent image as a difference in refractive index or absorptivity by generating a self-sensitized amplification. A photon mode recording method characterized by performing a dry process.   2. The photon mode recording method according to claim 1, wherein the sensitizing dye is a two-photon absorption compound, and the first step generates a latent image when two-photon absorption occurs by light irradiation.   3. The photon mode recording method according to claim 1, wherein the second step is any one of light irradiation, heat application, electric field application, and magnetic field application.   In the second step, the color former is self-exposed by irradiating the color former latent image with light in a wavelength region having a molar absorption coefficient of sensitizing dye linear absorption of 5000 or less to cause linear absorption of the color former latent image 4. The photon mode recording method according to claim 1, wherein the sensitized amplification is generated and recorded as a difference in refractive index or a difference in absorption rate.   The wavelength of the light for generating the latent image in the first step is the same as the wavelength of the light for amplifying the latent image in the second step to form a refractive index difference or an absorption difference, or the second 5. The photon mode recording method according to claim 4, wherein the wavelength of light in the process is a short wavelength.   Using the photon mode recording material recorded by the method according to any one of claims 1 to 5, irradiating the recording material with light, a difference in reflectance or transmittance due to a difference in refractive index or a difference in absorptance is obtained. An optical recording / reproducing method, wherein reproduction is performed by detection.   6. The photon mode recording method according to claim 1, wherein the recording component includes at least an acid color-forming dye precursor as a dye precursor and an acid generator.   The photon mode recording method according to claim 1, wherein the recording component includes at least a base color-forming dye precursor as a dye precursor and a base generator.   6. The photon mode recording method according to claim 1, wherein the sensitizing dye is represented by a methine dye or a phthalocyanine dye.   6. The photon mode recording material comprises an electron donating compound having an ability to reduce a radical cation of a color former generated from a sensitizing dye, a two-photon absorption compound or a dye precursor. The photon mode recording method according to claim 1.   11. The photon mode recording method according to claim 10, wherein the electron donating compound is a phenothiazine.   6. The photon mode recording material comprises an electron accepting compound having an ability to oxidize a radical anion of a color former generated from a sensitizing dye, a two-photon absorption compound or a dye precursor. The photon mode recording method according to claim 1.   Two-photon absorption induced by irradiating the two-photon absorption optical recording material with a laser beam having a wavelength longer than the linear absorption band of the two-photon absorption compound and having no linear absorption in the first step. 6. The photon mode recording method according to claim 2, wherein a latent image is formed by using the method.   A three-dimensional optical recording method using the photon mode recording method according to claim 1.