JP2005099754A - Hologram recording method and hologram recording material - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a hologram recording method applicable to a high density optical recording medium, a three-dimensional display, a holographic optical element etc. and capable of making a high sensitivity, a high diffraction efficiency, a satisfactory storage property, a low shrinkage rate, a dry processing, and a multiplex recording property compatible with each other. <P>SOLUTION: The hologram recording method comprises at least a first step of producing a latent image upon holographic exposure, and a second step of forming an interference fringe by amplifying the latent image, wherein the first and second steps are dry processing; particularly, the second step is a step of causing the the refractive index modulation by amplifying the latent image to form an interference fringe. <P>COPYRIGHT: (C)2005,JPO&NCIPI

Description

  The present invention relates to a hologram recording material and a hologram recording method applicable to a high-density optical recording medium, a three-dimensional display, a holographic optical element, and the like.

  General principles relating to hologram production are described in chapter 2 of several literatures and technical books such as “Holographic Display” (Junpei Uchinai, Sangyo Tosho [Non-Patent Document 1]). According to these, the photosensitive hologram recording material is placed at a position where one of the two light fluxes of the coherent laser light is irradiated onto the recording object and the total reflection light from the recording object can be received. The hologram recording material is directly irradiated with the other coherent light in addition to the reflected light from the object without hitting the object. Reflected light from the object is referred to as object light, and light directly applied to the recording material is referred to as reference light, and interference fringes between the reference light and object light are recorded as image information. Next, when the processed recording material is irradiated with the same light (reproduction illumination light) as the reference light, it is diffracted by the hologram so as to reproduce the wavefront of the reflected light that first reaches the recording material from the object during recording. As a result, an object image substantially the same as the real image of the object can be observed three-dimensionally.

A hologram formed by causing the reference light and the object light to enter the hologram recording material from the same direction is called a transmission hologram. The interference fringes are formed at intervals of about 1000 to 3000 per 1 mm in a form perpendicular or nearly perpendicular to the recording material film surface direction.
On the other hand, holograms formed by being incident on opposite sides of the hologram recording material are generally called reflection holograms. The interference fringes are formed at intervals of about 3000 to 7000 per 1 mm in a shape parallel or nearly parallel to the recording material film surface direction.
The transmission hologram can be created by a known method as disclosed in, for example, JP-A-6-43634 [Patent Document 1]. The reflection hologram can be created by a known method disclosed in, for example, JP-A-2-3082 [Patent Document 2] and JP-A-3-50588 [Patent Document 3].

On the other hand, a hologram whose film thickness is sufficiently thick with respect to the interference fringe interval (usually a film thickness of about 5 times the interference fringe interval or about 1 μm or more) is called a volume hologram.
On the other hand, a hologram whose film thickness is about 5 times or less of the interference fringe spacing or about 1 μm or less is called a planar type or a surface type.

  Further, a hologram that records interference fringes by absorption of a dye or silver is called an amplitude hologram, and a hologram that is recorded by surface relief or refractive index modulation is called a phase hologram. Amplitude holograms are not preferred in terms of light utilization efficiency because light diffraction efficiency or reflection efficiency is significantly reduced due to light absorption, and phase holograms are usually preferred.

Conventionally, a hologram can reproduce a three-dimensional stereoscopic image, and therefore has been used for a cover of a book, a magazine, a display such as a POP, and a gift because of its excellent design and decoration effect. In particular, it is also used for credit cards, banknotes, packaging and the like for security purposes for preventing counterfeiting, and currently forms a large market.
These holograms are planar surface relief phase holograms. Usually, it is also called an embossed hologram because it is embossed by a master made of a photoresist and mass-replicated.
However, surface relief phase holograms are difficult to achieve full color, white reproduction, high resolution, and high diffraction efficiency. Recently, volume phase holograms that enable them have been attracting attention.

In a volume phase hologram, the phase of light can be modulated without absorbing light by forming many interference fringes with different refractive indexes in the hologram recording material instead of optical absorption.
In particular, reflective volume phase holograms, also called Lippmann holograms, are capable of full color, white reproduction and high resolution with high diffraction efficiency due to wavelength selective reflection by black diffraction, and high resolution full color 3D display. Can be provided.
Recently, taking advantage of the wavelength selective reflection, a hologram optical element represented by a head-up display (HUD) mounted on an automobile, a pickup lens for an optical disk, a head-mounted display, a color filter for liquid crystal, a reflective liquid crystal reflector, and the like. (HOE) has been widely put into practical use.
In addition, for example, practical use or application is being studied for lenses, diffraction gratings, interference filters, optical fiber couplers, facsimile light polarizers, architectural window glass, and the like.

  Here, as a known volume phase hologram recording material, a dichromate gelatin method, a bleached silver halide salt method, a photopolymer method, and the like are known as a write-once method, and a photorefractive method and a photochromic polymer as a rewritable method. Methods are known.

However, in these known volume phase hologram recording materials, in particular, for high-sensitivity and high-resolution full-color three-dimensional display applications, materials that satisfy all the required requirements have not been improved.
Specifically, for example, the dichromated gelatin system has the advantages of high diffraction efficiency and low noise characteristics, but has a problem that storage stability is extremely poor, wet processing is required and low sensitivity is required.
The bleached silver halide method has the advantage of high sensitivity, but has a problem that wet processing is necessary, the bleaching processing is complicated, and light resistance is poor.
The photorefractive material has the advantage that it can be rewritten, but has a problem that a high electric field needs to be applied at the time of recording, and the recording storability is poor.
Although the photochromic polymer system represented by azobenzene polymer material has the advantage that it can be rewritten, it has a problem that the sensitivity is very low and the storage stability is poor.

Under such circumstances, the dry-processed photopolymer method disclosed in Patent Documents 1 to 3 described above has a basic composition of a binder, a monomer capable of radical polymerization, and a photopolymerization initiator. We have devised a difference in refractive index by using a compound having an aromatic ring or chlorine or bromine on one of the radically polymerizable monomers, and as a result, in the bright part of the interference fringes formed during hologram exposure The monomer can form a refractive index difference by polymerization while the binder gathers in the dark part. Therefore, it can be said that it is a relatively practical method that can achieve both high diffraction efficiency and dry processing.
However, compared with the bleached silver halide method, the sensitivity is about 1/1000, heat-fixing treatment of nearly 2 hours is required to increase the diffraction efficiency, and radical polymerization, so polymerization inhibition by oxygen is inhibited. Further, there is a problem that the diffraction wavelength and angle at the time of reproduction change due to the shrinkage of the recording material after exposure and fixing, and further improvement is desired.

By the way, in the recent trend of advanced information society, networks such as the Internet and high-definition TVs are rapidly spreading. In addition, HDTV (High Definition Television) will soon be broadcast, and there is an increasing demand for a high-density recording medium for easily and inexpensively recording image information of 100 GB or more in consumer use.
Furthermore, in the trend of increasing computer capacity, there is a need for ultra-high-density recording media that can record large volumes of information of about 1 TB or more at high speed and low cost for business use such as computer backup and broadcast backup. It has been.
Under such circumstances, a compact, inexpensive optical recording medium that is replaceable and randomly accessible has attracted more attention than a magnetic tape medium that cannot be randomly accessed and a hard disk that is not replaceable and easily failed. However, an existing two-dimensional optical recording medium such as a DVD-R is expected to have a recording capacity sufficiently large to meet future demands, even if the recording / reproducing wavelength is shortened, even if the recording / reproducing wavelength is shortened. It is a situation that cannot be said.

  Therefore, a three-dimensional optical recording medium that performs recording in the film thickness direction has attracted attention as the ultimate ultra-high density recording medium. As a promising method, there are a method using a two-photon absorption material and a method using holography (interference). Therefore, volume phase hologram recording materials have recently attracted attention as a three-dimensional optical recording medium.

  In an optical recording medium using a volume phase hologram recording material, two-dimensional digital information (referred to as signal light) using a spatial light modulation element (SLM) such as DMD or LCD instead of object light reflected from a three-dimensional object. Will be recorded a lot. At the time of recording, multiplex recording such as angle multiplexing, phase multiplexing, wavelength multiplexing, and shift multiplexing is performed, so that the capacity can be increased to 1 TB. In addition, a CCD, CMOS, or the like is usually used for reading, and the parallel transfer and reading thereof can increase the transfer rate up to 1 Gbps.

However, the requirements for hologram recording materials used for holographic memories are more severe than those for three-dimensional displays and HOE applications as described below.
(1) High sensitivity (2) High resolution (3) High hologram diffraction efficiency (4) Recording process is dry and quick (5) Multiple recording is possible (Wide dynamic range)
(6) Shrinkage after recording is small (7) Hologram storage stability is good

In particular, (1) high sensitivity, (3) high diffraction efficiency, (4) dry processing, (6) low shrinkage after recording, and (7) good storage stability. This is a contradictory physical property in terms of chemistry, and it is extremely difficult to achieve both.
For example, the bleached silver halide method is highly sensitive, but requires wet processing and is therefore generally not suitable for high density recording material applications.
Further, WO9744365A1 [Patent Document 4] presents a rewritable hologram recording material using refractive index anisotropy and orientation control of an azobenzene polymer (photochromic polymer). Although the yield is low and the system is accompanied by a change in orientation, the sensitivity is extremely low, and there is a problem in that the record storability is poor due to the contradiction of being rewritable, which is not suitable for implementation.
On the other hand, although the dry photopolymer method using radical polymerization described in Patent Documents 1 to 3 described above has a relatively high sensitivity among the photopolymer methods, it has a very high shrinkage rate and can withstand use as a holographic memory application. It is not a thing. Furthermore, since the film is soft, the storage stability is insufficient.

Here, in general, cationic polymerization, particularly cationic polymerization accompanied by ring opening of an epoxy compound or the like with respect to radical polymerization, gives less rigidity after polymerization and is not hindered by oxygen to give a rigid film. Therefore, some point out that cationic polymerization is more suitable for holographic memory applications.
For example, in JP-A-5-107999 [Patent Document 5] and JP-A-8-16078 [Patent Document 6], a cationically polymerizable compound (monomer or oligomer) is used instead of a binder, and further a sensitizing dye, radical A hologram recording material in which a polymerization initiator, a cationic polymerization initiator, and a radical polymerizable compound are combined is disclosed.
Further, JP-A-2001-523842 [Patent Document 7], JP-A-11-512847 [Patent Document 8] and the like disclose that a sensitizing dye, a cationic polymerization initiator, a cationic polymerizable compound, and a binder are used without using radical polymerization. A hologram recording material using only is disclosed.
However, although these cation polymerization methods show improvement in shrinkage rate compared to radical polymerization methods, the contradiction is that the sensitivity is lowered, and in practical use, it is considered to be a big problem in terms of transfer rate. . In addition, the diffraction efficiency is lowered, which is considered to be a problem in terms of S / N ratio and multiple recording.

  As described above, since the photopolymer method is a method involving mass transfer, when considering application to a holographic memory, if the storage property is good and the shrinkage is reduced, the sensitivity decreases (cation polymerization method). On the other hand, if the sensitivity is improved, storage stability and shrinkage deteriorate (radical polymerization method). Further, in order to improve the recording density of the holographic memory, multiplex recording exceeding 50 times and preferably exceeding 100 times is essential. However, in the photopolymer method, since polymerization with mass transfer is used for recording. In contrast to the initial recording speed of multiple recording, the recording speed in the latter stage of multiple recording after the polymerization of many compounds has progressed. By controlling this, the exposure amount is adjusted, and a wide dynamic range is achieved. This is a big problem in implementation.

On the other hand, the silver halide method, like a silver salt photograph, forms a latent image with a slight amount of light during hologram exposure and amplifies it during development processing, so it has higher sensitivity than other methods such as the photopolymer method. The point is the biggest attraction.
However, the silver halide method is a method in which the silver halide is changed to developed silver (black) at the time of development, but there are problems such as wet processing and the fact that the diffraction efficiency is extremely low because it is an amplitude type rather than a phase type. This is not suitable for holographic memory applications.
The bleached silver halide system that bleaches (oxidizes) developed silver and returns it to silver halide is a phase type and improves the diffraction efficiency, but the storage efficiency deteriorates, the scattering is large, the wet processing is complicated. New problems have also arisen, and they are not suitable for holographic memory applications.

Such problems of high sensitivity, good storage stability, low shrinkage, dry processing dilemma, and multiple recording characteristics are unavoidable in terms of physical laws as long as a photopolymer system with mass transfer is used. In addition, it is theoretically difficult to satisfy the requirements for holographic memory using a silver halide method, particularly in terms of dry processing.
Therefore, in order to apply hologram recording materials to holographic memory, such a problem has been drastically solved, and in particular, it is completely new that can achieve both high sensitivity and low shrinkage, good storage, dry processing, and multiple recording characteristics. Development of a recording system has been strongly desired.
"Holographic Display", Junpei Uchiuchi, Industrial Books JP-A-6-43634 JP-A-2-3082 Japanese Patent Laid-Open No. 3-50588 WO9744365A1 publication Japanese Patent Laid-Open No. 5-107999 JP-A-8-16078 Special table 2001-523842 Japanese National Patent Publication No. 11-512847

  Therefore, the object of the present invention is to achieve both high sensitivity and high diffraction efficiency, good storability, low shrinkage, dry processing, and multiple recording characteristics applicable to high-density optical recording media, three-dimensional displays, holographic optical elements, and the like. It is to provide a hologram recording material and a hologram recording method that can be performed.

As a result of intensive studies by the inventors, the object of the present invention has been achieved by the following means.
(1) A hologram having at least a first step of forming a latent image by hologram exposure and a second step of forming interference fringes by amplification of the latent image, and performing these by dry processing Recording method.
(2) The hologram recording method according to claim 1, wherein the second step forms an interference fringe by amplifying the latent image and performing refractive index modulation.
(3) The hologram recording method according to (1) or (2), wherein the second step is caused by any one of light irradiation, heat application, electric field application, and magnetic field application.
(4) The hologram recording method according to (3), wherein the second step is any one of light irradiation, heat application, and electric field application in (3) and the hologram described in (3) Recording material.
(5) The hologram recording method according to (3), wherein the second step is either light irradiation or heat application.
(6) A hologram recording method according to (3), wherein the second step is light irradiation.
(7) In the first step, a color former having no absorption at the hologram reproduction light wavelength is generated as a latent image, and in the second step, the color former latent image is irradiated with light having a wavelength different from that of the hologram exposure. The hologram recording method according to any one of (1) to (7), which is a step of recording interference fringes as refractive index modulation by self-sensitizing amplification generation of a color former.
(8) The hologram recording method according to any one of (1) to (7), wherein silver halide is not used in (1) to (7).
(9) The hologram recording method according to any one of (1) to (8), wherein the hologram recording cannot be rewritten in (1) to (8).
(10) A hologram recording material capable of hologram recording by the hologram recording method according to any one of (1) to (9), wherein the hologram recording material is at least as a compound group,
1) a sensitizing dye that absorbs light and generates an excited state by hologram exposure in the first step;
2) Includes a dye precursor that can be a color former that has a longer wavelength than the original state and that has no absorption at the hologram reproduction light wavelength, and electron transfer or energy transfer from a sensitizing dye or color former excited state. Interference fringe recording component capable of recording interference fringes using refractive index modulation by color development that occurs through the process,
A holographic recording material comprising:
(11) The dye precursor contained in the interference fringe recording component has a wavelength longer than that of the original state, has no absorption at the hologram reproduction light wavelength, and is shorter by 200 nm from the hologram reproduction light wavelength and the hologram reproduction light wavelength. The hologram recording material according to (10), which can be a color former having an absorption maximum in a region between wavelengths.
(12) In (11), the dye precursor contained in the interference fringe recording component has a longer absorption wavelength than the original state, and has no absorption at the hologram reproduction light wavelength. The hologram recording material according to (11), which can be a color former having an absorption maximum in a region between a light wavelength and a wavelength shorter than 100 nm.
(13) Using the hologram recording material described in (10) to (12), the electron transfer or energy transfer from the excited state of the sensitizing dye generated by hologram exposure to the interference fringe recording component results in absorption from the original state. The first step of generating a color development body having a longer wavelength and having no absorption at the hologram reproduction light wavelength as a latent image; unlike the hologram exposure wavelength, it has a shorter wavelength and a sensitizing dye molar extinction coefficient of 5000 or less. Second step of recording interference fringes using refractive index modulation by color development by irradiating light of a wavelength in a certain area and amplifying and generating the color former generated as a latent image in the first step by self-sensitization The hologram recording method according to any one of (10) to (12) and a hologram recording material capable of such recording, wherein the hologram recording method is performed by a dry process.
(14) In the second step of (13), light having a wavelength shorter than that of the hologram exposure wavelength and a wavelength in a region where the molar absorption coefficient of the sensitizing dye is 1000 or less is irradiated. The hologram recording method according to (13) and the recording, wherein the interference fringes are recorded using refractive index modulation by color development by amplifying and generating the color former generated as a latent image in the process by self-sensitization Hologram recording material that is possible.
(15) In the second step of (13), irradiation is performed with light having a wavelength shorter than that of the hologram exposure wavelength and in a region where the molar absorption coefficient of the sensitizing dye is 500 or less. The hologram recording method according to (13) and the recording, wherein the interference fringes are recorded using refractive index modulation by color development by amplifying and generating the color former generated as a latent image in the process by self-sensitization Hologram recording material that is possible.
(16) In the second step of (13), light having a wavelength shorter than that of the hologram exposure wavelength and having a wavelength in which the molar extinction coefficient of the color former is 1000 or more is irradiated. The hologram recording method according to any one of (10) to (15), wherein an interference fringe is recorded by using refractive index modulation by color development by amplifying and producing a color former produced as a latent image in the process by self-sensitization, and A hologram recording material capable of such recording.
(17) The (10) to (16) description, wherein the interference fringe recording component of (10) to (16) includes at least an acid-color-forming dye precursor as a dye precursor and an acid generator. Hologram recording material.
(18) The hologram recording material 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 in (17) .
(19) The hologram recording material according to (18), wherein the acid generator is a diaryliodonium salt, a sulfonium salt, or a sulfonic acid ester in (18).
(20) In (17), the color former generated from the acid color-formable dye precursor is a xanthene (preferably fluorane) dye or a triphenylmethane dye. The hologram recording material according to any one of the above.
(21) The hologram recording material according to any one of (17) to (20), wherein the interference fringe recording component further contains an acid proliferating agent in (17).
(22) The hologram recording material according to (21), wherein the acid proliferating agent is a compound represented by the following general formulas (4-1) to (4-6) in (21).

In the general formulas (4-1) to (4-6), 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 (4-1) to (4-6), R ₁₀₁ is a group in which R ₁₀₁ OH is either a sulfonic acid or an electron-withdrawing group-substituted carboxylic acid. (22) The hologram recording material according to the item.
(24) The interference fringe recording component described in (10) to (16) includes at least a base color-forming dye precursor as a dye precursor and a base generator, (10) to (16) The hologram recording material according to any one of the above.
(25) The hologram recording material according to (24), wherein, in (24), the base generator is a compound represented by the following general formulas (1-1) to (1-4).

In the general formulas (1-1) to (1-4), R ₁ , R ₂ , R ₁₃ , R ₁₄ and R ₁₅ are each independently a hydrogen atom, an alkyl group, an alkenyl group, a cycloalkyl group, an aryl group, hetero R ₁ or R ₂ may be connected to each other to form a ring, and R ₁₃ , R ₁₄ , or R ₁₅ may be connected to each other to form a ring. R ₃ , R ₆ , R ₇ and R ₉ each independently represent a substituent, R ₄ , R ₅ , R ₈ , R ₁₀ and R ₁₁ each independently represent a hydrogen atom or a substituent, R ₁₀ , R ₁₁ may be connected to each other to form a ring. R ₁₆ , R ₁₇ , R ₁₈ and R ₁₉ each independently represents an alkyl group or an aryl group, and R ₁₂ represents an aryl group or a heterocyclic group. n1 represents an integer of 0 or 1, and n2 to n4 each independently represents an integer of 0 to 5.
(26) The hologram recording material according to (25), wherein n1 is 1 in the general formulas (1-1) and (1-2).
(27) In the general formula (1-1), R ₃ is any one of a nitro group substituted at the 2-position or 2,6-position, or an alkoxy group substituted at the 3,5-position ( 25) The hologram recording material according to (26).
(28) The hologram recording material as described in (25) or (26), wherein in formula (1-2), R ₆ is an alkoxy group substituted at the 3,5-position.
(29) In (24), the base color-forming dye precursor is a dissociation azo dye, dissociation azomethine dye, dissociation oxonol dye, dissociation xanthene (preferably fluoran) dye, dissociation triphenylmethane dye The hologram recording material according to any one of (24) to (28), wherein the hologram recording material is a non-dissociated product.
(30) The hologram recording material as described in (24) to (29), wherein the interference fringe recording component further contains a base proliferating agent in (24).
(31) The hologram recording material according to (30), wherein the base proliferating agent is represented by the following general formula (5) in (30).

In general formula (5), 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, and R ₁₂₁ and R ₁₂₂ are linked 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 hologram recording material according to (31), wherein n102 is 1 in the general formula (5).
(33) The hologram recording material according to (31) or (32), wherein the base proliferating agent of the general formula (5) is a compound represented by the general formula (6-1) or (6-2) .

In general formulas (6-1) and (6-2), R ₁₂₁ and R ₁₂₂ have the same _{definitions as} in general formula (5).
(34) The hologram recording according to (10) to (16), wherein the interference fringe recording component of (10) to (16) includes at least a dye precursor represented by the following general formula (2): material.

In the general formula (2), A1 and PD are covalently bonded, and A1 is an organic compound site having a function of cleaving the covalent bond with PD by electron transfer or energy transfer with a sensitizing dye or a chromophore excited state. In addition, PD represents an organic compound moiety having a characteristic of becoming a color former when covalently bound to A1 and when the covalent bond with A1 is cleaved and released.
(35) The hologram recording material according to (34), wherein the dye precursor of the general formula (2) is represented by any one of the general formulas (3-1) to (3-6).

In the general formulas (3-1) to (3-6), PD has the same meaning as in the general formula (2), 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 (2) or (3-1) to (3-6), PD is any one of dissociable azo dye, dissociable azomethine dye, dissociable oxonol dye, triphenylmethane dye, and xanthene dye. The hologram recording material according to (34) or (35), wherein the hologram recording material is a group consisting of: and is covalently linked to A1 on the chromophore.
(37) An electron-donating compound, or a sensitizing dye or dye precursor having the ability of the hologram recording material according to (1) to (36) to reduce the radical cation of the color former generated from the sensitizing dye or dye precursor The hologram recording material (38) (37) according to any one of (1) to (36), comprising an electron-accepting compound having an ability to oxidize a radical anion of a color former produced from The hologram recording material has an electron donating compound, and the electron donating compound is an alkylamine, aniline, phenylenediamine, triphenylamine, carbazole, phenothiazine, phenoxazine, phenazine, hydroquinone, Catechols, alkoxybenzenes, aminophenols, imidazoles, pyridines, metalloses S, metal complexes, characterized in that either of the semiconductor fine particles (37) The hologram recording material according.
(39) The hologram recording material according to (38), wherein the electron donating compound is a phenothiazine in (38).
(40) In (37), the electron-accepting compound is an aromatic compound, a heterocyclic compound or an electron-withdrawing group into which an electron-withdrawing group is introduced, such as dinitrobenzene or dicyanobenzene. The hologram recording material according to (37), which is any one of a compound, an N-alkylpyridinium salt, a benzoquinone, an imide, a metal complex, and semiconductor fine particles.
(41) A volume phase hologram recording method comprising performing volume phase hologram recording using the hologram recording material according to any one of (1) to (40) and a volume phase capable of such volume phase recording. Hologram recording material.
(42) When performing hologram recording using the hologram recording material according to (1) to (41), after the hologram exposure, heat treatment is performed in the second step or further thereafter. (41) A hologram recording method according to (41) and a hologram recording material capable of such recording.
(43) Using the hologram recording material described in (1) to (42), a multiple hologram recording is performed 50 times or more in the first step to form a latent image, and then interference fringes are formed using the latent image. A hologram recording method according to any one of (1) to (42), and a hologram recording material capable of such recording, wherein the second step of forming the film is performed.
(44) The hologram recording material described in (43) is used to form a latent image by performing multiple hologram recording 100 times or more in the first step, and then to form interference fringes using the latent image. (2) The hologram recording method according to (43) and a hologram recording material capable of such recording.
(45) In (43), (1) to (44), wherein the exposure amount when performing multiplex hologram recording in the first step can be multiplex-recorded while being constant throughout the multiplex recording. The hologram recording material and the hologram recording method described.
(46) An optical recording medium using the hologram recording material described in (1) to (45) and a recording / reproducing method on an optical recording medium using the hologram recording / reproducing method described in (1) to (44).
(47) An optical recording medium, wherein the hologram recording material according to (1) to (45) is stored in a light-shielding cartridge at the time of storage.
(48) A three-dimensional display hologram using the hologram recording material according to (1) to (44) and a method for producing a three-dimensional display hologram using the hologram recording method according to (1) to (44).
(49) A holographic optical element using the hologram recording material according to (1) to (44) and a method for producing a holographic optical element using the hologram recording method according to (1) to (44).

  By using the hologram exposure latent image coloring-self-sensitizing amplification method hologram recording material and recording method of the present invention, high sensitivity and high diffraction efficiency, and further, the refractive index modulation amount increases linearly with respect to the exposure amount, so that hologram recording can be performed. Since it can be seen that there is no shrinkage at the time of recording, it is advantageous in terms of transfer speed, multiplex recording characteristics (recording density) and the like when applied to a holographic memory or the like.

  The hologram recording method and hologram recording material of the present invention will be described in detail below.

  The hologram recording method of the present invention and the hologram recording material capable of such recording include at least a first step of forming a latent image by hologram exposure and a second step of forming interference fringes by amplification of the latent image. And, more preferably, they are performed by dry processing, and more preferably, a hologram recording method having a second step of forming interference fringes by amplifying a latent image and performing refractive index modulation, and so on It is a hologram recording material capable of accurate recording.

  Here, the “latent image” in the first step of the present invention means “interference fringes that have been subjected to refractive index modulation that is preferably half or less of refractive index modulation formed after the second step”. (That is, preferably the amplification process is performed twice or more in the second process, or the diffraction efficiency is increased by 5 or more in the second process), more preferably the second process. Interference fringes that have been subjected to refractive index modulation that is less than 1/5, more preferably less than 1/10, more preferably less than 1/30 of the refractive index modulation formed after the process (that is, the second More preferably, the amplification step (increase in diffraction efficiency) is performed 5 times or more, more preferably 10 times or more, and even more preferably 30 times or more.

The second step is preferably caused by 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.

The hologram recording material of the present invention preferably does not use silver halide.
Further, it is preferable that the hologram recording is a system that cannot be rewritten. The system that cannot be rewritten here is a system that is recorded by an irreversible reaction, and indicates a system in which data is recorded once and can be stored without being overwritten (not 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.

  More preferably, as the hologram recording method of the present invention and a hologram recording material capable of such recording, a first step of generating, by hologram exposure, a colored body that does not absorb at least the hologram reproduction light wavelength as a latent image; It has a second step of recording interference fringes as refractive index modulation by irradiating light with a wavelength different from that of hologram exposure to the colored body latent image to generate dyes by self-sensitizing amplification. And a hologram recording material capable of such recording.

More preferably as a hologram recording material of the present invention, as a compound group capable of hologram recording, at least,
1) a sensitizing dye that absorbs light and generates an excited state by hologram exposure in the first step;
2) A dye precursor that can be a color former that has a longer wavelength than the original state and that has no absorption at the hologram reproduction light wavelength, and is an electron transfer or energy from the excited state of the sensitizing dye or the colored body excited state. An interference fringe recording component capable of recording an interference fringe using refractive index modulation by color development by moving,
And a hologram recording material characterized by comprising:
The dye precursor is preferably a color former having an absorption maximum in a region between the wavelength of the hologram reproduction light and the wavelength of the hologram reproduction light, more preferably 200 nm, and even more preferably 100 nm.

Furthermore, by using the above-mentioned hologram recording material, the electron transfer or energy transfer from the sensitizing dye excited state generated by hologram exposure to the interference fringe recording component makes the absorption longer wavelength from the original state and the hologram reproduction light. A first step of producing a color former having no absorption in the wavelength as a latent image, and light having a wavelength shorter than that of the hologram exposure wavelength and in a region where the molar absorption coefficient of the sensitizing dye is 5000 or less. And a second step of recording interference fringes using refractive index modulation by color development by amplifying and producing the color former generated as a latent image in the first step by self-sensitization. A hologram recording method and a hologram recording material capable of such recording are more preferable.
In the wavelength range of the light irradiated in the second step, the molar absorption coefficient of the sensitizing dye is more preferably 1000 or less, and further preferably 500 or less.
In the wavelength range of the light irradiated in the second step, it is preferable that the molar extinction coefficient of the color former is 1000 or more.

As the compound group capable of holographic recording of the present invention, at least,
1) a sensitizing dye that absorbs light and generates an excited state by hologram exposure in the first step;
2) Includes a dye precursor that can be a color former that has a longer wavelength than the original state and that has no absorption at the hologram reproduction light wavelength, and transfers electrons or energy from the excited state of the sensitizing dye or color former. Interference fringe recording component capable of recording interference fringes using refractive index modulation by color development,
Are preferably included.

In addition to the sensitizing dye and the interference fringe recording component, the hologram recording material of the present invention preferably further comprises a binder, and if necessary, an electron donating compound, an electron accepting compound, a polymerizable monomer, a polymerizable oligomer, a polymerization Additives such as an initiator, a crosslinking agent, a heat stabilizer, a plasticizer, and a solvent are used.
However, in the interference fringe recording (refractive index modulation) itself with the hologram recording material of the present invention, binders, polymerizable monomers, polymerizable oligomers and the like are not necessarily required. When these are used, film hardening and storage stability are improved. This is because of the purpose of lowering the shrinkage rate.

The hologram recording material of the present invention is preferably a recording material for performing volume phase hologram recording. As described above, the volume phase type hologram recording is a shape parallel to or nearly parallel to the film surface of the recording material (reflection type) or a shape perpendicular to or perpendicular (transmission type). A large number of interference fringes of ˜7000 are recorded as refractive index modulation.
In the hologram recording material of the present invention, it is preferable that the refractive index is different between an interference bright portion where color is developed by electron transfer or energy transfer from an excited state of a sensitizing dye or color former and an interference dark portion where color development does not occur.

The light used for the hologram exposure in the first step of the present invention is preferably any of ultraviolet light, visible light, and infrared light having a wavelength of 200 to 2000 nm, more preferably ultraviolet light or visible light having a wavelength of 300 to 700 nm. And more preferably visible light of 400 to 700 nm.
Furthermore, the light used in the present invention is preferably a coherent (phase and wavelength aligned) laser beam. The laser used may be any of a solid laser, a semiconductor laser, a gas laser, and a liquid laser. Preferred laser light is, for example, a 532 nm YAG laser double wave, a 355 nm YAG laser triple wave, and a wavelength around 405 to 415 nm. GaN laser, 488 or 515 nm Ar ion laser, 632 or 633 nm He—Ne laser, 647 nm Kr ion laser, 694 nm ruby laser, 636, 634, 538, 534, 442 nm He—Cd laser, etc. .
It is also preferable to use a nanosecond or picosecond order pulse laser.
When the hologram recording material of the present invention is used for an optical recording medium, it is preferable to use a 532 nm YAG laser double wave or a GaN laser near 405 to 415 nm.
The wavelength of light used for hologram reproduction is preferably the same or longer than the wavelength of light used for hologram exposure (recording), and more preferably the same.

In the hologram recording material of the present invention, after the hologram exposure, a fixing step may be performed by light, heat, or both.
In particular, when an acid proliferating agent or a base proliferating agent is used in the hologram recording material of the present invention, it is preferable to use heating for fixing in order to make the acid proliferating agent or the base proliferating agent function effectively.
In the case of light fixing, the entire area of the hologram 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.
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.

  Note that the refractive index modulation during interference fringe recording is preferably 0.00001 to 0.5, and more preferably 0.0001 to 0.3.

The diffraction efficiency η of the hologram recording material is given by the following equation.
η = Idiff / Io (Formula 1)
Here, Io is the incident light intensity, and Idiff is the diffracted (transmission type) or reflected (reflection type) light intensity. The diffraction efficiency takes any value from 0 to 100%, preferably 30% or more, more preferably 60% or more, and most preferably 80% or more.

The sensitivity of the hologram recording material is generally expressed by the exposure amount per unit area (mJ / cm ² ), and it can be said that the smaller the value, the higher the sensitivity. However, the exposure amount at which time is determined as sensitivity varies depending on the literature and patent. When the exposure amount starts recording (refractive index modulation), the exposure amount giving the maximum diffraction efficiency (maximum refractive index modulation) In this case, the exposure amount giving a diffraction efficiency half that of the maximum diffraction efficiency may be set to an exposure amount at which the gradient of the diffraction efficiency becomes the maximum with respect to the exposure amount E.
Further, from the Kugelnick's theoretical formula, the refractive index modulation amount Δn for giving a certain diffraction efficiency is inversely proportional to the film thickness d. That is, the sensitivity for giving a certain diffraction efficiency varies depending on the film thickness, and the smaller the refractive index modulation amount Δn is, the thicker the film thickness d is. Therefore, unless conditions such as film thickness are matched, the sensitivity cannot be generally compared.
In the present invention, sensitivity is defined as “exposure amount giving half the maximum diffraction efficiency (mJ / cm ² )”. The sensitivity of the hologram recording material of the present invention, for example, when the film thickness is about 10 to 200 [mu] m, is preferably 2J / cm ² or less, more preferably 1 J / cm ² or less, 500 mJ / cm ² or less More preferably, it is most preferably 200 mJ / cm ² or less.

  When the hologram recording material of the present invention is used as an optical recording medium in a holographic memory, a large amount of two-dimensional digital information (referred to as signal light) is recorded using a spatial light modulation element (SLM) such as DMD or LCD. Is preferred. In order to increase the recording density, it is preferable to use multiplex recording. The multiplex recording method includes multiplex recording such as angle multiplex, phase multiplex, wavelength multiplex, and shift multiplex. It is preferable to use shift multiple recording. Also, CCD and CMOS are preferably used for reading the reproduced two-dimensional data.

  When the hologram recording material of the present invention is used for an optical recording medium, it is essential to perform multiplex recording in order to improve the capacity (recording density). At that time, it is more preferable to perform multiplex recording 10 times or more, more preferably 50 times or more, and still more preferably 100 times or more. Furthermore, it is more preferable from the viewpoints of simplifying the recording system, improving the S / N ratio, etc. that the exposure amount in the multiple recording can be kept constant throughout the multiple recording.

The concept of the hologram recording of the present invention is shown below, but the present invention is naturally not limited to this. The following values are given for qualitative explanations only and do not necessarily reflect quantitative values.
For example, a hologram recording material is irradiated with a 532 nm YAG / SHG laser and absorbed by a sensitizing dye to generate an excited state. By transferring energy or electrons from the excited state of the sensitizing dye to the interference fringe recording component, a part of the dye precursor contained in the interference fringe recording component is changed to a color former to form a color former latent image ( First step). Next, light in the wavelength region of 400 to 450 nm is irradiated to cause the color former (latent image) to be absorbed, and the color former is amplified and produced (dye precursor → color former) by self-sensitization of the color former (the dye precursor → color former). Step 2). In the first step, a latent image is not generated so much in the interference dark portion, so that the self-sensitizing color reaction hardly occurs in the second step, and as a result, a large refractive index modulation is formed in the interference dark portion and the non-interference dark portion. Can be recorded as interference fringes. For example, when a 532 nm laser is used again to irradiate the recorded hologram recording material, the recorded information, images, etc. can be reproduced or function as a desired optical material.

  Hereinafter, each component for the hologram recording material of the present invention will be described in detail.

  First, the sensitizing dye that absorbs light and generates an excited state by hologram exposure in the first step in the hologram recording material of the present invention will be described in detail.

  The sensitizing dye of the present invention preferably generates an excited state by absorbing any of ultraviolet light, visible light, and infrared light having a wavelength of 200 to 2000 nm, more preferably ultraviolet light having a wavelength of 300 to 700 nm. It absorbs light or visible light to generate an excited state, and more preferably absorbs visible light of 400 to 700 nm to generate an excited state.

The sensitizing dye of the present invention is preferably a cyanine dye, squarylium cyanine dye, styryl dye, pyrylium dye, merocyanine dye, arylidene dye, oxonol dye, azurenium dye, coumarin dye, ketocoumarin dye, styrylcoumarin dye, pyran dye, xanthene dye. Thioxanthene dye, phenothiazine dye, phenoxazine dye, phenazine dye, phthalocyanine dye, azaporphyrin dye, porphyrin dye, condensed aromatic dye, perylene dye, azomethine dye, anthraquinone dye, metal complex dye, metallocene dye, etc. And more preferably cyanine dyes, squarylium cyanine dyes, pyrylium dyes, merocyanine dyes, oxonol dyes, coumarin dyes, ketocoumarin dyes, styryl coumarin dyes. Examples include pyran dyes, xanthene dyes, thioxanthene dyes, fused aromatic dyes, metal complex dyes, metallocene dyes, and more preferably cyanine dyes, merocyanine dyes, oxonol dyes, metal complex dyes, metallocene dyes. . As the metal complex dye, a Ru complex dye is particularly preferable, and as the metallocene dye, ferrocenes are particularly preferable.
In addition, “Dye Handbook” (Shin Okawara et al., Kodansha 1986), “Chemicals of Functional Dye” (Shin Okawara et al., CMC 1981), “Special Functional Materials” (Chemical Icmori, etc., CMC 1986) The dyes and dyes described in 1) can also be used as the sensitizing dye of the present invention. The sensitizing dye of the present invention is not limited to these, and any dye and dye that absorbs visible light can be used. These sensitizers can be selected in accordance with the wavelength of the radiation used as a light source according to the purpose of use, and two or more sensitizing dyes may be used in combination depending on the application.

  Since the hologram recording material is used in a thick film and light needs to pass through the film, the addition amount of the sensitizing dye can be increased as much as possible by reducing the molar extinction coefficient of the sensitizing dye at the hologram exposure wavelength. It is preferable for high sensitivity. The molar extinction coefficient of the sensitizing dye at the hologram exposure wavelength is preferably 1 or more and 10,000 or less, more preferably 1 or more and 5000 or less, further preferably 5 or more and 2500 or less, and more preferably 10 or more and 1000 or less. Most preferred.

  The recording wavelength light transmittance of the hologram recording material is preferably 10 to 99%, more preferably 20 to 95%, still more preferably 30 to 90%, and more preferably 40 to 85%. It is preferable in terms of diffraction efficiency, sensitivity, and recording density. Therefore, it is preferable to adjust the molar extinction coefficient and the added molar concentration at the recording wavelength of the sensitizing dye in accordance with the film thickness of the hologram recording material so as to be so. Further, λmax of the sensitizing dye is preferably in the range of the same wavelength as the hologram recording wavelength to a wavelength shorter than 100 nm. Furthermore, the molar extinction coefficient at the recording wavelength of the sensitizing dye is preferably 1/5 or less of the molar extinction coefficient of λmax, and more preferably 1/10 or less. In particular, when the sensitizing dye is an organic dye such as a cyanine dye or a merocyanine dye, it is preferably 1/20 or less, more preferably 1/50 or less, and 1/100 or less. Most preferred.

  Specific examples of the sensitizing dye of the present invention are given below, but the present invention is not limited thereto.

The sensitizing dye of the present invention is a commercially available product or can be synthesized by a known method.
In the case of a YAG laser double wave with a hologram recording wavelength of 532 nm, the sensitizing dye is particularly preferably a trimethine cyanine dye having a benzoxazole ring, a Ru complex dye, or a ferrocene. In the case of a 405 to 415 nm GaN laser, Monomethine cyanine dyes, Ru complex dyes and ferrocenes having a benzoxazole ring are particularly preferred.

  Next, the hologram recording material 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 no absorption at the hologram reproduction light wavelength, and is a sensitizing dye or color former excitation An interference fringe recording component capable of recording an interference fringe using refractive index modulation by color development by electron movement or energy movement from the state will be described in detail.

At that time, it is important that the refractive index is different between a place where a color reaction occurs (interference bright part) and a place where no color reaction occurs (interference dark part). In general, the refractive index of a dye takes a high value in the region where the wavelength is longer than that near the absorption maximum wavelength (λmax), and particularly takes a very high value in a region where the wavelength is longer than λmax by 200 nm from λmax. It takes a high value exceeding 2 and even 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 interference fringe recording component of the present invention transfers electrons directly from the sensitizing dye or color former excited state or by energy transfer or from the sensitizing dye or color former excited state to the acid generator or base generator. Alternatively, it is preferable to include a dye precursor that can be a colored body whose absorption is changed from the original state by an acid or a base generated by energy transfer.

In addition, the hologram recording material of the present invention is preferably a phase-type hologram recording material that records interference fringes by refractive index modulation in terms of high diffraction efficiency. That is, at the time of hologram reproduction, it is preferable that the hologram recording material has no absorption or little absorption at the reproduction light wavelength.
Therefore, the dye precursor contained in the interference fringe recording component in the hologram recording material of the present invention can be transferred directly from the sensitizing dye or color former excited state by electron transfer or energy transfer, or the sensitizing dye or color former excited state. It is preferable that an acid or base generated by electron transfer or energy transfer from the acid generator to the acid generator or base generator can be a colored body having a wavelength longer than that of the original state. When a color body is formed, it is preferable that the color body does not have absorption at the hologram reproduction light wavelength but has absorption at a shorter wavelength side than that. The sensitizing dye is preferably decomposed during hologram recording or subsequent fixing to lose its absorption and sensitizing functions.
As a result, the hologram recording material of the present invention can provide a phase hologram recording material capable of recording interference fringes by refractive index modulation.

Furthermore, in order to give a large refractive index modulation, the dye precursor contained in the interference fringe recording component does not absorb the hologram reproduction light wavelength after hologram exposure, and is 200 nm from the hologram reproduction light wavelength and the hologram reproduction light wavelength. It is preferable that the color body has an absorption maximum in a region between short wavelengths, and the color body has an absorption maximum in a region between the hologram reproduction light wavelength and the wavelength between the hologram reproduction light wavelength and 100 nm short wavelength. It is more preferable.
As described above, since the wavelength of light used for hologram exposure (recording) and the wavelength of light used for hologram reproduction are more preferably the same, the colored body has absorption at the wavelengths of hologram recording light and reproduction light. Preferably not.

  Preferred examples of the interference fringe recording component in the hologram recording material of the present invention include the following combinations.

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 or a color former excited state, and a feature that becomes a color former when covalently bonded and released Including compounds where the organic compound moiety is covalently bonded. Or a combination further containing a base.
D) When it contains a compound capable of changing the absorption form by reacting with an electron transfer with a sensitizing dye or a colored body excited state.

In either case, the energy transfer mechanism from the excited state of the sensitizing dye or chromophore is the same as the Forster mechanism in which energy transfer occurs from the singlet excited state of the sensitizing dye or chromogen. Either 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 of the sensitizing dye or the color former is larger than the excitation energy of the dye precursor.

On the other hand, in the case of an electron transfer mechanism from an excited state of a sensitizing dye or color former, a mechanism in which electron transfer occurs from a triplet excited state even when the electron transfer occurs from a singlet excited state of the sensitizing dye or color former. But either is fine.
Further, the excited state of the sensitizing dye or the color former may give an electron to the dye precursor, the acid generator or the base generator or may receive the electron. When electrons are supplied from a sensitizing dye or color former excited state, in order for electron transfer to occur efficiently, the orbital (LUMO) energy of the excited electrons in the excited state of the sensitizing dye or color former is determined by the dye precursor, It is preferably higher than the LUMO orbital energy of the acid generator or base generator.
When the sensitizing dye or chromophore excited state receives electrons, the electron orbital (HOMO) energy in the excited state of the sensitizing dye or chromophore is determined by the dye precursor, acid, It is preferably lower than the energy of the HOMO orbit of the generator or base generator.

  Hereinafter, preferred combinations of the interference fringe recording components in the hologram recording material of the present invention will be described in detail.

  First, the case where the interference fringe recording component in the hologram recording material of the present invention contains at least an acid color-forming 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 a sensitizing dye or colored body excited state. 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 or color former excited state.

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.
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.

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, such as 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, pyrrolidino Piperidino, morpholino), alkynyl groups (preferably having 2 to 20 carbon atoms, such as ethynyl, 2-propynyl, 1,3-butadiynyl, 2-phenylethynyl), halogen atoms (for example, 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, 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 6 To 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, 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-methylsulfamoyl) N-phenylsulfamoyl), a carbamoyl group (preferably having a C number of 1 to 20, for example, carbamoyl, N-methylcarbamoyl, N, N-dimethylcarbamoyl, N-phenylcarbamoyl), an acylamino group (preferably having a C number of 1). -20, for example acetylamino, Nzoylamino), imino group (preferably C 2-20, eg phthalimino), acyloxy group (preferably C 1-20, eg acetyloxy, benzoyloxy), alkoxycarbonyl group (preferably C 2-20, eg , Methoxycarbonyl, phenoxycarbonyl), or carbamoylamino group (preferably having 1 to 20 carbon atoms, such as carbamoylamino, N-methylcarbamoylamino, N-phenylcarbamoylamino), more preferably alkyl group, 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 preferably represents —CR ₂₁ R ₂₂ R ₂₃ , more preferably —CCl ₃ group, and 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 represent a substituent (preferably the same as the examples of substituents mentioned for R ₂₄ as substituents above), preferably an alkyl group, an alkoxy group, a halogen atom, a cyano group, nitro Represents a 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 hologram recording material of the present invention can be used in combination with a polymerizable monomer, a polymerizable binder, a reactive binder, or a crosslinking agent to cure a film by polymerization, crosslinking, or the like while performing hologram recording.

  Next, the acid coloring type dye precursor when the interference fringe recording component in the hologram 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.

  The acid-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 an acid generated by an acid generator. As the acid-coloring type dye precursor of the present invention, a compound whose absorption is prolonged by an acid is preferable, and a compound which develops a color from colorless to an acid is more preferable.

  The acid coloring dye precursor is preferably triphenylmethane, phthalide (including indolylphthalide, azaphthalide, or triphenylmethanephthalide), phenothiazine, phenoxazine, fluoran, thiofluorane, Xanthene, diphenylmethane, chromenopyrazole, leucooramine, methine, azomethine, rhodamine lactam, quinazoline, diazaxanthene, fluorene, or 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 interference fringe recording component of the present invention, the dye produced from the acid color-forming dye precursor is preferably a xanthene dye, a 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 interference fringe 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 examples 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 general formula (21), the groups represented by R ₃₃ and R ₃₄ are preferably groups represented by the following general formula (22).

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 mentioned in 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, 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 and an alkoxy group having 1 to 20 carbon atoms. These groups may further have a substituent, and examples of the preferred substituent include the groups listed 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 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 having an aryl group having 6 to 24 carbon atoms 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 of 2 or more, multiple R ₄₁ R _42, R ₄₃ each independently represent the group above. These groups may further have a substituent, and examples of the preferred substituent include the groups listed 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 , 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 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 C6-14 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 it Independently represent the group above. 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.

In particular, R-2 and R-3 are preferred as the acid color-forming dye precursor of the present invention.
Furthermore, the dye precursor of the present invention may be a leucocyanine dye that develops color upon addition of an acid (proton). An example in which a leuco cyanine dye develops color as a cyanine dye by an acid is shown below.

  Preferred examples of the leucocyanine dye of the present invention are shown below, but the present invention is not limited thereto.

When the interference fringe recording component of the present invention contains at least an acid coloring type dye precursor as a dye precursor and an acid generator, it may further contain an acid proliferation 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 general formulas (4-1) to (4-6).

In the general formulas (4-1) to (4-6), 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 general formula (4-1), _R102 is any one of 2-alkyl-2-propyl group, 2-aryl-2-propyl group, cyclohexyl group, tetrahydropyranyl group, and 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 the general formula (4-1), R ₁₀₃ and R ₁₀₄ each independently represents a substituent (the substituent is preferably the same as the example of the substituent listed for R ₂₄ above), more preferably each independently an alkyl. A group, an alkenyl group, a cycloalkyl group, an aryl group, or a heterocyclic group, more preferably an alkyl group or an aryl group, and most preferably an alkyl group.

In the general formulas (4-1) to (4-6), 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 listed 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. Represents a group.
R ₁₀₅ , R ₁₀₆ and R ₁₁₆ are all preferably hydrogen atoms. R ₁₀₇ , R ₁₁₀ and R ₁₁₃ are more preferably alkyl groups.

In general formula (4-2), 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 (4-3), 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 the general formula (4-4), 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 the general formula (4-6), R ₁₁₇ represents a substituent (more preferably as a substituent, the same as the examples of the substituent mentioned in R ₂₄ ), and more preferably each independently an alkyl group, an alkenyl group, a cyclo 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 (4-1), (4-3), and (4-4), and is represented by the general formula (4-1). 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 hologram exposure.

  Next, the case where the interference fringe recording component in the hologram recording material of the present invention contains at least a base color-forming 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 a sensitizing dye or colored body excited state. 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 or a colored body excited state.
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 (1-1) to (1-4). In addition, you may use these base generators as 2 or more types of mixtures by arbitrary ratios as needed.

In the general formula (1-1) or (1-2), R ₁ and R ₂ are each independently a hydrogen atom, an alkyl group (preferably 1 to 20 carbon atoms (hereinafter referred to as C number), for example, methyl, Ethyl, n-propyl, isopropyl, n-butyl, n-pentyl, n-octadecyl, benzyl, 3-sulfopropyl, 4-sulfobutyl, carboxymethyl, 5-carboxypentyl), alkenyl group (preferably C 2-20 , For example, 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-methylphenyl, 1-naphthyl, 2-naphthyl), a heterocyclic group (preferably C Any one of 1 to 20, for example, pyridyl, thienyl, furyl, thiazolyl, imidazolyl, pyrazolyl, pyrrolidino, piperidino, morpholino), more preferably a hydrogen atom, an alkyl group, or a cycloalkyl group. Represents a hydrogen atom, a methyl group, an ethyl group, a cyclohexyl group, or a cyclopentyl group.
R ₁ and R ₂ may be linked to each other to form a ring, and the heterocycle formed is preferably a piperidine ring, a pyrrolidine ring, a piperazine ring, a morphophorin ring, a pyridine ring, a quinoline ring, or an imidazole ring, A piperidine ring, a pyrrolidine ring, or an imidazole ring is more preferable, and a piperidine ring is most preferable.
As a more preferable combination of R ₁ and R ₂ , R ₁ is a cyclohexyl group which may be substituted, R ₂ is a hydrogen atom, R ₁ is an alkyl group which may be substituted, R ₂ is a hydrogen atom, R ₁ , R 2 ₂ may be linked to form a piperidine ring or an imidazole ring.

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

In the general formula (1-1), R ₃ 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), alkenyl group (preferably having 2 to 20 carbon atoms, such as 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-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), 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 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), aryl An oxy group (preferably having 6 to 26 carbon atoms such as Xy, 1-naphthoxy), alkylthio group (preferably having 1 to 20 carbon atoms, such as methylthio, ethylthio), arylthio group (preferably having 6 to 20 carbon atoms, 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) , For example, 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 (preferred Or C1-20, such as acetylamino, benzoylamino), imino group (preferably C2-20, such as phthalimino), acyloxy group (preferably C1-20, such as acetyloxy, benzoyloxy), Alkoxycarbonyl group (preferably C 2-20, such as methoxycarbonyl, phenoxycarbonyl), or carbamoylamino group (preferably C 1-20, such as carbamoylamino, N-methylcarbamoylamino, N-phenylcarbamoylamino) 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 al It is a alkoxycarbonyl group.

In the general formula (1-1), R ₃ is preferably a nitro group or an alkoxy group, more preferably a nitro group or a methoxy group, and most preferably a nitro group.
In General formula (1-1), n2 is an integer of 0-5, Preferably it is an integer of 0-3, More preferably, it is 1 or 2. When n2 is 2 or more, a plurality of R _{3 s} 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 (1-1), when R ₃ is a nitro group, it is preferably substituted at the 2-position or 2,6-position, and when R ₃ is an alkoxy group, it is substituted at the 3, 5-position. Is preferred.

In the formula _{(1-1), R 4, R} 5 ( preferably the same as the substituents exemplified in R ₃ as a substituent) Preferred examples each independently represent a hydrogen atom or a substituent R ₃ The hydrogen atom, an alkyl group, or an aryl group, and more preferably any one of a hydrogen atom, a methyl group, and a 2-nitrophenyl group.
R _4, a more preferable combination of R _5, R _4, R ₅ both hydrogen atoms, R ₅ is a hydrogen atom in R ₄ is a methyl group, R _4, R ₅ both methyl, R ₄ is 2-nitrophenyl group R ₅ is a hydrogen atom, and the like, more preferably R ₄ and R _{5 are} co-hydrogen atoms.

In the general formula (1-2), R ₆ and R ₇ each independently represents a substituent (preferably the same as the substituents exemplified in R ₃ as the substituent), preferably an alkoxy group, alkylthio Represents a group, a nitro group or an alkyl group, more preferably a methoxy group.
In the general formula (1-2), n3 and n4 each independently represents an integer of 0 to 5, preferably an integer of 0 to 2. When n3 and n4 are 2 or more, a plurality of R ₆ and R ₇ may be the same or different, and may be connected to form a ring. Preferred examples of the ring formed include a benzene ring and a naphthalene ring. .
In general formula (1-2), R ₆ is more preferably an alkoxy group substituted at the 3,5-position, and even more preferably a methoxy group substituted at the 3,5-position.

In the general formula (1-2), R ₈ represents a hydrogen atom or a substituent (preferably the same as the substituents exemplified in R ₃ as the substituent), preferably a hydrogen atom or an aryl group, More preferably, it is a hydrogen atom.

In the general formula (1-3), R ₉ represents a substituent (preferably the same as the examples of the substituent listed as R ₃ 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 (1-3) may be a compound connected from R ₉ in the polymer chain.

In the general formula (1-3), R ₁₀ and R ₁₁ each independently represent a hydrogen atom or a substituent (preferably the same as the substituents exemplified in R ₃ as the substituent), preferably an alkyl group Or an aryl group is represented, More preferably, a methyl group, a phenyl group, or a 2-naphthyl group is represented.
R ₁₀ and R ₁₁ may be connected to each other to form a ring, and the ring formed is preferably, for example, a fluorene ring.

In General Formula (1-4), R ₁₂ represents an aryl group or a heterocyclic group, and more preferably the following aryl group or heterocyclic group.

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

In the general formula (1-4), R ₁₆ , R ₁₇ , R ₁₈ and R ₁₉ each independently represents an alkyl group or an aryl group, and R ₁₆ , R ₁₇ and R ₁₈ are all phenyl groups, and R ₁₉ 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 (1-1) or (1-3), and more preferably represented by the general formula (1-1).

  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 in the case where the interference fringe recording component in the hologram recording material of the present invention contains at least a base color-forming dye precursor as a dye precursor and a base generator will be described.

  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. The base color-forming dye precursor of the present invention is preferably a compound whose absorption is increased in wavelength by a base, and more preferably a compound that develops color from colorless by a base.

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 ₃ ), preferably 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 ₃ ), preferably an alkyl group which may be substituted or an aryl which may be substituted It is more preferably an alkyl group which represents a 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 substituents listed for R ₃ as the substituent), but an electron-withdrawing substituent is preferable, such as a cyano group, alkoxycarbonyl Group, carbamoyl group, acyl group, alkylsulfonyl group and arylsulfonyl group are preferred.
As the dissociation group of the dissociation type dye of the present invention, OH group, COOH group, NHSO ₂ R ₉₃ group, NHR ₉₆ group, CHR ₉₄ R ₉₅ group are more preferable, OH group, CHR ₉₄ R ₉₅ group are more preferable, OH Groups are most preferred.

  Examples of preferred dissociable dye non-dissociated as a base color developing dye precursor in the present invention include dissociable azo dyes, dissociable azomethine dyes, dissociable oxonol dyes, dissociable arylidene dyes, dissociable xanthene dyes, dissociable fluorane dyes, Alternatively, it is a non-dissociated form of a dissociation-type triphenylamine dye, and more preferably a non-dissociation form of a dissociation-type azo dye, dissociation-type azomethine dye, dissociation-type oxonol dye, or dissociation-type arylidene 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 interference fringe 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 a compound represented by the general formula (5).

In the general formula (5), 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 substituent is preferably exemplified as R _{1 above)} . The same as the examples of substituents), more preferably a hydrogen atom, an alkyl group, or a cycloalkyl group, and still more preferably a hydrogen atom, a methyl group, an ethyl group, a cyclohexyl group, or a cyclopentyl group.
R ₁₂₁ and R ₁₂₂ may be linked to each other to form a ring, and the heterocycle formed is preferably a piperidine ring, a pyrrolidine ring, a piperazine ring, a morphophorin ring, a pyridine ring, a quinoline ring, or an imidazole ring, More preferred is a piperidine ring, pyrrolidine ring, or imidazole ring, and most preferred is a piperidine ring.
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 represents a hydrogen atom or a substituent (preferably the same as the examples of substituents mentioned in R ₃ 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 ₃ as the substituent), preferably a hydrogen atom or an alkyl group, more preferably hydrogen. 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 represented by the general formula (6-1) or (6-2).
In general formulas (6-1) and (6-2), R ₁₂₁ and R ₁₂₂ have the same _{definitions as} in general formula (5).

  The base proliferating agent of the present invention is more preferably represented by the general formula (6-1).

  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 proliferation, when using a base proliferation agent in the hologram recording material of the present invention, it is preferable to heat-treat after hologram exposure.

  Next, the interference fringe recording component of the present invention is released when it is covalently bonded to an organic compound moiety having a function of breaking a covalent bond by electron transfer or energy transfer with a sensitizing dye or a colored body excited state. The case where the organic compound site | part which has the characteristics used as a color development body contains the compound which has covalently bonded is demonstrated.

  In that case, it is preferable that the interference fringe recording component of the present invention contains at least a dye precursor represented by the general formula (2).

In the general formula (2), A1 and PD are covalently bonded, and A1 is an organic compound site having a function of cleaving the covalent bond with PD by electron transfer or energy transfer with a sensitizing dye or a chromophore excited state. In addition, PD represents an organic compound moiety having a characteristic of becoming a color former when covalently bound to A1 and when the covalent bond with A1 is cleaved and released.
A1 is more preferably an organic compound moiety having a function of cleaving a covalent bond with PD by electron transfer with a sensitizing dye or a colored body excited state.

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

  As PD, colorless or light color when covalently bonded to A1, or absorption is short wavelength, and when released by cleavage of the covalent bond with A1, it is preferable that coloring or absorption is long wavelength. .

  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 to any part of A1 as long as it is on the dye chromophore, but it is preferably covalently bonded to A1 at the atom indicated by the arrow in the above figure.

  More preferably, the dye precursor of the general formula (2) is represented by any one of the general formulas (3-1) to (3-6).

  In the general formulas (3-1) to (3-6), PD is synonymous with the general formula (2).

In the general formula (3-1), R ₇₁ represents a hydrogen atom or a substituent (preferably the same as the substituents exemplified in R ₃ as the substituent), preferably an alkyl group or an aryl group, More preferred are t-butyl group, methyl group and phenyl group, and further preferred are methyl group or t-butyl group.
R ₇₂ represents a substituent (preferably the same as the substituents exemplified in R ₃ 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 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-position or 4-position.

In the general formula (3-2), R ₇₃ represents a substituent (preferably the same as the example of the substituent listed for R ₃ as a substituent), preferably 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 (3-3), R _{74 to} R ₇₇ each independently represents an alkyl group, and preferably all represent a methyl group.

In the general formula (3-4), R ₇₈ and R ₇₉ each independently represent a substituent (the above substituents are preferably the same as the examples of the substituents listed for R ₃ ), and R ₇₉ is preferably alkoxy. Represents a group, more preferably a methoxy group. a74 and a75 each independently represent 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 3 and 5 positions.
a76 represents 0 or 1;

In the formula _{(3-5), R 80, R} 81 ( preferably the same as the substituents exemplified in R ₃ as above substituents) represent each independently a hydrogen atom or a substituent, and 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 (3-6), R ₈₂ and R ₈₃ each independently represent a substituent (preferably the same as the examples of substituents mentioned in R ₃ as substituents), preferably an alkyl group or alkenyl. Represents a group or an aryl group. R ₈₂ and R ₈₃ are preferably connected to each other to form a ring, and the formed ring is preferably a fluorene ring, a dibenzopyran ring, or a tetrahydronaphthalene ring.

  The dye precursor represented by the general formula (2) is preferably represented by the general formulas (3-1), (3-2), and (3-4).

  Although the preferable example of the pigment | dye precursor of this invention represented by general formula (3-1)-(3-6) below is shown, this invention is not limited to this.

  In addition, when the interference fringe recording component of the present invention includes at least a dye precursor represented by the following general formula (2) or (3-1) to (3-6), the hologram recording material of the present invention includes: For the purpose of dissociating the generated dissociation-type dye, it is also preferable to further contain a base as necessary. 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 interference fringe recording component of the present invention contains a compound capable of reacting by electron transfer with a sensitizing dye or a colored body excited state 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 interference fringe recording component of the present invention is a commercial product or can be synthesized by a known method.

  The hologram recording material of the present invention comprises an electron donating compound having the ability to reduce the radical cation of the sensitizing dye or color former, or an electron accepting compound having the ability to oxidize the radical anion of the sensitizing dye or color former. It can be preferably used.

  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), triphenylamine (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′-dimethyl) Phenazine, 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), aminophenol (Preferably, for example, 4- (N, N-diethylamino) phenol, N-octylaminophenol), imidazoles (preferably, for example, imidazole, N-methylimidazole, N-octylimidazole, N-butyl-2-methyl) Imidazole), 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, 2,3,4,5-teto Chlorobenzoquinone, 2,6-dichloro-3,5-dicyanobenzoquinone, 2,3-dichloro-5,6-dicyanobenzoquinone, naphthoquinone, anthraquinone), imides (preferably, for example, N, N′-dioctylpyromellitimide) 4-nitro-N-octylphthalimide), metal complexes (preferably Ru trisbipyridine complexes, Ru bisbipyridine complexes, Co trisbipyridine complexes, Cr trisbipyridine complexes, PtCl ₆ complexes, etc. also Ru, Fe, Re, Pt, Cu, Co, Ni, Pd, W, Mo, Cr, Mn, Ir, Ag complexes, 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 or color former, or the reduced potential of the sensitizing dye or color former in the excited state. The potential is preferably nobler (plus side) than the reduction potential of the sensitizing dye or color former or the oxidation potential in the excited state of the sensitizing dye or color former.

In the hologram 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 and the interference fringe 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 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), and polycarbonates composed of bisphenol and carbonate.

  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 weight.

  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.

  As the binder used in the hologram recording material of the present invention, a binder having a refractive index of 1.5 or less is preferable.

  In the hologram 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 using a polymerizable monomer, a polymerizable oligomer, and a crosslinking agent in the hologram recording material of the present invention include those described in Japanese Patent Application No. 2003-82732.

A heat stabilizer can be added to the hologram recording material of the present invention in order to improve 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. The dinitroso dimers described in Pazos US Pat. No. 4,168,982 are also useful.

  The plasticizer is used to change the adhesiveness, flexibility, hardness, antiscattering and other mechanical properties of the hologram recording material. Examples of the plasticizer include triethylene glycol dicaprylate, triethylene glycol bis (2-ethylhexanoate), tetraethylene glycol diheptanoate, diethyl sebacate, dibutyl suberate, tris (2-ethylhexyl) phosphate, Examples include tricresyl phosphate and dibutyl phthalate. It is also preferable to use alcohol or phenol as an additive.

In general, the proportion of each component in the hologram recording material of the present invention is preferably in the range of the following% 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,
Interference fringe recording component: preferably 3-70% by mass, more preferably 5-70% by mass,
Sensitizing dye: preferably 0.01 to 10% by mass, more preferably 0.1 to 3% by mass
Electron donating compound or electron accepting compound:
Preferably 0 to 40% by mass, more preferably 0 to 30% by mass

The hologram recording material of the present invention may be prepared by a usual method.
For example, as a method for forming a hologram recording material of the present invention, the binder or each component may be dissolved in a solvent or the like and applied using a spin coater or a bar coater.
In this case, the solvent is preferably a ketone solvent such as methyl ethyl ketone, methyl isobutyl ketone, acetone or cyclohexanone, an ester solvent such as ethyl acetate, butyl acetate, ethylene glycol diacetate, ethyl lactate or cellosolve acetate, cyclohexane or toluene. , Hydrocarbon solvents such as xylene, ether solvents such as tetrahydrofuran, dioxane, diethyl ether, cellosolve solvents such as methyl cellosolve, ethyl cellosolve, butyl cellosolve, dimethyl cellosolve, methanol, ethanol, n-propanol, 2-propanol, n Alcohol solvents such as butanol and diacetone alcohol, fluorine solvents such as 2,2,3,3-tetrafluoropropanol, dichloromethane, chloroform Arm, 1,2 halogenated hydrocarbon solvents such as dichloroethane, N, N-amide solvents such as dimethylformamide, acetonitrile, nitrile solvents such as propionitrile and the like.

The hologram 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 laminated on the substrate by a usual method. It can be a hologram recording material.
Here, “substrate” means any natural or synthetic support, preferably one that can exist in the form of a flexible or rigid film, sheet or plate.
Preferred examples of the substrate include polyethylene terephthalate, resin-primed polyethylene terephthalate, polyethylene terephthalate subjected to flame or electrostatic discharge treatment, cellulose acetate, polycarbonate, polymethyl methacrylate, polyester, polyvinyl alcohol, and glass.
The solvent used can be removed by evaporation during drying. Heating or reduced pressure may be used for evaporation removal.

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

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

When the hologram recording material of the present invention is used for holographic optical memory applications, it is more preferable that the hologram recording material does not shrink before and after hologram recording from the viewpoint of improving the S / N ratio during signal reproduction.
Therefore, for example, an expansion agent described in JP-A-2000-86914 is used for the hologram recording material of the present invention, or a shrink-resistant binder described in JP-A-2000-250382, 2000-172154, and JP-A-11-344917 is used. It is also preferable to use it.
In addition, it is also preferable to adjust the interference fringe interval by using a diffusing element described in JP-A-3-46687, 5-204288, JP-A-9-506441 and the like.

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.
Here, in principle, the reproduction wavelength is preferably the same as the recording wavelength in holography.
Therefore, in the hologram recording material of the present invention, the refractive index of the dye formed from the interference fringe recording component is preferably maximized near the laser wavelength used for recording (reproduction). The refractive index at the recording wavelength of the dye alone film formed from the interference fringe recording component is more preferably 1.7 or more, further preferably 1.8 or more, and 2.0 or more. Most preferred.

As described above, using the hologram recording material method of the present invention described above, color is generated using the excitation energy obtained by the sensitizing dye by the hologram exposure in the first step or the excitation energy obtained by the color former in the second step ( By increasing the absorption wavelength, the refractive index can be greatly modulated in the interference bright part and the interference dark part as compared with known photopolymer systems such as Patent Documents 1 to 3 and 5 to 8.
Moreover, in the hologram recording method of the present invention, which has a first step of forming a latent image by hologram exposure and a second step of amplifying the latent image and performing refractive index modulation to form interference fringes, It is possible to record with extremely high sensitivity compared to the method.

Further, since the hologram recording material of the present invention does not involve mass transfer or polymerization in the interference fringe recording itself as in the photopolymer method, it removes from the trade-off dilemma and achieves high sensitivity, low shrinkage, and good storage stability. It can be compatible. In addition, since the recording itself is not accompanied by superposition, many multiplex recordings are possible. Further, the multiplex recording can be performed while the exposure amount in the multiplex recording is constant throughout the multiplex recording. Can take a range. In particular, the method of the present invention using a latent image amplification method is very advantageous in view of the above-mentioned suitability for multiple recording.
These are preferable from the viewpoint of increasing the capacity, simplifying the recording system, improving the S / N ratio, and the like.

  On the other hand, compared with the recording method disclosed in Patent Document 4 by changing the orientation of a compound having a birefringence such as an azobenzene polymer, the method of the present invention is highly sensitive because of its high quantum yield, Furthermore, since non-destructive reproduction is possible at the time of hologram recording, heat or light fixing after recording, or by decomposing the sensitizing dye in the first and second steps, the storage stability is also excellent.

As described above, the hologram recording material of the present invention provides a completely new recording method that can solve both of the above-mentioned problems and can achieve both high sensitivity and low shrinkage, good storage stability, dry processing, and multiple recording characteristics. In particular, it is preferably used for an optical recording medium (holographic optical memory).
When the hologram recording material of the present invention is used for an optical recording medium, it is preferable that the hologram recording material during storage is stored in a light shielding cartridge.
In addition, a light shielding filter capable of cutting a part of the wavelength range of ultraviolet light, visible light, and infrared light other than the recording light and reproduction light wavelengths may be provided on the front surface, back surface, or both surfaces of the hologram recording material. preferable.

When the hologram recording material of the present invention is used for an optical recording medium, the optical recording medium may be disk-shaped, card-shaped, tape-shaped, or any shape.
In addition to the optical recording medium, the hologram recording material of the present invention includes a three-dimensional display hologram, a holographic optical element (HOE, for example, a head-up display (HUD) mounted on an automobile, a pickup lens for an optical disk, a head mount, etc. Displays, color filters for liquid crystals, reflective liquid crystal reflectors, lenses, diffraction gratings, interference filters, optical fiber couplers, optical polarizers for facsimiles, architectural window glass), covers for books, magazines, displays such as POPs, It can be preferably used for credit cards, banknotes, packaging and the like for security purposes for preventing gifts and counterfeiting.

[Example]
Examples of the present invention will be described below, but the present invention is not limited thereto.

PMMA-EA (poly (methyl methacrylate-5% ethyl acrylate) copolymer MW101000) as a sensitizing dye, electron donating compound, interference fringe recording component, additive and binder shown in Table 1 under a red light Was dissolved in 2 to 4 times the mass of methylene chloride (with acetone or acetonitrile if necessary) to prepare compositions 101 to 104 for hologram recording material. In addition, all% shows the mass% with respect to binder PMMA-EA.
Under a red light, 0.5% by mass of the sensitizing dye shown in Table 1, 15% by mass of the interference fringe recording component, 4% by mass of the electron donating compound, and 80.5% by mass of polymethyl methacrylate as a binder were added to chloroform 300. It melt | dissolved in the mass% and prepared the hologram recording materials 101-104.

  The hologram recording materials 101 to 104 are coated on a glass substrate with a blade so that the thickness is about 80 μm (overcoated if necessary) to form a photosensitive layer, and then dried by heating at 40 ° C. for 3 minutes. Distilled off. Furthermore, hologram recording materials 101 to 104 were produced by covering the photosensitive layer with a TAC film.

The hologram recording material was exposed and recorded using a YAG laser double wave (532 nm, output 2 W) as a light source by the two-beam optical system for transmission hologram recording shown in FIG. The angle between the object beam and the reference beam is 30 degrees. The beam has a diameter of 0.6 cm and an intensity of 8 mW / cm ² , and the holographic exposure time varies from 0.1 to 40 seconds (irradiation energy ranges from 0.08 to 320 mJ / cm ² ). (First step) A He—Ne laser beam of 632 nm was passed through the center of the exposure region at a black angle, and the ratio of the diffracted light to the incident light (diffraction efficiency) was measured in real time. Further, the entire surface was irradiated with light in the wavelength range of 370 to 410 nm (second step), and the diffraction efficiency was measured.

  As described above, in the hologram recording materials 101 to 104, the diffraction efficiency after the hologram exposure in the first step, the maximum diffraction efficiency with respect to the exposure amount after the light irradiation in the second step, and the shrinkage ratio (calculated from the film thickness ratio before and after recording). The evaluation results are shown in Table 2.

The amplification factor is obtained by dividing the irradiation light amount necessary for obtaining the maximum diffraction efficiency in the first step without using the second step by the irradiation light amount necessary for the first step when using the second step. .
From Table 2, the comparative example described in Japanese Patent Application Laid-Open No. 6-43634 has high diffraction efficiency but is a photopolymer system with radical polymerization, and therefore has a large shrinkage exceeding 5%. It can be seen that N is extremely deteriorated and unsuitable. On the other hand, the hologram recording materials 101 to 104 of the present invention are recording methods that are completely different from known hologram recording materials that perform hologram recording by refractive index modulation using color development reaction without using mass transfer and polymerization. It has been found that a high diffraction efficiency and an extremely small shrinkage rate of 0.01% or less can be achieved at the same time, and is particularly suitable for holographic memory applications.
Further, from Table 2, in the hologram recording material of the present invention, the amount of light applied to the first step can be reduced to 1/5 to 1/6 as compared with the case where the second step is used. Since the second step can be collectively exposed, the amplification of the refractive index modulation recording by the self-sensitized color development of the color former itself with the color former of the first step in the second step as a latent image is used. It can be seen that shortening, that is, high sensitivity is possible. Of course, with known materials, it is impossible to increase the sensitivity by such amplification.
Furthermore, the hologram recording material of the present invention is linear after the first step and after the second step, depending on the exposure dose (mJ / cm ² ), and Δn (refractive index modulation amount, diffraction efficiency and film thickness from Kugelnik (Calculation based on the above equation) increased, and it was also found that this is advantageous for multiple recording.
Actually, the hologram recording material of the present invention was used, and the multiplex recording was performed 10 times at the same place by changing the angle of the reference light by 2 degrees with the light amount of 1/10 of the exposure amount in the first step. After (first step), the entire surface is irradiated with light in the wavelength range of 370 to 410 nm (second step), and after hologram multiplex recording is performed, the angle of the reproduction light is changed by 2 degrees and irradiated. It was confirmed that each object light can be reproduced. That is, it can be seen that the hologram recording material of the present invention can perform multiple recording with the same exposure amount and has multiple recording suitability. That is, the hologram recording material of the present invention can perform multiple multiplex recording, and can perform high density (capacity) recording.
On the other hand, known photopolymer hologram recording materials such as JP-A-6-43634 perform the same recording in the latter stage of multiple recording because the polymerization of the photopolymer proceeds and the movement of the monomer necessary for recording slows down. At this time, it was found that a larger amount of irradiation light was required than in the initial stage, which proved to be a problem in improving the multiplicity, that is, the recording density.

In hologram recording materials (samples) 101 to 104, sensitizing dyes are D-1, D-8, D-17, D-22, D-31, D-33, D-34, D-46, D-49, D-50, D-55, D-74, D-87, D-91, D-93, D-94, D-95, D-97, D-100, D-101, D- 107, D-116, D-119, D-120, D-121, binder is polymethyl methacrylate (Mw 996000, 350,000, 120,000), poly (methyl methacrylate-butyl methacrylate copolymer (Mw 75000), polyvinyl acetate (Mw 83000) The same effect was obtained even if it was changed.
Further, in Samples 101 and 102, the acid generator of the interference fringe 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- (4-diphenylsulfonium) phenyl sulfide ditriflate, benzoin tosylate, 2,6-dinitrobenzyl tosylate, N-tosylphthalimide, I-101, I-102, I-103 Sample 101, 1 In 02, the same effect was obtained even when the acid coloring dye precursor of the interference fringe recording component was changed to R-1, R-2, R-4, R-6, R-7.
Further, the base generator of the interference fringe recording component in the sample 103 is PB-4, PB-8, PB-10, PB-12, PB-13, PB-19, PB-22, PB-32, PB-. Even if it changes to 33 and PB-52, the base color development type | mold dye precursor (dissociation type | mold non-dissociation body) is changed to DD-1, DD-4, DD-7, DD-10, DD-16 in the sample 103. The same effect was obtained even when changed to DD-23, DD-25, DD-35, DD-39, DD-43, DD-47, DD-48, DD-49.
Further, the interference fringe recording component in the sample 104 is E-4, E-5, E-13, E-15, E-16, E-18, E-24, E-25, E-28, E-29. , E-32, E-33, E-37, E-38, E-42, E-44, the same effect was obtained.
In addition, in the above case, the light for performing the whole surface exposure uses an optimum wavelength in each system, and when an electron donating compound is necessary, it is changed to an optimum one.

It is the schematic explaining the two-beam optical system for hologram exposure.

Explanation of symbols

10 YAG laser 12 Laser beam 14 Mirror 20 Beam splitter 22 Beam segment 24 Mirror 26 Spatial filter 40 Beam expander 30 Hologram recording material 28 Sample 32 He-Ne laser beam 34 He-Ne laser 36 Detector 38 Rotating stage

Claims (16)

  A hologram recording method characterized by comprising at least a first step of forming a latent image by hologram exposure and a second step of forming interference fringes by amplification of the latent image, which are performed by dry processing.   The hologram recording method according to claim 1, wherein the second step forms an interference fringe by amplifying the latent image and performing refractive index modulation.   3. The hologram recording method according to claim 1, wherein the second step is caused by any one of light irradiation, heat application, electric field application, and magnetic field application.   In the first step, a color developing body that does not absorb the hologram reproduction light wavelength is generated as a latent image, and in the second step, the color developing body is irradiated with light having a wavelength different from that of the hologram exposure. 4. The hologram recording method according to claim 1, which is a step of recording interference fringes as refractive index modulation by generating self-sensitized amplification.   The hologram recording method according to claim 1, wherein the hologram recording is a system that cannot be rewritten. A hologram recording material capable of hologram recording by the hologram recording method according to claim 1, wherein the hologram recording material is at least as a compound group,
1) a sensitizing dye that absorbs light and generates an excited state by hologram exposure in the first step;
2) Includes a dye precursor that can be a color former that has a longer wavelength than the original state and that has no absorption at the hologram reproduction light wavelength, and electron transfer or energy transfer from a sensitizing dye or color former excited state. Interference fringe recording component capable of recording interference fringes using refractive index modulation by color development that occurs through the process,
A holographic recording material comprising:   The dye precursor contained in the interference fringe recording component has a wavelength that is longer than that of the original state, has no absorption at the hologram reproduction light wavelength, and has a wavelength shorter by 200 nm from the hologram reproduction light wavelength and the hologram reproduction light wavelength. The hologram recording material according to claim 6, wherein the hologram recording material can be a color former having an absorption maximum in a region between the two.   The hologram recording material according to claim 6 or 7, wherein the interference fringe recording component includes at least an acid coloring type dye precursor as a dye precursor and an acid generator.   The hologram recording material according to claim 6 or 7, wherein the interference fringe recording component includes at least a base color-forming dye precursor as a dye precursor and a base generator.   An electron-donating compound having the ability to reduce the radical cation of the color former produced from the sensitizing dye or dye precursor, or the ability to oxidize the radical anion of the color former produced from the sensitizing dye or dye precursor The hologram recording material according to claim 6, comprising an electron-accepting compound.   11. The hologram recording material according to claim 10, wherein the hologram recording contains phenothiazines as an electron donating compound.   The hologram recording method according to claim 1, wherein the hologram recording method is volume phase hologram recording.   2. The method according to claim 1, wherein after forming a latent image by performing multiple hologram recording 10 times or more in the first step, a second step of forming interference fringes using the latent image is performed. 6. The hologram recording method according to any one of 5 above.   14. The hologram recording method according to claim 13, wherein the multiple hologram recording is performed while the exposure amount when performing the multiple hologram recording in the first step is constant throughout the multiple recording.   An optical recording medium using the hologram recording material according to claim 6.   The optical recording medium according to claim 15, wherein the optical recording medium is stored in a light shielding cartridge at the time of storage.

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